ELECTROCHEMICAL WASTEWATER TREATMENT FOR DENITRIFICATION AND TOXIC ORGANIC DEGRADATION USING Ti-BASED SnO2 AND RuO2 ELECTRODES

Xie, Zhaoming Ph. D. THESIS

DEPARTMENT OF CIVIL ENGINEERING THE UNIVERSITY OF HONG KONG
2006

Abstract of thesis entitled

Electrochemical Wastewater Treatment for Denitrification and Toxic Organic Degradation Using Ti-based SnO2 and RuO2 Electrodes
submitted by

Xie, Zhaoming
for the degree of Doctor of Philosophy at the University of Hong Kong in December 2006

Many wastewater pollutants, including toxic organic compounds and nutrients at a high concentration, are difficult to treat with conventional treatment processes. Wastewater treatment technologies require continuous advances to ensure that the effluent continues to comply with more stringent discharge standards and to improve the cost-effectiveness of the practice. The electrochemical (EC) method is an advanced oxidation process that has shown promise as an effective treatment alternative for wastewater containing toxic substances. This study focused on the development of the electrochemical technology for degradation of aromatic and chlorinated aromatic organic pollutants and for nitrogen removal from landfill leachate and sewage sludge liquor. A double-layer coating technique was employed to make titanium-based catalytic active electrodes in Ti/SnO2-Sb-Al for EC organic oxidation. The experimental results show that the Ti/SnO2-Sb-Al anode is much more effective for electrolysis of phenol and chlorophenol than other conventional anodes of Pt, Ti/RuO2 and Ti/IrO2. For phenol (100 mg/L) treatment, complete organic removal was

achieved after 5 hrs on anode Ti/SnO2-Sb-Al at 20 mA/cm2, compared with only 36% and 12% organic reductions provided by the Pt and Ti/RuO2 anodes, respectively. Similarly, for chlorophenol electrolysis, the best treatment performance was obtained with anode Ti/SnO2-Sb-Al, followed by Pt and then Ti/RuO2. Analysis with the High Performance Liquid Chromatography (HPLC) revealed many intermediate products during the EC process, from aromatic compounds to aliphatic acids, which were oxidized rapidly by Ti/SnO2-Sb-Al but accumulated in the Pt and Ti/RuO2 cells. In addition, formation of colored polymeric materials occurred in the Pt and Ti/RuO2 electrolyzed solutions. Based on the EC degradation performance and the HPLC results, modified pathways of phenol and chlorophenol electrolysis at different types of electrodes were proposed. The different electrodes were characterized for their electrochemical behavior and surface properties. Compared to the Pt and Ti/RuO2 anodes, Ti/SnO2-Sb-Al had a considerably higher overpotential of oxygen evolution according to the voltammograms, which would facilitate the production of hydroxyl radicals. Direct phenol and chlorophenol oxidation could take place on the Ti/SnO2-Sb-Al surface but not on the Pt and Ti/RuO2 anodes. The Ti/SnO2-Sb-Al electrode also had apparently a higher affinity with organic substances than Ti/RuO2. It is argued that the anodic property has a significant influence on the kinetics, pathway and mechanism of organic electrolysis. Specific surface treatment such as the SnO2-Sb-Al coating provides the anode with a catalytic function for rapid degradation of toxic organics. In addition, electrochemical denitrification experiments were performed using a lab-scale system with Ti/RuO2-based mesh electrode plates for treating saline sewage sludge liquor and raw landfill leachate. Complete ammonia nitrogen removal was achieved in 1 hour of electrolysis for the sludge liquor (500 mg/L) and in 3 hours for the leachate (1600 mg/L). Electro-chlorination is considered to be the major mechanism of EC ammonia oxidation. Additional electro-flocculation with a pair of iron needle electrodes was able to increase the organic removal by sedimentation from below 30% to about 70%. The experimental results suggest that the EC treatment can be developed as a cost-effective method of denitrification for high-strength wastewater.

China MEng Wuhan University. December 2006 .Electrochemical Wastewater Treatment for Denitrification and Toxic Organic Degradation Using Ti-based SnO2 and RuO2 Electrodes By Xie. China A thesis submitted in partial fulfillment of the requirements for the Degree of Doctor of Philosophy at The University of Hong Kong Hong Kong. Zhaoming (谢 昭 明) BEng Wuhan Univ H & E Eng.

Signed Xie. and that it has not been previously included in a thesis. expect where due acknowledgement is made. dissertation or report submitted to this University or to any other institution for a degree. diploma.Declaration I hereby declare that this thesis represents my own work. or other qualification. Zhaoming i .

inspiration. Chan. for his guidance. K. I would express my deepest appreciation to my dear great mother for her accompany in the road of pursuing the degree. I am especially grateful to the help of Mr. JiDong Gu for that they so generously shared with me and for the assistance in using their instruments. His giving of concern for my professional and personal development in these years is appreciated. Lastly.Y. I would like to thank Prof. for their technical assistance and enthusiastic discussion during my studies. love and support during the course of this work at HKU. iii . patience.Acknowledgements I am sincerely grateful to my supervisor. for their friendship and making my PhD study enjoyable. I am indebted to all the staffs and postgraduate students in the Department of Civil Engineering and Department of Chemistry. Prof. and enthusiasm for academic research that has greatly affected my attitude towards the acquisition of knowledge. Herbert Fang and Dr. Dr. Keith Wong during daily experiments and Mr. for their understanding. Yunhai Wang in carrying out the electrochemical analysis. and also to my families. Xiaoyan Li. I also wish to express my gratitude to my labmates.

.........3 Scope of this study .. 1................................................................ Abbreviations ................ xi Chapter 1 Introduction ............1......................... Preparation of catalytic active anodes for organic oxidation..................1 1........ 1 Electrochemical treatment of toxic organic pollutants ............................................. 1...........2 1........3........2 Electrochemical treatment of saline sludge centrate and landfill leachate...............................1....... 9 2.......2 Toxic organic pollutants and nutrients in wastewater discharge ........................................................................................... 1 1.......1................................................................ different electrodes.................1 2...................................1 Wastewater treatment for removal of toxic organics and nutrients ..............................................3 Advance oxidation processes and electrochemical method for wastewater treatment............Table of Contents Declaration .......3......1....3........................1 Problem statement................................. 1.........3 Degradation of phenol and chlorophenol by electrolysis at 2 1 Chapter 2 Literature review..............................1......... Electrochemical denitrification for high-strength 4 5 6 7 7 7 wastewater.............................................................................................................................................................. 8 1..................................................................................................................3.......................................................... Acknowledgements....................................... Conventional wastewater treatment technologies......... 2...................................................... iii 9 10 9 ............................. i ii iii xv List of Illustrations/Figures/Tables.....2 Objectives of this study.................... 1............... 1........4 Characterization of the electrochemical and surface properties of different electrodes and their effects on organic electrolysis ...........................................................................1 1...... Table of Contents .....................................................

.......4 Limitations of AOPs . 2......2 EC degradation of chlorophenol ....1 The substrate base materials: Titanium. 2.....2 Antimony doped tin oxide ...............3...................................3 Electrochemistry for toxic organic degradation. 10 10 11 12 12 13 13 14 15 16 16 16 17 17 17 18 19 19 20 21 22 23 24 25 25 26 2........................3 Electro-chlorination for wastewater disinfection........3 Electro-catalytic oxidation of toxic organic pollutants......................... Dimensionally stable anodes (DSA) for organic oxidation .....2 Potolysis... 2..2..2.2.1.......4 Reaction pathways and mechanisms of electrochemical degradation of toxic organics................1..................4...... 2. electro-flocculation and electro-flotation....2.....2...........................3 Hydrogen peroxide/Ultraviolet light............................. 2...................... 2.....3...3...1 2....4 Advanced oxidation processes (AOPs)......... 2..........3 Wastewater treatment.1 Degradation pathway of aromatic compounds ..............1 EC degradation of phenol ......2.............4............... 2.............3 Direct oxidation ............... 2...................2 Electro-chlorination for wastewater treatment. 2.2.. 2...4......2........... 15 2..........1..........1..........1............................. 30 iv .......1...............................1 ·OH generation..1..................... 2...............2................................4......................................................... 2..................1 Ozonation...3 Sol-gel coating and thermo-decomposition .4....... 21 Preparation of catalytic active anodes..4...1 Electro-coagulation... 2.......4..........2... 2............3........................ 2.1.............. 2.............................2 Physical-chemical treatment methods..3..........2 Mechanisms of electro-catalytic organic oxidation ..4.....3.....1.... 2..2 2...........................3...1 2..2 Development of electrochemical wastewater treatment .........2........................1.........2 Electrochemistry in wastewater treatment ............1 Biological treatment processes .....4............2....3. 2........................ Application of electrochemical technologies in wastewater treatment .. 2.............. 2.......................... 2...............4.......3...4............3................ 19 Chapter 3 Preparation of Ti-based electrodes......... 2....................................3....2 Electron transfer...................................

.........1. 3................. 3......3.........................3.......4 Energy Dispersive X-ray (EDX) analysis............................................................3......... 3............1.......3 Linear sweep voltammetry (LSV) . Annealing........................... 3........ Cathodic electro-plating.......................................................................... Coating materials ....................3......................................4 Electroplating for the inner layer of Ti/SnO2-Sb-Al electrodes.........................................................2 Pretreatment of titanium plates ..............3 Annealing at a high temperature ...... 3............................. Procedure of the Ti/SnO2-Sb-Al electrode preparation .............. 3.................................................7..............1 Metal substrate and the coating materials.............................................5....................5..... Surface contact angle measurement.3........4.................................... 3..........2 Scanning electron microscopy (SEM) .....3.......... 3.....1 Electrochemical denitrification.......................4 3...................2 Coating solution ...1 Microscopic observations ............... 44 v .6.............................................6.......2 3..5.. 31 3............1..............................1........................ Platinium electrodes........................... 44 4.........7..1 3..........................1 3....................................7...........................................1 3........... Dipping and drying procedures....................... 3................3 3.............. 3..................................7....4..3 X-ray Photoelectron Spectroscope (XPS).................3 Preparation of Ti/RuO2 and Ti/IrO2 electrodes.. Dimensionally stable anodes (DSA) ................................................5 Thermal decomposition of the outer layer of the Ti/SnO2-Sb-Al electrodes ...............4.........................1 3.3........................... 3......... 3......................................................7.2 3........ 42 Chapter 4 Experimental materials and methods ..................6 Other electrodes used for the experimental research .................1 3............................. Surface morphology......3 Metal substrate: Titanium ........ 36 3........7 Characterization of the electrodes............7.. Ti/RuO2 mesh electrodes used for electrochemical 40 40 40 41 41 41 42 42 denitrification.....7..............................2 SnO2-based coating film .....5...........2 3......1 RuO2 coating film .......... 3......1...... 37 37 38 38 39 39 39 3...2 Electroplating solution .. 30 30 30 31 31 32 34 35 35 36 3..........

...............2 Operation and sampling .........3..... 4................................................... 4............................................................2 4..4 Electro-denitrification and electro-flocculation reactions ..............1...........1......... 4........1.......1...1.....................5...........4.. 4.................1......5............. 4........................1....1....... 4....................................1..............................2.......3......3 Continous flow stirred tank reactor (CFSTR) for denitrification of landfill leachate..3......................2..2.........2 4.1 Experimental set-up ...............................1 Batch denitrification tests for sludge liquor.... Rate constants for EC oxidation of organic chemicals ......... 4...........5....1 4......... 4...1...................................................................1................... 4.......................1...........2 Electrochemical degradation of aromatic organic pollutants..1........5.................................. 4....1. vi ..... 4........2... 55 4.........1 Wastewater samples...1.............2 Nitrogen (NH3-N. 4.....1..............2..........................1 Chlorine compounds and chloride ..........1.................2.... NO3--N) concentrations...3 Electrochemical denitrification set-up .......... 4............1 Saline sludge centrate ......3 Analytical methods ..1 Electro-chlorination reactions....................1........3........................1....3 Solutions of the intermediate organics of EC phenol degradation.............1 Phenol solution..........5 Current efficiency of EC denitrification ................................ 4...4...........1.......1............... 4...... 4......1....2 Electro-flocculation reactions ..................... 4.... Experimental conditions ......... 4......2 Landfill leachate.. NO2--N........1 Wastewater samples...2...............3..........................3 Trihalomathane (THM) formation potential measurement ........................ 4...........................2 Experimental set-up and operational conditions.......... Current efficiency and TOC removal efficiency ...5...................................5 Analytical methods ..............3..3 High performance liquid chromatography (HPLC)...2 Denitrification plus electro-flocculation for organic removal .......... 4.... 44 44 44 46 48 48 49 49 49 49 50 51 51 51 51 53 55 55 55 55 55 56 56 57 58 58 59 60 4...... 4... 4... 4......................2 Chlorophenol solution.....4...........2......2........4 Other water quality parameters.

..... Polymeric compounds produced during the EC process .......... 5................. Current efficiency and TOC removal efficiency ...............1 Performances of selected anodes in EC phenol degradation ..1 Phenol degradation and TOC removal..2 Intermediate products and reaction routs for different electrodes .................3........... 74 6..........................................3...............2.... electrolysis .....................................................1 5.Chapter 5 Nitrogen removal from wastewater by electrochemical denitrification .........2.................. 6.. Chapter 6 Electrochemical degradation kinetics of phenol and its intermediate products.................2...................2......1 6.........................................2 Electrochemical denitrification of sludge centrate liquor....... 74 6..........3............. 6.................................................2............................. Aliphatic acids from phenol oxidation..............2 6........................................... 5...... 61 5..3..........................2 6.... Electro-chlorination for denitrification of the sludge centrate................................................................... 5..........2............................................... Direct products of phenol oxidation ........................... Pathways of EC phenol degradation .1 5... polymerization .......1........... 6......................... 74 76 78 78 78 83 83 84 84 86 86 86 87 6...............2 5........................3 Major phenol electrolysis reactions . Grouping of intermediate organic compounds ........2 6....3 EC phenol degradation pathways on different types of electrodes............................3........1 6...............3 Electrochemical denitrification.............. 6................4 Electro-flocculation for organic removal. EC denitrification during the continuous flow process....1 General characteristics of the waste liquor samples and EC treatment ....................4 Solution pH during the EC process......1...... Power consumption and current efficiency................. Power consumption and current efficiency.............2.4 Summary ......................... 5..1........2.............. 64 65 68 68 70 71 73 61 62 62 5... 66 5........2 5.....3 Electrochemical denitrification of landfill leachate............. Aromatic ring cleavage vs..5 EC destruction of the intermediate products of phenol vii ............3.........3 Batch EC leachate treatment tests.....3 6...........2..3 6..........

1....3 8.......................................................1 EC chlorophenol oxidation .2 Electrochemical phenol oxidation mechanisms..1..............1... The solution pH during electrolysis.............................................. 7.........1 8...............4 Summary .........................................................2 LSV of the electrodes in the electrolyte without phenol................. Oxygen evolution...............1......................2 LSV curves in the solutions with phenol addition .............1 8....4 Effect of phenol concentration on the LSV curve ...................1 Anode Ti/SnO2-Sb-Al....... 108 viii .....1..................................................... 8................. 7................. 7..1 LSV and oxidation potentials............................................. 97 7.....2 Anode Pt...........................................1..... Current efficiency ............1 Two electrochemical reactions: phenol oxidation and oxygen evolution................. Grouping of the intermediate organic compounds..................................2...........1.......................... 7.....1...1. 93 7....1 7............ 7...1...........................1 Characterization of the electrodes by linear sweep voltammetry (LSV) ................. 7.............1...................................................................................... 7..........................2..2........2 Chlorophenol oxidation and TOC removal by electrolysis .........................1............................. 98 99 100 101 102 102 95 95 95 95 97 94 93 93 7....2................ 104 8. Chapter 8 Electrochemical degradation of chlorophenol 104 104 106 106 108 109 kinetics and pathways ..2..1.....3 Anode Ti/RuO2 ..........................3 Effect of the solution pH on the phenol oxidation overpotential................. 7............................................... 8........3 Summary ........................2 8............................2........................3 EC phenol oxidation process and mass transfer .2................................... HPLC analysis of intermediate compounds........2...........................2......... 88 Chapter 7 Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms .................................1.....2 Intermediates and pathways of EC chlorophenol degradation .....................................2 7..... 7...... 7....... EC phenol degradation steps.................6......

2 9.....3.. Stability of the electrodes..2 Comparison of different electrodes for organic electrolysis..................................................................................................1 8............. 9...5 Summary ............1 8.....1......................................2............................ 110 115 116 116 119 119 119 120 121 8............................... 8..................................... 9................... 9............. LSV of the electrodes in chlorophenol solution ....... EC chlorophenol degradation pathways .........4...................2...............3 Future work.................3............................. 9.2 Transformation and degradation of chlorophenol during electrolysis ................... 124 9................... 9.. 123 9............ Investigation of EC organic oxidation mechanisms ..................1 9...1 XPS analysis .............3.........3 Voltammetric study of anodes in monichlorophenol solutions .................... LSV scan rate....................1...................3 8.............1....................................4 9.......... Surface electrochemical properties ...1 Surface properties ....................... Organic degradation pathways....... 126 9.3..... Electrolysis mechanisms...1 9.....................1.......2 Imagines of the titanium plates ....... 9........................................2 EDX analysis ......................... 133 ix .......1..........3 9............................1 9....2 8......3.................2 Coating density ................3.......... Basic pathways of EC chlorophenol degradation ....2...............2 Contact angle and hydropilicity .....3 Coating surface components ..1........4 8..4 9.2..... 8........4..........................................1..5 9.............4 EC chlorophenol degradation mechanisms............1........ Organic adsorption onto the electrodes.......2.......................... EC oxidation mechanisms.................8..2..................1...... Improvement of electrode preparation techniques...2.................2........5 9............... 123 123 123 124 126 126 128 129 131 131 132 132 133 134 134 134 Deactivation of electrode Ti/SnO2-Sb-Al ....... 123 9........2.................. EC degradation of organic matters .1 The mechanism of deactivation ............................................................................... Chapter 9 Discussion: comparison of the surface morphology and properties between different electrodes......................3 The process of deactivation .. 9................. Peak current density vs...1.....................................................................................2..................................

.................. 138 137 136 References................................ 136 10........................ 140 x ......................................................2 Degradation of phenol and chlorophenol by electrolysis with the Ti/SnO2-Sb-Al and other electrodes .................................3 Surface properties of electrode Ti/SnO2-Sb-Al and their effects on EC organic degradation................................................................................Chapter 10 Conclusions ............... 10....................... 10.........1 Electrochemical treatment of saline sludge centrate and landfill leachate for denitrification and organic removal ................................

.......... denitrification set-up................... Landfill leachate CFSTR set-up............ Shimadzu) ... (a) Nitrogen removal as a function of treatment time............. Well treated electrode Ti/SnO2-Sb-Al ............ 63 xi . Figure 4... Figure 4.... 52 Electrochemical organic degradation experiment set-up............. 22 28 33 36 39 43 45 Dewatering systems in Shatin Wasterwater Treatment Works.....6.......... 57 58 59 62 Figure 4...................... Figure 2.4............................... TIN removal as a function of contact time and current density with a gap distance of 8 mm between the electrodes.............................. 56 (HP 6890 ).................... Figure 3.................9........................ Gas chromatograph – mass spectrum (GC-MS) for HTM analysis Figure 4...1.2......................................List of Illustrations Figures Figure 2..................8........ (B) Electrochemical Figure 4..............................1......... Flow chart of the Ti/SnO2-Sb-Al electrode preparation procedures Landfill facility in New West Territories of Hong Kong ... HACH)....... (C) Ti/RuO2-ZrO2 47 50 52 54 54 electrode mesh plates .... Surface morphology of Titanium plate ....7.......... Figure 4.................... TOC analyzer (TOC-5000A........... HACH).......... (b) Chlorine compounds during the EC process at a current density of 125 mA/cm2 with an electrode gap of 3 mm .5................ Figure 4............ Summary of the reaction mechanisms of electrochemical phenol degradation............................................ Electro plating set-up .......................... 45 Portable datalogging spectrophotometer (DR/2010............................3.. Figure 5..............................4.. Figure 4.... Figure 3.... Figure 3........................2......2...................... UV/Visible spectrometer (Lambda 12.... Figure 4.. Characterization of different anodes..11... Turbidimeter (2100N.................. (A) Electrochemical denitrification system illustration.............................. Figure 5..........1....... Figure 3. Perkin Elmer) ...... High performance liquid chromatography (HPLC) (Waters 2695 2996) ..3.... Reaction mechanism of anodic organic oxidation ..........................1.............10.........................2.................12........ Figure 4............. Figure 4........................ Figure 4...................................................

........8.. Figure 5................................. Figure 6.........1....... Figure 5..................... Figure 6..... Figure 6.. (B) EC-denitrification only... TIN removal as a function of the electrolysis time for different chloride concentrations in EC denitrification of landfill leachate ...2................. TIN removal as a function of power consumption for different electrode gaps at the same current intensity of 75 mA/cm2 ............................................................. Figure 6....5.... TOC and solution pH vs.... and Ti/RuO2 (right) ... 66 65 Figure 5...... (C) EC-flocculation only. Current efficiency on TOC removal ..........3............ Comparison in removals of TOC... Phenol destruction on the three types of anodes.................. Figure 5............. HPLC analysis of aromatic compounds.Figure 5....................4...............7. Figure 6.............................................6............... Figure 6. Figure 6..9............... Figure 6.........11........................... Degradation of pure intermediate chemicals on the three anodes ..............................12...8...................... TIN removal and chloride concentration as a function of contact time in the CFSTR for EC denitrification............................... HPLC analysis of aliphatic acids ... Current efficiency on phenol removal ........................3.. Figure 6........ Figure 6..... Figure 6..6.............................11........10.. Untreated leachate (left) and EC treated leachate(right)....................... 75 81 82 89 89 Figure 6......................................7.............. Figure 5...9...... TOC components of intermediates of EC phenol degradation by the three anodes: Ti/SnO2-Sb-Al (left)......... Current efficiency as a function of current input for different electrode gaps in EC denitrification.......... Figure 5.......................10... Figure 5........ time during phenol degradation ...................................4..... sludge production and TIN degradation for conditions of (A) ECdenitrification + EC-flocculation..... COD and SS.. Figure 5.... Phenol degradation pathway for electrode Ti/SnO2-Sb-Al. TIN removal as a function of power consumption ...... Current efficiency and TIN degradation as the function of reaction time in continous........................ Phenol removal by the three types of anodes. TOC and solution pH during EC phenol degradation..................................................... (D) EC-denitrification + chemical 68 69 70 71 72 72 73 75 77 77 79 79 80 flocculation .. 90 xii ........ Pt (middle).. Current efficiency and TIN degradation as the function of reaction time in batch operation............5......... HPLC analysis of intermediates of EC phenol degradation on the three anodes .................

........................................ and Ti/RuO2 (right) ..........................................................12......................10...... Phenol oxidation for electrode Ti/SnO2-Sb-Al to different concentrations .11.8.. LSV of anode Ti/RuO2 in MCP solution ................................................. Figure 7...... Figure 8.....6.....................................2....................... Figure 8......... Figure 8....... HPLC analysis of intermediates of EC MCP degradation on the three anodes (aliphatic acids).2..... Figure 8...............4.............................. Current density as a function of the scan rate square root ............ Titanium plate under microscope.................. Pt (middle)......... Figure 9.....Figure 6. EC phenol oxidation reactions .............5........ 117 SEM images of the electrode in different service stage............. Phenol oxidation for electrode Ti/RuO2 to different 91 92 Phenol oxidation on the three types of anodes.................... Figure 8.........7....7................. Figure 8........................................ A typical full-width XPS spectrum of the Ti/SnO2-Sb-Al electrode..................................................... Phenol degradation pathway for electrode Ti/RuO2 ... Figure 7....... 113 114 115 116 118 124 112 111 109 107 100 101 105 MCP destruction by the three types of anodes............................ Phenol degradation pathway for electrode Pt .. MCP degradation as a function of the charge input to different anodes .............. 96 concentrations ............ HPLC analysis of intermediates of EC MCP degradation on the three anodes (aromatic compounds) ............. TOC degradation as a function of charge input at different current density .... 98 Phenol oxidation for electrode Pt to different pH..... Figure 7....................................................5...................... 93 94 Phenol oxidation for electrode Pt to different concentrations ....1........4.......... TOC removal on the three types of anodes.. TOC components of intermediates of EC MCP degradation by the three anodes: Ti/SnO2-Sb-Al (left)..................... Figure 7...14............. Figure 7........... 96 Phenol oxidation for electrode Ti/SnO2-Sb-Al to different pH .................. Figure 8............... Figure 7............ Figure 9..6........... Figure 8.................................................... 99 Phenol oxidation for electrode Ti/RuO2 to different pH.............. Figure 6. Figure 9...................... LSV of anode Pt in MCP solution .....3..........1.... xiii Figure 8..............3..9.................3................ 125 126 ..................... Figure 8.... MCP electrolysis pathways for the three anodes ........8....................................................................................................2................... Figure 8............ LSV of anode Ti/SnO2-Sb-Al in MCP solution.......................1............ 104 Figure 8.............13....... Figure 7........ Figure 7..

.................2......... Basic water quality parameters of the sludge centrate samples.............. Table 3.......... Table 4... Table 3................................... 127 EDX analysis of electrode Ti/SnO2-Sb-Al ............................ 67 Effect of electro-flocculation on sludge liquor treatment ..1.............................. Table 9........... Table 5... Electroplating conditions tested and selected ..........6. Table 4.....2..........................................3.............. 85 Contact angle (advancing and receding contact 128 131 angle)measurement ... Coating solution for the Ti/RuO2 electrodes. Contact angle measurement .............5...............4...................... xiv .Figure 9....... Table 9............... Basic water quality parameters of the landfill leachate samples .................................... Figure 9......... Coating solution (100 mL) for the outer layer of the Ti/SnO2-SbAl electrodes .......2... Coating solution for the Ti/IrO2 electrodes. Table 6...................2.... Thermal deposition conditions tested and selected....... Table 3................................... Coating solution (100 mL) for inner layer electro-plating of the Ti/SnO2-Sb-Al electrodes ........6...1.......... 129 130 Tables Table 3......... 38 39 46 46 35 37 34 34 Effect of electro-flocculation on the sludge liquor treatment .........1....... The quantities of organic adsorption on different electrodes........................... Table 3...... EDX analysis of electrode Ti/RuO2 ...... 55 Kinetic constants comparison for different species incineration ......................4... Figure 9..............1.. Table 5......................5....1... Table 3...

Abbreviations AOP o advanced oxidation processes degree Celsius chemical oxygen demand cyclic voltammetry Dimensionally stable anodes Electrochemical Energy Dispersive X-ray granular activated carbon gas chromatography mass spectrum High performance liquid chromatography linear sweep voltammetry mono-chlorophenol ammonia nitrogen nitrite nitrogen nitrate nitrogen platinum electrode plate suspended solids scanning electron microscopy trihalomethane titanium electrode plate titanium electrode coated with iridium oxide film titanium electrode coated with ruthenium oxide film titanium electrode coated with tin oxide film dopped with antimony and aluminium C COD CV DSA EC EDX GAC GC-MS HPLC LSV MCP NH3-N NO2--N NO3--N Pt SS SEM THM Ti Ti/IrO2 Ti/RuO2 Ti/SnO2-Sb-Al TIN TOC UV XPS total inorganic nitrogen total organic carbon ultraviolet X-ray Photoelectron Spectroscopy xv .

Recalcitrant and toxic organic chemicals from industrial discharges are more difficult to deal with using conventional treatment methods. In addition. Therefore. Conventional wastewater treatment is a combination of physical. wastewater treatment technologies require continuous advances to keep up with the development in industrial and commercial activity.Chapter 1: Introduction Chapter 1 Introduction 1. Therefore. resulting in algal blooms and red tides. new treatment methods have to be developed to allow compliance with more stringent 1 .1 Problem statement 1. wastewater treatment for effective removal of a wide variety of contaminants is essential to the protection of public health and the environment. Many conventional treatment processes are neither capable nor cost-effective for treating high-strength wastewater and various types of industrial effluents. suspended solids and pathogenic microorganisms. Toxic compounds in the wastewater will increase the toxicity of the natural water and upset the ecological system. The treatment system is usually designed for the removal of domestic organic matter. Decomposition of the wastewaterderived organic matter will consume dissolved oxygen in the receiving water and lead to nuisance conditions. Discharge of untreated wastewater into natural waters can cause serious water pollution problems.1. chemical and biological processes. For example. a high ammonium content in the wastewater influent has always been a challenge to the biological nitrogen removal system. Nutrients such as nitrogen and phosphorus can stimulate rapid growth of algae.1 Advanced oxidation processes and electrochemical methods for wastewater treatment All communities and industrial activities produce liquid waste – wastewater – that contains various contaminants.

With the unique features. Chen. synthetic chemical plants. 2006). detergent. 2005).1. 2006). the application of the EC process for nitrogen removal from landfill leachate and sewage sludge liquor is also investigated. and pharmaceutical plants. UV/H2O2 oxidation. AOPs have been proven to be able to destroy numerous toxic organic and halogenated organic chemicals (Azbar et al. Recently. The present study focuses on the development of the EC treatment technology for the degradation of aromatic and chlorinated aromatic organic pollutants in wastewater. 2005). pulp and paper.. Many AOP technologies generate hydroxyl radicals that are a powerful. phenol and phenolic substances have attracted great attention in the last 2 . textiles. 1... plastics. Kajitvichyanukul et al. In addition.. particularly for low-volume applications (Li et al. 1995. 2002). Research has shown that toxic organics in various types of wastewater effluents can be effectively oxidized by electrochemical reactions (Vlyssides et al. Advanced oxidation processes (AOP).. 2002. Among the harmful organic chemicals in industrial wastewaters.. the EC process has the potential to be developed as a cost-effective technology for treating toxic and refractory organic pollutants. 2004). The principal mechanism of AOPs involves the generation of highly reactive free radicals (Agustina et al. non-selective chemical oxidant capable of destructing a wide range of recalcitrant organic compounds. photo-Fenton process. CO2 and H2O without generation of secondary pollution commonly associated with conventional treatment processes. such as ozonation. such as petroleum refineries. Yonar et al.2 Electrochemical treatment of toxic organic pollutants Aromatic toxic organic compounds are common pollutants in the waste effluent from many industrial sectors. Fenton’s reaction.. Electrochemical oxidation is another new AOP alternative. there has been an increasing research interest in the use of electrochemical (EC) methods for water purification and wastewater treatment (Vlyssides et al.. AOPs have the potential to completely mineralize organic contaminants to inorganic salts. sonolysis and supercritical wet oxidation. 2004. The EC process is simple in configuration and robust in operation. have shown promise as alternative techniques for the detoxification of wastewaters containing toxic substances (Shen et al. pesticide and herbicider.Chapter 1: Introduction wastewater discharge standards and to meet the requirements for many special applications.

However. 1999). the discharge limit is 20 µg/L. yet it is difficult to extract phenol from wastewater when its concentration is lower than 4000 mg/L.. 1999.. durability and reproducibility have been problems for these electrodes. less toxic. the stability. Biological treatment. Bonfatti et al. such as PbO2 and SnO2 based coating. are not applicable for organic degradation (Rodgers et al. Recent research has demonstrated that electrochemical technologies can be applied to the treatment of wastewater containing organic pollutants such as phenol and phenolics (Polcaro and Palmas.. 1990). In the case of phenol. chlorinated phenols are often recalcitrant and must be treated differently.. phenol is often an intermediate product in the oxidation pathway of higher molecular weight aromatic hydrocarbons. 1990. This makes recycling/recovery impractical and hence the phenolic waste must be treated. Kim et al. Gu et al. 2002). However. have been introduced to improve the treatment performance. 1999. Rossi and Boodts. 1997. the effectiveness of EC wastewater treatment depends on the types and properties of the anodes used in the application (Trasatti. is normally the cheapest and simplest technology to remove waste organics. If a recalcitrant compound such as phenol and chlorophenol cannot be treated by a conventional biological approach.Chapter 1: Introduction two decades owing to their toxicity and quantity in industrial discharges. Chen.. 2000. The coating techniques 3 . Treatment of industrial effluents containing toxic organics such as phenol and chlorinated phenols is a difficult task. 2006). phenol and chlorinated phenols have been commonly taken as model compounds for studying the effectiveness of various advanced wastewater treatment technologies. such as graphite and nickel... Traditional electrodes. Kim et al.. Chen et al. or towards complete oxidization to CO2. 2004). 2004). an alternate treatment technology will be directed towards modifying its chemical structure to make it more biodegradable. 2000). Titanium based dimensionally stable anodes (DSAs) are found to have a different degree of success.. Moreover. These types of electrodes appear to be more reactive toward organic destruction (Trasatti. Two separate reports showed that wastewaters containing 200 mg/L or more of 2MCP could not be effectively treated at biological treatment facilities (Bonfatti et al. However. 1998. The commonly used RuO2 and IrO2 coating surface does not show a high reactivity for organic oxidation (Arikawa et al. such as the activated sludge process. Other DSA coating materials. Thus. 2002. Phenolic substances are persistent pollutants with high toxicity that are released in the wastewaters of a considerable number of industries (Morao et al.

. 1991. 1993). Pretreatment of landfill leachate is normally required before its flow into a municipal 4 . Leachate from landfills is a special municipal waste liquid that probably is most difficult and expensive to treat. 2000.3 Electrochemical denitrification for high-strength wastewater Many types of wastewaters. 2001. The ammonia loading from sludge liquor contributes to 10-20% of the influent nitrogen loading. The difference in the effectiveness of different anode materials also demonstrates the complexity of the EC oxidation mechanisms involved. 1997). 2000). Phenol oxidation could stop with the products such as maleic acid for the Pt anode (Comninellis and Pulgarin. the oxidation pathway of aromatic chemicals on different anodes remains a subject for investigation. Although the flow rate of the sludge liquor is low. such as the sewage sludge liquor and landfill leachate. Gattrell and Kirk. 2003). it has a high nitrogen content with a NH4+-N concentration between 500 to 800 mg/L. The sludge liquor from the dewatering unit is then returned to the inlet of the treatment system. The effect of the anode surface property on the EC reaction mechanism and reaction kinetics also needs to be characterized in greater details. complete phenol degradation could be delivered by the PbO2 electrodes (Iniesta et al.1. Inflow of raw leachate into a municipal wastewater treatment plant will considerably increase the loading of the treatment facility. 1. Feng and Li. contain a high ammonia concentration. Kolisch and Rolfs. However. Landfill leachate usually has a NH4+-N concentration of more than 3000 mg/L together with about the same amount of refractory organic pollutants. separate treatment of the sludge liquor can take advantage of the high NH4+ concentration in the liquor. Therefore. accounting for about 1% of the influent. The sludge is usually treated by anaerobic digestion followed by dewatering prior to its final disposal.Chapter 1: Introduction still need to be modified to improve the quality of the coating surface for better wastewater treatment performance and more cost-effective application... In addition. which eventually increases the overall cost-effectiveness of a municipal wastewater treatment plant (Arnold et al. Secondary biological wastewater treatment produces a large volume of sludge. Removing this ammonia loading will either improve the performance or increase the capacity of the mainstream wastewater treatment process for nutrient removal (Jetten et al.

For example. including air stripping and biological processes. in Hong Kong and a few coastal cities in China. which can largely improve the performance of the EC denitrification process (Li et al. 1995).. Phenol and chlorophenol were selected as the model aromatic compounds for EC treatment.. are either too expensive or less effective in actual applications. As for the landfill leachate. Current leachate treatment methods. increasing the treatment cost. The EC method can be developed as an effective leachate treatment alternative for ammonia oxidization and nitrogen removal. 1. there is a growing need for development of more cost-effective treatment technologies for the leachate from aged landfill facilities. a coating technique was developed for making Ti-based electrodes. In the following decades. seawater has been increasingly used for domestic purposes.Chapter 1: Introduction wastewater works (Lau. During EC treatment the waste liquid will be forced through a reactor of electrolysis. Thus. the biodegradability of the leachate has an inverse trend with the landfill age. An EC system is simple and robust in structure and operation. The inclusion of seawater in sewage increases its salinity content. The Ti electrodes were coated with a layer of SnO2 doped with Sb and Al (Ti/SnO2-Sb-Al). 2003). and only young landfill leachate is fit to the biological treatment process (Chiang et al. the effluent quality of EC denitrification is expected to be more consistent and reliable due to its simple working conditions compared to other nitrogen removal processes. Diao et al. Due to the shortage of freshwater supply in recent years. 2000). such as toilet flushing.2 Objectives of this study In the present study. 2002. Laboratory experiments were carried out to examine the reactivity of the Ti/SnO2-Sb-Al anodes toward destruction and oxidation of toxic organics. Moreover. a large amount of readily biodegradable organic needs to be dosed into the system. in which electrochlorination and the subsequent ammonia oxidization are expected. The electrochemical (EC) method can be considered for nitrogen removal in treatment of high-strength wastewater such as sludge liquor and landfill leachate. In using a biological nitrogen removal process.. Comparative experiments of organic degradation were conducted with the 5 . its chloride concentration is usually high at a level of around 3000 mg/L. landfill will continuously be employed as an option for solid waste disposal.

Ti/RuO2 and Ti/IrO2. to evaluate the treatment efficiency of EC denitrification and to optimize the process configuration and operation. The effectiveness and performance of different anode types for toxic organic reduction were investigated. The study focused on the reactivity of the 6 . and to investigate the underlining mechanisms of EC organic degradation by different types of electrods. • To determine the reaction kinetics. in comparison with the treatment performance of the Pt anode and the conventional DSA Ti/RuO2 and Ti/IrO2 electrodes. the objectives of the present study are: • To make Ti/SnO2-Sb-Al electrodes using a modified coating method to improve the reactivity of the electrodes toward organic oxidation and the stability and durability of the electrodes in EC wastewater treatment. • To examine the effectiveness of the Ti/SnO2-Sb-Al electrodes for the degradation of phenol and chlorophenol. Pt and Ti/RuO2. The intermediate products of the EC process with different anodes were measured by HPLC for determination of the phenol and chlorophenol degradation kinetics and pathways. 1. • To characterize the surface and electrochemical properties of the different electrodes in relation to their performance in organic electrolysis.3 Scope of this study This research began with the preparation of effective catalytic active anodes in Ti/SnO2-Sb-Al for organic oxidation. The surface properties of different anodes were characterized and the related EC reaction mechanisms were proposed. The capacity and efficiency of EC denitrification for treatment of landfill leachate and sewage sludge liquor were evaluated. In summary. • To develop the EC process for both ammonia removal and organic reduction from sewage sludge liquor and landfill leachate. intermediate products and degradation pathways of electrolysis of phenol and chlorophenol on the three different anodes of Ti/SnO2-Sb-Al.Chapter 1: Introduction Pt electrode and standard DSA electrodes. The system configuration and operation parameters for better treatment process performance were determined. In addition. laboratory research was conducted for ammonia removal by electrochemical oxidation on the Ti/RuO2 electrode.

Chapter 8 summarized the findings of a similar electrolysis study for chlorophenol degradation. including organic oxidation and related mechanisms. experiment results of electrochemical denitrification and organic matters removal were reported.3. In Chapter 5.1 Electrochemical treatment of saline sludge centrate and landfill leachate Laboratory experiments were carried out to investigate the effectiveness of EC treatment of saline sewage sludge liquor and landfill leachate for denitrification and organic removals. In Chapter 9. previous studies on wastewater treatment using electrochemical methods were reviewed.3. chloride content. gap distance between the electrodes. including the reaction kinetics. intermediate products and possible degradation pathways. Chapters 6 and 7 presented the results of EC phenol treatment by different electrodes. on the performance of EC denitrification were evaluated. 1. power input and contact time. The following Chapter 4 added the materials and methods of the wastewater treatment experiments. Electrode Ti/RuO2 was also prepared by coating in accordance with the conventional thermal deposition method . the effects of the surface properties of different anode types on the degradation of toxic organic matter and the underling EC treatment mechanisms were discussed. 7 . The influences of system and operational parameters. such as the current intensity. 1.Chapter 1: Introduction anodes toward electrolysis of phenol and chlorophenol in comparison with other electrodes. electrolysis experiment procedures. wastewater samples. operational conditions and analytical methods.2 Preparation of catalytic active anodes for organic oxidation Titanium-based catalytic active metal oxide anodes in Ti/SnO2-Sb-Al were prepared using a modified coating approach. The formation of chlorination by-products during the EC treatment was also determined. The outer layer was prepared by sol-gel methods for metal element deposition followed by oxidation in a high temperature oven. Chapter 3 described the methodologies used in preparation of electrodes Ti/SnO2-Sb-Al and Ti/RuO2 and characterization of the electrodes. In Chapter 2. The electrode was coated on Ti substrate with double layers of Sn-Sb-Al oxides. The internal layer was deposited by electroplating and calcified at high temperature in an oven.

hydrophobicity and element components. Rates of aromatic destruction and organic reduction. the coating surface properties of the electrodes were analyzed for their morphology. phenol and chlorophenol oxidation. EC oxidation tests were also conducted for individual pure chemicals that were intermediates of EC phenol degradation in order to identify the possible rate limiting steps in EC organic degradation. 1. The intermediate products of the EC treatment process were measured by HPLC in great details. In addition. including oxygen evolution.3.Chapter 1: Introduction 1. The findings suggest the influences of the anode surface on the performance of EC organic degradation and the underlining mechanisms. The comparative degradation experiments were also conducted with other electrodes. Ti/RuO2 and Ti/IrO2 electrodes. current efficiency and degradation kinetics of the organic electrolysis on different anodes were determined.4 Characterization of the electrochemical and surface properties of different electrodes and their effects on organic electrolysis The electrochemical properties of different types of anodes were characterized by voltammetry in a pure electrolyte solution and organic solutions of different concentrations.3. including the Pt. and the degradation pathways of phenol and chlorophenol by different types of anodes were formulated. 8 . The responses of the current intensity to an increase in potential input in different solutions offered important information about the electrochemical reactions.3 Degradation of phenol and chlorophenol by electrolysis at different electrodes Phenol and chlorophenol were selected as model toxic organic chemicals for testing the treatment capacity of the Ti/SnO2-Sb-Al electrode.

and strong tendency for bioaccumulation in human and animal tissues. face discharges containing a complex mixture of various organic and inorganic substances (Farre et al.1 Toxic organic pollutants and nutrients in wastewater discharge Water is the most ubiquitous biological compound and is imperative to life. 2004. floatables. wastewater treatment plants (WWTPs). 2006). 1997). 2003.. 2004). pesticide and herbicide. 2006). These compounds are characterized by pronounced persistence against chemical/biological degradation. pulp and paper. POPs constitute a wide group of compounds. The combined sewer contains many contaminants.1. polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCs). textiles. especially those located in industrial areas. such as aromatic compounds (Breivik et al.Chapter 2: Literature review Chapter 2 Literature review 2. In cities that have combined sewer systems. Blanchard et al. biochemical oxygen demand. including potentially high concentrations of suspended solids.. 2004. Katsoyiannis et al. Additional to municipal wastewater. high environmental mobility. Pham and Proulx. and pharmaceutical factories. toxics. nutrients. such as petroleum refineries. 2000).. Karvelas et al.. 2003. the runoff is treated with municipal wastewater in sewage treatment plants (Reemtsma et al. oils and grease. Runoff from urban settings has significant impact on the quality of the receiving waters (Amvrossios et al. significant impacts on human health and the environment 9 .1 Wastewater treatment for removal of toxic organics and nutrients 2. detergent. pathogenic microorganisms.. chlorinated aromatic compounds. synthetic chemical plants.. Persistent Organic Pollutants (POPs) are common pollutants in the waste effluent from many industrial sectors. plastics. and other pollutants (Amvrossios et al...

Su et al. Beline et al. 2006). organic solids to minerals or relatively stable chemicals. are preliminary.. Cao et al. Conventional wastewater treatment consists of a combination of physical. or more completely oxidize. nutrients from wastewater. primary.. which would modify the chemical structure of the organic to make it more biodegradable.. Biological wastewater treatment most 10 . 2001. 2004).. 2004. 2. Joo. Carrera et al.2 Biological treatment processes Microorganisms have been used for decades for the treatment of municipal wastewaters.. Ammonium treatment is essential in wastewater treatment plants for preventing eutrophication of the receiving water. and more recently for the treatment of industrial waste liquids.. 1997).1. 2004). and tertiary and/or advanced wastewater treatment (Sonune and Ghate. 2003.1.2 Conventional wastewater treatment technologies 2. Alternative technologies should be applied for toxic organic removal.1. chemical. secondary. Katsoyiannis and Samara. 2000. Their low biodegradability makes them refractory to the biological wastewater treatment (Katsoyiannis et al. Removing this ammonia loading will either improve the performance or increase the capacity of the mainstream wastewater treatment process for nutrient removal (Jetten et al. Among the nitrogenous compounds. although these are not always achievable in practice. sometimes the ammonium concentration can reach 1000–3000 mg/L. which is 50–100 times higher than in municipal wastewater (Ra et al. Its advantages include low cost and easy operation. The traditional biological nitrogen removal can be achieved by a sequence of nitrification and denitrification processes (Kim et al. Uygur and Kargi. 2.2. and biological processes and operations to remove solids.. 2001. sometimes.. 2003. and public acceptance. organic matter and.Chapter 2: Literature review even at extremely low concentrations. less toxic. General terms used to describe different degrees of treatment. 2006).1 Wastewater treatment Wastewater treatment is a process in which the pollutants in wastewater are partially removed and partially changed by decomposition from highly complex. putrescible.2. 2004. in order of increasing treatment level.

Chapter 2: Literature review often employs aerobic conditions, in order to mineralize organic compounds to CO2 and H2O. In general, aerobic bioreactors achieve satisfactory levels of organic removals, with problems of sludge formation and by-product off-odors (Sonune and Ghate, 2004). Biological denitrification is known to occur by the action of heterotrophic bacteria using available carbon sources (John and Robert, 1985; Lee et al., 1995 and Lee et al., 1997). Because the influent with a low C/N ratio is deficient in organic carbon and the low carbon source level can limit the overall biological denitrification results, sufficient organic source must be provided for proper denitrification (Itokawa et al., 2001; Kim et al., 2004). Thus, conventional nitrification can be implemented only after pretreating the wastewater to adjust the C/N ratio (Khin and Annachhatre, 2004) or diluting the wastewater (Rostron et al., 2001; Jung et al., 2004). Although the activated sludge process has been successfully used for treating various domestic and industrial wastewaters, the high concentration of toxic pollutants such as phenol, chlorophenol and other aromatic compounds severely inhibits biological activities of activated sludge (Amor et al., 2005; Liu et al., 2005; Young et al., 2006). Only granular activated carbon (GAC) and specially designed bio-treatment processes have been used commercially for treatment of toxic organic pollutants. There still remains the need for reliable, economic and safe treatment alternatives. Electrochemical oxidation is one of conceivable candidates for such a treatment technology. 2.1.2.3 Physical-chemical treatment methods Other methods for wastewater treatment that are being used or are in the development stage are physical and chemical processes, including flocculation, solvent extraction, precipitation, coagulation and sedimentation, sand filtration, activated carbon adsorption, membrane filtration, chemical or electrochemical oxidation (El-Geundi, 1991, Janos et al., 2003 and Meshko et al., 2001). For example, amongst chemical methods, Milstein et al. (1991) reported 75%, 59% and 80% removal of Adsorbable organic halides (AOX), COD and color, respectively, with the help of a mixture of polyethylene and modified starches (Savant, 2006). Using ultrafiltration, 99% reduction in AOX was achieved by Yao et al. (1994).

11

Chapter 2: Literature review Although these physical and chemical treatment processes might be effective for organic and color removal, they use more energy and chemicals than biological treatment processes, and chemical wastes are also generated from these processes (Sirianuntapiboon et al., 2006). In general, physical and chemical treatment technologies for removal of toxic compounds are uneconomical when applied alone in field scale operations. Additionally, physical and chemical treatment methods such as flocculation, adsorption and oxidation are not effective in removing the high concentration of toxic organics from the wastewater (Zhang et al., 2006). Chemical oxidants such as permanganate and hypochlorite may be applied when wastewater concentrations are too high for acclimatized biological treatment (Savant, 2006). The chlorine and hypochlorite generated by electrolysis of chlorides can be used to oxidize organic compounds in the wastewater. 2.1.3 Advanced oxidation processes (AOPs) 2.1.3.1 Ozonation The conventional municipal wastewater treatment does not fully eliminate toxic organic pollutants. It has been shown that this may be achieved upon treating the effluents with ozone (Huber et al., 2003, Huber et al., 2004, Huber et al., 2005 and Ternes et al., 2003). Ozonation has been shown to have a high potential for the oxidation of various types of toxic and refractory organics in wastewater discharge (Ternes et al., 2003; Huber et al., 2003, 2005). Ozone can generate ·OH radicals through the formation of an ozonide radical (·O3−) in the adsorption layer (Equation 2.1). The generated O3− species rapidly reacts with H+ in the solution to give ·HO3 radical, which evolves to give O2 and ·OH as shown in Equation 2.2 and 2.3 below (Agustina et al., 2005):
O3 + e − → ⋅O3
− −

(2.1) (2.2) (2.3)

⋅ O3 + H + → ⋅HO3

⋅ HO3 → O2 + ⋅OH

In wastewater, O3 doses ranging from 5 to 15 mg/L led to a complete disappearance of most of the pharmaceutical organics (Huber et al., 2003; Huber et al., 2005). Ozonation is also considered as an effective process for the removal of 12

Chapter 2: Literature review ammonium nitrogen. The application of 15.4 mg/L ozone dose resulted in a nitrogen reduction of up to 35% (Petala et al., 2006). Pretreatment with ozone or peroxide hydrogen also enhances the biodegradability of wastewater such as kraft mill caustic extraction effluents (Savant et al., 2006). Hostachy et al. (1997) reported complete detoxification and removal of residual COD of bleached kraft mill effluent at low ozone doses of 0.5–1.0 mg/L. Mobius and Helble (2004) have described a combination of ozonation followed by biodegradation in a biofilm reactor to achieve a far reaching elimination of adsorbable organic halides (AOX), color and other toxic organic substances. A major limitation of the ozonation process is the relatively high cost of ozone generation process coupled with a very short half-life period of ozone. Moreover, the process efficiency is severely dependent on the efficient gas liquid mass transfer, which is quite difficult to achieve due to the low solubility of ozone in the aqueous solutions (Gogate and Pandit 2004). 2.1.3.2 Photolysis The photo-activated chemical reactions are characterized by a free radical mechanism initiated by the interaction of photons of a proper energy level with the molecules of chemical species present in the solution, with or without the presence of the catalyst (Bhatkhande et al., 2002; Agustina et al., 2005). A major advantage of the photo-catalytic oxidation based processes is the possibility to effectively use sunlight or near UV light for irradiation. This should result in considerable economic savings especially for large-scale operations (Bauer, 1994; Yawalkar et al., 2001; Agustina et al., 2005). Moiseev et al. (2004) have also shown that the use of photo-catalytic oxidation as a pretreatment step enhances the biodegradability of wastewater containing recalcitrant or inhibitory compounds and is an alternative to a long and energy intensive total pollutant mineralization. A major problem in the successful application of photo-catalytic oxidation is the non-uniform irradiation of the catalyst. This would result in a substantial loss of the incident energy and hence the overall economics may not be favorable. Groups of Ray Beenackers (Ray 1999; Mukherjee and Ray, 1999), Li and Yue (1998a,b, 1999) have tried to address this problem, but not much success has been reported yet. Still the efficiency of photo-catalytic oxidation cannot be underestimated as there is also 13

Krutzler and Bauer 1999.4) for wastewater treatment. which is named as the photo-Fenton reaction that produces additional ·OH radicals and leads to the regeneration of the catalyst (Equation 2.Chapter 2: Literature review large potential for the combination of photo-catalytic oxidation with other advanced oxidation processes (Agustina et al. 2001). 2001. it was found that the reaction can be enhanced by UV/VIS light (artificial or natural). can easily oxidize organic compounds.4 Limitations of AOPs Advanced oxidation processes (AOPs) are frequently selected as a treatment option to oxidize toxic organic compounds present in contaminated waters. ·OH (Valdés 2006). Fe 2+ + H 2 O2 → Fe 3+ + OH − + ⋅OH Fe 3+ + H 2 O + hv → Fe 2+ + H + + ⋅OH (2. Fallmann et al.. Furthermore. However. Such oxidation reactions are based on radical formation. However. Lee and Hosomi 2001). a mixture of Fe2+ salts with hydrogen peroxide (H2O2). 2.3.. This reagent is an attractive oxidative system. 2005). These scavengers terminate the radical-type chain reactions. Kositzi 2004).. 1997. 14 . Arana et al.3. the presence of radical scavengers such as carbonates. ·OH is highly reactive and non-selective. 1999. These reactions are known to be the primary actions of the photochemical selfcleaning of atmospheric and aquatic environment (Faust and Zepp 1993. Fenton’s reaction has been applied for wastewater treatment only in recent years (Bidga 1995. Iron is a very abundant and non-toxic element and hydrogen peroxide is easy to handle and is environmentally safe..5) (Oliveros et al. with the reaction rate constants with organics generally in the order of 105–109/M·s (Valdés 2006).4) (2.. inhibiting propagation reactions and consequently reduce the application of AOPs in industrial scales (Valdés 2006).g.5) 2. e.1. Chamarro et al. which produces in a very simple way ·OH radicals (Equation 2. bicarbonates and natural organic matter impairs ·OH formation.1.3 Hydrogen peroxide/Ultraviolet light It is well known for some time that Fenton’s reagent.

The reason for activity has been identified in the surface redox reactions taking place at transition metal ions that act as active sites (Trasatti..2.2 Electrochemistry in wastewater treatment 2. These redox centers. such as O2 evolution. had only revealed a linear variation of overpotential with the enthalpy of hydroxide formation (Trasatti. 1999. For example. have soon shown their activity for almost all other more common electrocatalytic reactions. as well as organic oxidation. Currently. a certain organic compound can hardly be degraded by ozonation or photolysis alone and the treated wastewater may be more dangerous as a result of ozonation (Lambert and Graham 1995. RuO2 and IrO2 are widely used surface coating materials. are able to catalyze a variety of electrode reactions occurring in a potential range close to that of the surface redox couple. and UV/H2O2 (ultraviolet/hydrogen peroxide). Due to their high overpotential for water electrolysis large enough electrochemical windows are gained to produce hydroxyl radicals (Gerger and Haubner 2005). usually titanium. a majority of these AOP oxidation technologies are still too complex and expensive and less effective for actual application in wastewater treatment (Agustina et al. DSA are prepared by the deposition of a thin layer of metal oxides on a base metal. based on metals. One of the most stringent reasons for the success of DSA is the hydroxide formation. 1998). 2.Chapter 2: Literature review In general. These electrodes. Camel and Bermond 1998).. a combination of several methods gives high treatment efficiency compared with individual treatment. can effectively improve the removal of organic pollutants from the wastewater (Hu et al. It was shown that organic carbon can be completely converted to 15 . 2005). 2000). Nonetheless. The same approach by Rüetschi and Delahay. coupled with the moderate interaction of intermediates with the oxide surface. made for chlorine evolution. a combination of several treatment methods. Transition metal oxides are among the most versatile electrocatalysts (as much as catalysts) ever known. However.1 Development of electrochemical wastewater treatment Dimensionally Stable Anodes (DSA®) have been introduced for the electrochemical technology for several decades. 2000). Plummer and Edzwald. even H2 evolution. O2 reduction. such as O3/H2O2/UV (ozone/hydrogen peroxide/ultraviolet).

2004). The method of electro-chlorination has been successfully employed for treating various types of industrial wastewater (Lin et al.2. They have been studied for treatment of municipal and industry wastewater and recovery of chemicals (Buso et al. 1997). Chen. 2004). 2005). 2004).2. Many industrial wastewaters have been found to be of highly saline content (in terms of NaCl).2 Application of electrochemical technologies in wastewater treatment 2.Chapter 2: Literature review carbon dioxide without the formation of by-products. the high cost normally involved in these processes limits their widespread application. However.2.. 1997. 2..2. Even with a long chain structure. 2003). 2004)... such as removal of phosphate from aqueous solutions (Bekta et al. To take advantage of this characteristic. organic molecules can be mineralized without the accumulation of intermediate products. electro-flocculation and electro-flotation are the electrochemical techniques which may be used separately in different reactors or combined in the same reactors... the main drawback of the indirect electrochemical organic degradation by chlorination is the formation of chlorinated compounds. removal of sulfide. especially in the case of low pollutant concentrations (Buso et al. However. olive oil mill wastewater treatment (Inan et al.. 2002. sulfate and sulfite ions (Murugananthan et al. a plausible alternative for dealing with saline wastewater is to use the electrochemical methods. electro-flocculation and electro-flotation Electro-coagulation..1 Electro-coagulation. 1998).2 Electro-chlorination for wastewater treatment Dimensionally stable anodes have been used in chlorine production for about 30 years. and oxide electrodes for chlorine evolution in acidic chloride solutions have been well studied (Cornell et al. 16 .2.. These properties of new DSA electrodes come up to the requirements for an efficient electrochemical wastewater treatment (Gerger and Haubner 2005). the wastewater has a rather high conductivity. With a high saline content. 2. Lin and Wang (2003) had found the formation of chlorinated organic compounds using chromatography while treating anionic surfactants. Jiang et al. and treatment of metal finishing effluents (Khelifa et al.

Grahl and Markl. 1996. through converting it into gaseous nitrogen (Vanlangendonck et al.Chapter 2: Literature review Indirect electro-oxidation. (2003). particularly for saline sewage effluents encountered in Hong Kong (Li et al. (2002) applied an electrochemical treatment to domestic wastewater using 0. The results show that T–N..3 Electro-chlorination for wastewater disinfection Electro-chlorination has been increasingly used for wastewater disinfection. The authors used a pilot reactor with a treatment capacity of 0. During direct EC disinfection. 1990.3 Electro-catalytic oxidation of toxic organics 2. a stream of seawater is electrolyzed to produce a flow of chlorine solution that is injected into a wastewater flow. 1982. The process is pH sensitive. 2003). 2002). Patermaraxis and Fountoukidis. is a possible answer to an ammonia–nitrogen problem.8% (w/v) sodium chloride as electrolyte and an electrolytic cell with Ti/Pt as the anode and stainless steel 304 as the cathode. the alkaline environment appeared to be beneficial to the ammonia removal. T–P and COD could be removed from domestic wastewater effectively by the electrochemical treatment system.3 m3/h. 2005). Organic phosphorus content of the wastewater 17 . NH4–N..3.2. The EC process has the potential to be developed as a cost-effective and environmental friendly alternative of disinfection.2. In electro-chlorination. and Lin and Wu (1996) repoeted that while the acidic environment favored the nitrite removal. 2. 2. all wastewater is forced through a disinfector that is equipped with electrodes on which current is applied. Vlyssides et al. It also has been reported that direct electrochemical disinfection can destroy a wide variety of microorganisms from viruses to bacteria and larger species such as Euglena (Stoner and Cahen.1 Electrochemistry for toxic organic degradation Electrochemical treatment for the purpose of treating domestic wastewater was evaluated by Feng et al. through hypochlorite formation. Organic carbon and nitrogen content of the wastewater was wet oxidized to carbon dioxide and nitrogen gas.. On the other hand. A current density of 3 mA/cm2 was applied with 500 V pulse voltage at a frequency of 25 kHz. Park et al.

respectively (Yonar et al.. 90%. volatile suspended solids (VSS). Vlyssides et al. Kim et al. Many researches have demonstrated that electrochemical technologies can be efficiently applied to the treatment of wastewater containing organic pollutants (Polcaro and Palmas 1997.2 Dimensionally stable anodes (DSA) for organic oxidation Electrochemistry is an treatment alternative for organic degradation that has attracted considerable research attention (Comninellis.... 1991... 1990.. 2004). 2006). DSAs are found to have a varying degree of success. Bidga (1995) performed an electrochemical degradation test with carbon electrodes and achieved 82% surfactant removal on the total organic carbon (TOC) basis.. Greet et al. Gu et al. 1994. show a poor current efficiency in organic degradation (Rodgers et al. 82% and 98%. Up to now... 2000. COD. Examples of the anodes for the treatment purpose include glassy carbon electrode. Chiang et al. Chen. Bonfatti et al. Stucki et al. such as graphite and nickel. Feng and Li. 1995. Pt/Ti and graphite (Polcaro and Palmas 1997.3.. 2006). particularly for lowvolume applications. The effectiveness of EC wastewater treatment depends on the nature of the anodes (Feng and Li.. The authors achieved a complete surfactant removal with an electrolyte addition of 0.. Traditional electrodes. Complete oxidation of linear alkyl surfactants (LAS) and alkyl benzene surfactants (ABS) at bipolar dimensional stable anodes also has been studied (Panizza et al. 1999. 1994. ammonia nitrogen and total phosphorus were reduced by 89%. Kötz et al. 2003. many works have been done to develop high performance anodes for a high catalytic activity and long service life. 2000). 2003. 1991. 2003. 1999.Chapter 2: Literature review was removed by precipitation. The commonly used RuO2 and IrO2-based coating surface does not appear to have a high reactivity for organic oxidation (Comninellis.8 mA/cm2 in conjunction with chemical coagulation (Panizza et al. With unique features such as simplicity and robustness in structure and operation. Feng and Li. 2005). Johnson et al.. 1999. 1999). Brillas et al. 2003). 2006). 1999. Gu et al. 2005).05 M NaCl at a current density of 16. carbon felt. Simod and 18 .. Rodgers et al. 2. the EC process has the potential to be developed as a costeffective technology for the treatment of aromatic pollutants.. Toxic organics can be effectively oxidized by electrochemical (EC) reaction (Brillas et al..

SnO2 anodes are expected to offer a better solution for the enhancement and application of the EC process to organic degradation in wastewater treatment..3. Tahar and Savall. Polcaro et al. Feng and Johnson. 1991. The preparation of dimensionally stable anodes consists of a coating (painting) of a surface layer of metals on the titanium surface. Feng et al. With further development and characterization.. EC incineration (Comninellis. PbO2 and similar anodes are considered to be of sufficient electro-catalytic capacity for organic oxidation (Comninellis.3. e. Other DSA coating materials. 1997). 2002). chlorate and other chemicals (Krysa and Mraz. Feng and Li. such as PbO2. The SnO2-based coating has shown a similar reactivity as that of PbO2 for EC organic degradation (Rodgers et al. Houk et al.3 Preparation of Ti-based catalytic active anodes 2. 1995.g. To achieve good adhesion of the coating. The tin 5s states are 19 . PbO2 electrodes can be highly effective for complete organic destruction. Schumann and Grundler. concern over the possible toxicity of Pb leaching from the working anode would hinder the actual application of PbO2 electrodes. Correa-Lozano et al. the surface of the base metal must be pretreated to an appropriate degree of roughness.and SnO2-based coatings. 1997... Titanium is used in the chemical industry not only as a construction material but also for the preparation of dimensionally stable anodes for the production of chlorine. 1999).1 The substrate base material: Titanium Titanium has recently found increasing use in industrial application due to its high strength to weight ratio and excellent resistance in a variety of environment. 2. However. 2. 1998.. have been introduced to improve the treatment performance. 1999.3.3.Chapter 2: Literature review Comninellis. Hence. 1994. The valence band arises due to the overlap of filled oxygen 2p levels. Kötz et al. Kryasa and Mraz (1994) also confirmed that the real surface area after etching by HCl is larger than treated by other acids such as HF. 1998).3.. 1999. Etching in concentrated HCl is commonly used as a pretreatment of Ti.5 eV... Tanaka et al. 1994. 1994).2 Antimony doped tin oxide Pure SnO2 is an n-type semiconductor with a band gap of about 3. 2003. 1991.

5 M H2SO4 electrolyte. sol-gel.3.Chapter 2: Literature review at the bottom of the conduction band. In electrochemical application. Doped SnO2 films are usually used as transparent electrodes in high efficiency solar cells.5 and temperature = 70°C. the resulting electrodes had a reduced overpotential of O2 evolution at 1. while the values for PbO2. P and Sb. 1990. The current efficiency obtained on Ti/SnO2-Sb2O5 was about five times higher than that on Pt. The conductive SnO2 films can be prepared by chemical vapor deposition (Kadam et al. Lipp and Pletcher (1997) conducted a long term test of SnO2–Sb2O5 in 0. reactive sputtering (Czapla et al.3 Sol-gel coating and thermo-decomposition Sb doped SnO2 can be effective electrode coating materials for the oxidation of hazardous organics in water (Comninellis. and brush-dry-bake techniques. However.5 V versus NHE in 0.1 M H2SO4 solution at a constant potential of 2.. 2004).1 A within a few hours and to 0. (1991) first reported anodic oxidation of pollutants on Sb-doped SnO2-coated titanium electrodes (Ti/SnO2-Sb2O5). Correa-Lozano et al. 1989).06 A after 700 h.14 and 0. B. This kind of oxide exhibits a very high resistance at room temperature and thus cannot be used as an electrode material directly.3. Comninellis (1994) measured the current efficiency (CE) of SnO2-Sb2O5 to be 0. F. 2. 1989). Grimm et al. 0.58 for 71% degradation of phenol from 10 mM. far IR detectors and transparent heating elements (Chen. 0. 1994). respectively. spray pyrolysis (Popova et al. Czapla et al. The dip-coating sol-gel method has previously been used for the preparation of catalytically active membrane film (Maier. The 20 . Kotz et al. However. gas detectors. its conductivity can be improved significantly by doping Ar. Addition of IrO2 into the SnO2–Sb2O5 mixture increased the service life significantly.44 V versus normal hydrogen electrode (NHE) and found that the current dropped from initial 0. 1990).17. pH = 12.2 to about 0. 1993). RuO2 and Pt were. 2004).13 at I = 500 A/m2. 0. (1997) also examined the stability of SnO2-Sb2O5 electrodes and found that the service life of Ti/ SnO2-Sb2O5 was only 12 h under an accelerated life test performed at a current density of 1000 A/m2 in 1 M H2SO4 solution. IrO2.18. SnO2-Sb2O5 electrodes lack sufficient electrochemical stability just like PbO2 (Chen. Despite the high efficiency for pollutant oxidation. Sb is the most common dopant of SnO2. (2000) investigated phenol oxidation on SnO2-Sb2O5 and PbO2 using a cycle voltammetric method and also found that the former was more active. Bi.

2000): such as a high purity of the coating materials. Moreover. the preparation of electrodes uses a standard DSA procedure. Total mineralization of the refractory chemical compounds can be often prohibitively expensive. Moreover... low cost and easiness of coating large and complex-shaped substrates. The oxidation route of phenol has been the subject of research work in the last two decades. phenol and phenolic substances have attracted much attention in the last two decades.Chapter 2: Literature review method has major advantages (Lange et al. 1997). formic acid. 2. but to various organic intermediate products (Thornton et al. the film provides a porous structure which enlarges the catalytic surface area of the film. the end products of the EC oxidation are organic acids of short chains. In many cases. Very high quality SnO2 layers with respect to structure and morphology can be obtained on the Ti surface by the sol-gel dipping technique. which consists of the thermal decomposition of the suitable inorganic precursor salts onto a metallic Ti base. 1992.. Duprez et al.4. 1996). Most of the papers try 21 . Ding et al. phenol is considered to be an intermediate product in the oxidation pathway of higher molecular weight aromatic hydrocarbons (Ding 1995)... Osimond et al. Among the harmful organic compounds in industrial wastewaters.1 Degradation pathway of aromatic compounds It is generally agreed that the industrial organic pollutants initially present in the wastewaters are not directly oxidized to CO2. 1995. This is due to their toxicity and the frequency of industrial usage and discharge. In general.. The coating film is then fixed on the surface by oxidation at high temperature in an oven. Chemical modifications for the enhancement of the electrode catalytic activity also can be achieved readily by the addition of doping elements. Lin et al. Manzanares et al. 1996.. such as acetic acid. A direct relationship between the preparation method and the amount of SnO2 loaded on the electrode surface has been suggested (Comninellis and Battisti. 1996.4 Reaction pathways and mechanisms of electrochemical degradation of toxic organics 2. 1996. The precursors was prepared by a sol-gel solution and coated on the substrate. oxalic acids and others independently of what initial organic compounds were present in the wastewater.

2001).. 1993. (Santos et al. 2003. 2. Alejandre et al.. Comninellis and Pulgarin... Andreescu et al.1. 1991. Gattrell and Kirk. Summary of the reaction mechanisms of electrochemical phenol degradation. Levec et al.. Pintar et al.Chapter 2: Literature review to identify the intermediates and to propose reaction schemes of different complexity (Ding et al. 1997. 1995. 1991).1 EC degradation of phenol The routes of phenol oxidation usually consider the hydroxylation of phenol to hydroquinone and catechol as the first step with a further oxidation to benzoquinones. Iniesta et al. 1991. Rodgers et al. 1994. radical disproportionation. 22 . 1998). 1995. Possible reactions related Figure 2. 1996. Feng and Li. and further oxidized into 1. Duprez et al.. 2002) to phenoxy radicals include radical–radical coupling. 1996. The further consideration is that phenol oxidation begins with an electron transfer that leads to phenoxy radical reactions (Lund and Baizer.4. The hydroxyl radical attacks the ortho position to form the catechol... Lund and Baizer.1. Eisenhauer (1964) has proposed the oxidation mechanism for phenol as the hydroxylation on the ortho-position (Chu. The kinetics and mechanisms of phenol degradation by EC oxidation have been the subject of several investigations (Duprez et al... 2003. 1999.2-benzoquinoe. Maugans et al.. 1995).

. 2000). 1995). Chu. However. and the hydroxyl radicals attack 2-chlorophenol to form chlorodihydroxy-cyclohexadienyl as confirmed by Metelitsa in 1971. which realized the ring cleavage (Chu. When this process is repeated at the para position. Chlorophenol degradation then follows the same pathway as phenol oxidation mentioned above (Eisenhauer. it is the dimerization and disproportionation. Iniesta et al. and radical oxidation of cations. 1995). Lund and Baizer. 1995). which is believed to be an important intermediate of phenol degradation (Comninellis and Pulgarin.. then the carbon that is double-bonded with the oxygen will be attacked by a neighboring hydroxyl radical generated from water electrolysis (Li et al. 1998. 1964.1 (Santos et al. Several mechanisms have been proposed for benzoquinone degradation. Hydroxylation on the ortho position is the second rout. If benzoquinone is adsorbed onto the anode surface and gives up an electron. The chlorocatechol.4. benzoquinone can be degraded with ring breakage to various carboxylic acids. no differences between hydroquinone and catechol are made and it is assumed that both dihydroxylbenzenes follow the same oxidation route. 1991. product of hydroxylation will degrade quickly to chloromuconic acid via chlorohydroquinone (Sedlak and Andren. In an oxygen saturated system. Benzoquinone. 2002). 1991b.Chapter 2: Literature review radical elimination. 1995).. A summary of these electrochemical phenol oxidation schemes can be found in Figure 2. dimerization and polymerization are not the major reactions comparing with ring oxidation (Chu. the confirmation of the scheme by stoichiometry and the influence of the variables 23 . 2. 2001). 1995). the hydroxyl radical attack on the para position is another kind of mechanism.1. The degradation of chlorophenol could be split into three routes while the hydroxyl radical generation is a continuous actin (Rodgers. Radical reactions result in the formation of benzoquinone.. In the subsequent stage. 2005). 3-chlorocatechol and proceed to the mineralization (Chu. 1991). Firstly. the ring could be opened and the benzoquinone would be broken down into small organic molecules such as carboxylic acids (Houk et al. Chu.2 EC degradation of chlorophenol EC oxidation of chlorophenol is also a radical involving repulsive process. At this step. Thirdly. a diol-compound. is directly oxidized to muconic acid. The product is chlorohydroquinone which will rearrange to the ortho form.

Comninellis and Pulgarin. 1999. The more recent research work further confirmed the existence of those complex intermediates. As for the EC organic degradation pathways for different anodes.Chapter 2: Literature review such as temperature. 1995. Further research work should be conducted on the comparison of degradation routes and underlying reaction mechanisms for different types of electrodes. Feng and Li. two different pathways for the anodic oxidation of undesirable organics are described in the literature by 24 .. It has been proposed in some cases (Ding. The continuous oxidation effects by hydroxyl radicals will finalize the carbon dioxide transformation. The effects of the anode surface properties on the pathway and mechanism of organic electrolysis have not been well addressed. followed by oxidation at the anode to malonic acid and then to acetic acid.. Many possible intermediates have not been identified and a more elaborate description has to be drawn. 1991). the subsequent degradation will convert the aliphatic compound through ethers and simple alcohols. 1995) that oligomerization or polymerization reactions occur in the liquid phase yielding non-oxidizable compounds. 1998. Houk et al. With continuous electrolysis..4. 1999. Houk et al. 1998). 2. Levic et al. Houk et al. The intermediate maleic acid has been experimentally proven (Johnson et al. the formation and destruction of many intermediates are still unclear. 2003. and finally to CO2 (Johnson et al. oxygen pressure and catalyst concentration in the formation and disappearance of the different intermediates are still an open question.. However.. Once the ring cleavage takes place.. formic acid and carbon dioxide (Devlin and Harris. 2001). All these reaction details mainly suggest a general result of hydroxyl radical oxidation in a particular reaction system. 1998. and eventually mineralize to acetic acid. The oxidation proceeds further to break down the C = C bond and decarboxylation to form smaller acids. 1984. maleic acid would first be reduced to succinic acid at the cathode.. The reactions that follow are oxidation of the unsaturated bonds in aliphatic acids such as muconic acid and fractionation into maleic acid anhydride which later changes into maleic acid.2 Mechanisms of electro-catalytic organic oxidation According to the final products after EC treatment. different mechanisms and different reaction pathways may lead organic oxidation carried out by different active and non-active electrodes. Iniesta et al.

The majority of ·OH is produced by the decomposition of water on the anode surface. Bonfatti et al.0. 1990.. The hydroxyl radical formation potential from water electrolysis is around 2. In comparison. 2000. 2000): electrochemical conversion and electrochemical combustion.Chapter 2: Literature review Comninellis and co-workers (Comninellis. 2006).. and biological treatment is still required after the electrochemical oxidation. Grimm. Tanka et al.2. This means that the production of ·OH should be pH dependent at pH > 7. 2. Gu et al.80 V (Chen. 2004). 1999). accompanied with the oxidation of organic matters on the anode is the oxygen evolution reaction. electrochemical oxidation of organic matters is a free radical involving processes.(Chen et al.2.0 due to oxidation of OH-. Electrochemical conversion transforms only the toxic. 1994. According to the two equations below. electrochemical combustion or incineration yields carbon dioxide and water and no further purifications are necessary. 1999. non-biodegradable pollutants into biocompatible organics. Kim et al. however. 2 H 2 O → 2 ⋅ OH + 2 H + + 2e − 2 ⋅ OH → 2 H + + O2 + 2e − (2.7) The generation of hydroxyl radical (·OH) can be realized from the electrolytic oxidation of H2O/OH. 1997. ·OH can be effectively generated if the electrode materials present an over-potential that is low for water decomposition and high for oxygen evolution (Polcaro s et al.4.1 ·OH generation Under most situations. For most EC treatment conditions. 2002). such as tannery waste water and dye wastewater (Polcaro and Palmas 1997. Electrochemical reaction is based on the decomposition of water.2 Electron transfer It is generally believed that organic compounds in aqueous solution can be oxidized on an anode by direct electron transfer or by oxygen atom transfer (Rodgers 25 . Simninellis and Comninellis.. This method has been utilized industrial wastewater treatment as a pretreatment unit. 2..4.6) (2. organic oxidation is an acid generation process and the pH value usually is lower than 7.

1997). Iniesta et al.2 describes the reaction procedures (Simod et al. However.3 Direct oxidation There is a widely accepted concept of direct organic oxidation on the anode (Comninellis..8) to form hydroxyl radicals. 2001. reaction (2. R.11) is the formation of the higher metal oxide.. The electrically generated ozone is also reported for wastewater treatment (Stucki et al.. Chiang et al. via the higher metal oxide. Kirk et al. 1997.4.. The current input causes the electron transfer from the organic molecules to the anode surface. 1994. 2001. With the oxygen atom transfer. 2004). Figure 2. Wang et al. Chen.. organics are adsorbed on the anode surface and give up electrons to the anode. MOx+1). 2. 2005).Chapter 2: Literature review et al. reaction (2. making it unsuitable to wastewater treatment (Gomes. 2003). 2004). and conversion or oxidation of organics. Li et al. play a critical role in the EC oxidation of organic substances (Comninellis. reaction (2. Pollutants can also be oxidized by the electrochemically generated hydrogen peroxide (Brillas et al.12) is the partial (selective) oxidation of the organic compounds. 1999. 1994). 2006).. Fe2+ can be added as catalytic reagent for the initiation of the electro-Fenton reaction. 1999. The physically adsorbed "active oxygen" causes the complete combustion of organic compounds (R) and the chemisorbed "active oxygen"(MOx+1) participates in the formation of selective oxidation products. MOx is the special metal oxide anode materials.13) is for oxygen evolution by chemical decomposition of the 26 ..2. In the electron transfer process. The EC organic degradation begins from the reaction (2. the strong adsorption of organic compounds to anode Pt may lead to rapid anode fouling. In this system. 1995. 1987. ·OH) or chemisorbed "active oxygen" (oxygen in the oxide lattice. Brillas et al. it is generally considered that oxygen radicals.. Iniesta et al. The organic oxidation on electrode Pt follows this pattern. 1998. ·OH is more effective for pollutant oxidation than O in MOx+1 (Chan. 1997... Carmem et al. UV exposition and oxygen injection could be utilized to assist. 1996.. Polcaro et al. In general. 2002. Li et al. 1995.. Electro-oxidation of pollutants can occur directly on anodes by generating physically adsorbed "active oxygen" (adsorbed hydroxyl radicals... resulting in direct oxidation of double-bonds and hydrogenation. especially the hydroxyl radicals generated from water electrolysis. Simod et al. Sometimes. 1985. 2004).

Comninellis (1994) measured the concentration of ·OH accumulated on different kinds of anode materials and found that the Ti/SnO2 prefer to the accumulation of ·OH on the anode surface. it leads a complete electrochemical combustion of organic matters.8).9) (2.12) and (2. 1995). Physically adsorption coating electrode is usually a kind of non-active anode. while the concentration was zero on Pt and Ti/IrO2. Tanaka (1998) also found hydroxyl radicals formed and accumulated on the diamond anodes by using p-nitrosodimethylaniline as a selective scavenger.13) the oxidation or conversion of organic pollutants is achieved. Chemical adsorption is the property of active anodes. such as Sn-Sb. (2. MOx + H 2 O → MOx (⋅OH ) + H + + e − R + MOx (⋅OH ) n → CO2 + nH + + ne − + MOx MOx (⋅OH ) → MOx + 1 / 2O2 + H + + e − (2. while this process was also called as direct oxidation (Chu. 1999). (2.Chapter 2: Literature review higher metal oxide.13) MOx+1 → MOx + 1 / 2 H 2 R + MOx +1 → MO x + RO In order to provide more evidence on the description of physical adsorption and chemical adsorption of hydroxyl radicals.11) (2.10) is for oxygen evolution by electrochemical oxidation of hydroxyl radicals. such as RuO2 and IrO2.11). which also is called as indirect oxidation (Chu.12) (2.8) (2. outer sphere reactions (when the reactant and product do not interact strongly with the electrode surface) and water discharge (since the electrode is considered to be covered by at least one adsorbed layer of water molecules). in principle.9) is the combustion of the organic compound via hydroxyl radicals. a kind of non-selective powerful reagent (Chen.10) to accomplish pollutants oxidation.10) For the oxidant as ·OH. At non-active electrodes the possible anode reactions are. Through the step of (2. (2. MOx (⋅OH ) → MOx +1 + H + + e − (2.8).9) and (2. The non-active anodes have been defined as the electrodes that do not provide any catalytic active site for adsorption and oxidation of reactants and/or products in aqueous media. Chemical adsorption causes the oxygen atom transfer to the 27 . 1995). The difference between physical adsorption and chemical adsorption is defined by the characteristics of MOx. and through the steps of (2. which defines active anodes and non-active anodes. reaction (2. and reaction (2.

Characterization of the electrochemical properties of different types of anode materials and their different performance in organic electrolysis is of great importance to the development of more effective EC 28 . The electron and mass transfers in relation to organic electrolysis at the anode surface also should be considered for investigation of the EC reaction kinetics. Figure 2. Several years later. the different effects of various anode coating elements on EC reactions have not been well addressed. 1998).Chapter 2: Literature review internal of oxide lattice for the formation of the oxidant intermediate MOx+1. the adsorption capacities of other metal oxide electrodes remain to be determined.2. the organic pollutant incineration mechanisms mentioned above had been further modified by Simond (1997). This model has been confirmed by his subsequent tests on aliphatic acids oxidation on electrode Ti/IrO2 (Simond et al. who provided a theoretical model on organic oxidation on metal oxide anodes.. The nature of many coating metal oxides as a kind of semiconductor materials needs to be taken into account in analyzing the electrochemical behaviors of the anodes. The strong organic adsorption on electrode Pt has been confirmed. however. Reaction mechanism of anodic organic oxidation. which is selective to the objective organic matters. Although the oxidation mechanism mentioned above has been examined by the detection of surface hydroxyl radicals.

Chapter 2: Literature review techniques for toxic organic wastewater treatment as well as to the elucidation of the underlining mechanisms involved in EC organic degradation. 29 .

The TiO2 film formed on titanium surface is nonconductive. anticorrosion. 2002). The Ti plate was cut into small squares with a dimension of 2 × 2 cm2 and a 10 cm handrail for handling and electric connection.6%. Proper surface coating can prevent Ti electrodes from rapid oxidation and hence largely extend their service life from a few minutes to thousands of hours. The titanium (purity > 99. Goodfellow Cambridge) was supplied in a large plate 1. 2001.Chapter 3: Preparation of Ti-based electrodes Chapter 3 Preparation of Ti-based electrodes 3. The well known DSA® (Dimensional Stable Anode). Ti-based electrodes are commonly employed in electrochemical applications.1 Metal substrate: Titanium Titanium was selected as the base substrate for making the electrodes in the present study. 3. respectively. which was first developed 40 years ago. Habazaki et al.1.1 Metal substrate and coating materials 3..2 Dimensionally stable anodes (DSA) Titanium as an anode can be easily oxidized electrochemically to TiO2 in an electrolyte solution. which makes the Ti electrode no longer useful for any electrochemical purposes. Titanium is a metal with unique features such as high strength and durability.1.0 mm in thickness. The Ti anodes with different types of conductive metal oxide coating layers are not only more stable in chemical application but also bring in different surface properties for electrochemical reactions. high conductivity and easiness for treatment.. Small Ti plates were polished thoroughly before surface coating. including water and wastewater treatment (Pintar et al. It is the most reliable and widely used support metal of electrodes for semi-conductive metal oxide coating. Ti plate was used for preparation of different types of anodes coated with RuO2 and SnO2. has changed the practice of the chlorine-alkali 30 . In this work.

. Pure SnO2 itself is nearly nonconductive. 2003). 2002. 2000. The SnO2-Sb 31 . The RuO2 coating has a proven high stability in electrolysis of chloride ions.3 Coating materials 3. 1994).3. Polcaro et al.Chapter 3: Preparation of Ti-based electrodes industry (Trasatti. 1998. The RuO2 or IrO2 coating layer on Ti electrodes has been found to greatly decrease the overpotential of chlorine evolution in seawater and chloride salt solutions (Lin et al. For the purpose of organic oxidation in wastewater treatment. oxygen evolution and organic oxidation. However.3. RuO2 was chosen in the present study for making one type of the Ti electrodes.1. The traditional RuO2 electrodes are low in chlorine and oxygen evolution overpotentials. 3. As a typical coating material. 2002). the Ti electrode coated with RuO2 may not be the best choice due to its low catalytic activity towards free radical generation and organic oxidation (Vaidya and Mahajani. 3.1. Tanka et al. 2004). 2000). 2000). Lin and Wang. Comninellis . doping with Sb in the coating solution can dramatically increase the conductivity of the SnO2 film by the formation of a large number of electron holes (Rodgers. SnO2based coating film has been reported to have a high electrochemical catalytic capability towards ·OH free radical generation (Comninellis and Pulgarin 1993. 2000. the low oxygen evolution potential has a negative effect on the formation of ·OH free radicals during water electrolysis (Polcaro et al.. For direct organic electrolysis. The oxide coating composition strongly affects the electrochemical behavior of the electrode. Chen.2 SnO2-based coating film A few other metal oxides also may be used for making DSA electrodes. In DSA titanium is coated with a layer of RuO2 or IrO2 with or without other dopants.1.1 RuO2 coating film RuO2 is the most common DSA coating layer used in the alkaline industry. The oxidation reactions in the anodic zone in an electrolyte containing organics include two main competitive reactions. The RuO2 coating film is therefore more favorable to chlorine and oxygen evolution and less favorable to other electrochemical reactions such as organic oxidation.

1998. Pretreatment helps to construct a fundamental Ti base for better coating quality. deactivation of the SnO2-Sb coating layer is mainly caused by the peeling of the coating materials and the formation of nonconductive TiO2 interlayer (Pilla et al. 2003. 2005). 1998. 400CW.Chapter 3: Preparation of Ti-based electrodes coating layer presents a high oxygen evolution overpotential. Flying Parrot) were used to remove the entire surface layer from the Ti plates. 1997. The major drawback of the SnO2-Sb electrode has been its low stability and short service life under anodic polarization. and the surface dioxide is inert for the protection of internal metal. The polished plates were then immersed in ethanol solution and cleaned in an ultrasonic bath for 20 minutes to remove all of the metal particles from the Ti plates. 3.. Generally speaking. 1998... P-220. 800CW. The metal crystal of titanium is difficult to match the SnO2-Sb crystal in size. 32 . Alves et al. The reaction of oxygen with substrate titanium forms TiO2 on the metal surface. Thus. Kőrösi et al.. Alves et al.. 1997. Silicon carbird. Zanta et al.. Arikawa et al.): Step 1 was to remove the surface TiO2 film by physical polishing. Arikawa et al. The new SnO2-Sb coating layer had an improved stability and performed well in organic wastewater treatment.. Vicent et al. Pure titanium can be easily oxidized in air.2 Pretreatment of titanium plates Pretreatment is an important step before surface coating. The quality of pretreatment affects the coating results and the electrochemical performance of the electrode. TiO2 crystallites in a rutile type structure are quite inert towards chemical etching with common acid or alkalis.. The porous structure and the cracks of the coating film would allow the penetration of active oxygen atoms through the coating layer to reach the Ti surface. 2003. which causes an increase of the stress at the interface between the two crystals and hence weakens the attachment of the coating layer to titanium (Ulrike. resulting in passivation of the electrodes. Commercial titanium plates usually carry this dioxide surface film. In the pretreatment. Chen et al. a sandblasting roller and grand paper (Silicon carbird. pretreatment included three steps (Pilla et al. which is more suitable than RuO2 for use in electrochemical treatment of organic pollutants. 2004 etc. 1998. a modified method was developed to coat SnO2-Sb on Ti plates. In this experimental study. 1998)... Lynx Abrasives.

These procedures should be carefully handled using a forceps to avoid recontamination. The plates were then washed thoroughly with DI water. A shallow etching. A B Figure 3. The other was to modify the surface morphology of the Ti plates. There were two purposes for this surface etching step. weak acid itching at room temperature may not be able to achieve the 33 .1 Surface morphology of Ti plate: (A) under microscope. Step 3 was acid etching of the Ti plates. The Ti plates were degreased completely in 40% NaOH at 80oC for 2 hrs. The treated Ti plates became gray with a rough surface under a microscope (Fig 3. It should be noted that an improper degree of acid etching could cause various adverse effects on the quality of subsequent Ti surface coating (Krysa and Mraz. A rough and porous surface structure after acid etching could effectively enhance the attachment of a coating layer on the plate surface and to ensure the conductivity of the finished electrode. The plates were then retrieved from the alkaline solution and washed thoroughly with DI water. The well treated Ti plates were immersed in ethanol solution before surface coating.1) and lost their metallic sheen. 1994). The Ti plates after previous treatment were etched in 15% oxalic acid boiling at 98oC for 2 hrs. Shipping. The naked and uncovered points of the Ti surface would then allow rapid titanium oxidation and TiO2 formation in the rest coating procedures. In general.Chapter 3: Preparation of Ti-based electrodes Step 2 was to remove oil and grease from the Ti plates. (B) SEM photo. One was to compensate the physical polishing step for complete removal of the TiO2 layer from the surface. polishing and even contacting with hands could contaminate the plate surface. however. would lead to a loose attachment of the coating solution on the Ti plates and possibly incomplete coverage of the plate surface by the coating materials. Strong acid etching may cause a high level of passivation of the coated Ti electrodes.

the Ti plate was heated in airflow at an annealing temperature of 450 °C in a muffle oven for 1 hr.5 M RuCl3 (Aldrich) in n-butanol (99+%.5 M Comment Precursor salt Table 3.1 Coating solution for the Ti/RuO2 electrodes. The above procedure was repeated three times to produce the Ti/RuO2 electrode. Ti/IrO2 is another popular type of DSA used in industry. Montilla et al. After repeating the dipping and drying 5 times.2 Coating solution for the Ti/IrO2 electrodes. Aldrich) with 10% by volume of concentrated HCl (37%). 2004). Chemical 1 2 3 RuCl3 HCl (37%) n-butanol 10% Solvent (no water) Concentration 0.3 Preparation of Ti/RuO2 and Ti/IrO2 electrodes The Ti/RuO2 electrodes were prepared by the thermal decomposition of RuO2 on the Ti plates. After repeating the dipping and drying ten times... Boiling oxalic acid is therefore often used for acid etching of Ti plates (Arikawa et al. A fully polished Ti plate was dipped into a coating solution (Table 3. Alves et al. The IrO2 coating solution contained 0.1 M IrCl3 (Aldrich) in nbutanol (99+%. 1998. Chemical 1 2 3 IrCl3 HCl (37%) n-butanol 10% Concentration 0.1) that consisted of 0.Chapter 3: Preparation of Ti-based electrodes desired degree of surface roughness.1 M 48 hrs Solvent (no water) Comment Precursor salt A similar thermal decomposition procedure was followed to make Ti/IrO2 electrodes. 3.. Aldrich) with 10% by volume of concentrated HCl (37%). the Ti plate was heated in airflow at 450 °C 34 . The wet coating surface was dried in an oven at 60 °C for 30 min. Similar to Ti/RuO2 electrodes. A Ti plate was dipped into the solution and then dried in an oven at 60 °C for 30 min. 1998. Table 3.

followed by annealing at a high temperature. The first was the inner layer coating by electroplating. The above procedure was repeated 3 times to produce the Ti/IrO2 electrode.73 g 2 ml Solvent Comments Sn = 0. Chemical 1 2 3 4 3 SnCl4·5H2O Sb2O3 HCl Ethanol Ti(BuO)4 3% Concentration 17. 2005).1 Electroplating solution The sol-gel method was used to prepare the coating solutions by dissolving the metal chemicals into an organic solvent.3 Coating solution (100 mL) for inner layer electro-plating of the Ti/SnO2Sb-Al electrodes. For electro-deposition. SnCl4 and Sb2O3 had a molar ratio of 10:1. Ti(BuO)4 was added at a concentration of 3% by volume to increase the viscosity of the coating solution during electroplating. HCl (37%) was added in proportion to help dissolve Sb2O3.25 M Sn:Sb = 10:1 3. The final solution appeared a color of lemon yellow.5 g 0.73 g Sb2O3 (Aldrich) and 2 ml concentrated HCl (37%) (Table 3.4.5 g SnCl4⋅5H2O (Aldrich). 0. Table 3.. 3. The inner layer electroplating on the Ti plates is essential for the improvement of the durability and stability of the SnO2 coating layer on the Ti anodes (Li et al.Chapter 3: Preparation of Ti-based electrodes in a muffle oven for 1 hr.4 Electroplating for the inner layer of Ti/SnO2-Sb-Al electrodes Coating of SnO2-Sb oxides on Ti plates consisted of two major phases.4. 3. the coating solution in 100 ml of ethanol contained 17.3). The second phase was the conventional thermal decomposition after dipping and brushing the coating materials onto the Ti plates for the outer layer. Sb2O3 could not be dissolved directly into ethanol.2 Cathodic electro-plating 35 .

a higher current density would result in a larger size of metal oxide crystals to be formed on the substrate surface. A constant current density 40 mA/cm2 was charged and sustained for 20 min for electro-deposition on Sn and Sb on the cathode. The Ti plate was a cathode which faced two anodes on both sides of the Ti cathode. the coating surface would be smoother with a lower roughness.Chapter 3: Preparation of Ti-based electrodes A well treated Ti plate was immersed in 100 ml of the coating solution placed in a 150-ml beaker for electroplating (Figure 3. In general. 3. Figure 3. This was not preferred for the inner layer coating of the Ti/SnO2-Sb-Al electrodes.4. the dark electrode was placed into a muffle oven for hydration and oxidation. which expanded to a 36 . The electroplating process was carried out under a static condition without any disturbing and mixing. If the solution was stirred during electroplating. Crystals were generated from the crystal nucleus and clusters to the crystal island formation.3 Annealing at a high temperature After electroplating. However.2 Electro-plating set-up.2). Annealing at a high temperature would transform the metals to catalytic metal oxides of SnO2 and Sb2O5. pure metal atoms were not stable and had little catalytic capability in electrochemical reactions. Sn and Sb atoms had been deposited on the Ti surface. Ti/RuO2 electrodes were used as the counter anodes for their high stability and low possibility of contamination by the organic in the coating solution.

500. 5 ml hydrochloride acid was added. The concentration of Sn in the coating solution was 0. 10.04. 0. A proper heating temperature was the key for the formation of desired metal oxide crystals.e.125. 0. To dissolve Sb2O3 into butanol.5.. instead of formation of metal oxides at the preferred oxidation values.02. It was found that doping Al into the coating solution could improve the 37 . 20. 0.25 mol/L 0. 400. Parameters of electroplating 1 2 3 4 5 6 7 8 Components of plating solution Concentration of plating solution 0. 3 Coating density Comment Sn : Sb = 10 : 1 0. 600 Heating time Repeat 1. 0. 0. the coating solution in 100 ml n-butanol consisted of 30 g SnCl4⋅5H2O. Table 3.5 ml concentrated HCl (37%) (Table 3. 0. aluminum was dosed in Al2O3 at a rate of 1% of Sn by weight into the coating solution. and the solution contained Sn and Sb with a molar ratio of 15:1.075 Input current 0.Chapter 3: Preparation of Ti-based electrodes complete crystal layer on the Ti surface.1 g AlCl3 and 2.8 g Sb2O3. A complete oxidation could not be achieved under a low temperature. i. 120 Heating temperature 200. In addition. 0.16 A 20 min 500ºC 120 mins 1 15-20 mg/cm2 3.5 Thermal decomposition of the outer layer of the Ti/SnO2-Sb-Al electrodes 3.16 Electroplating time 5.5.5 M. For the thermal decomposition.25. 0.1 Coating solution A traditional thermal decomposition method was employed to coat the outer layer on Ti electrodes.08. Sn (IV) and Sb (V).5).4 Electroplating conditions tested and selected. whilst a too high temperature would result in overoxidation.

5 M Sn:Sb = 15:1 Sn-Sb-Al = 100:7:1 Con. The final solution for dipping Ti plates was a clean and viscous liquid without color. including a heat preservation period of 30 min at 100 °C to accomplish hydration before the oxidation reactions.5. The plate was heated over an electric oven (500 W) to evaporate the solvent and dry the surface.3 Annealing The Ti plate was then placed in a muffle oven for complete hydration and the formation of metal oxide crystals. This dipping and drying procedure was repeated for 5 times to ensure sufficient decomposition of the coating materials on the Ti surface. A temperature program below was designed for the annealing process.1 g 37% Sn = 0.5 Coating solution (100 mL) for the outer layer of the Ti/SnO2-Sb-Al electrodes. Table 3. as solvent Solvent (no water) 3.5.Chapter 3: Preparation of Ti-based electrodes stability and reproducibility of the Ti/SnO2-Sb-Al electrodes.8 g 0. Chemical 1 2 3 4 5 SnCl4·5H2O Sb2O3 Al2O3 HCl Butanol Amount / Concentration Comments 30 g 0. a Ti plate with the inner coating layer was dipped into the coating solution and drawn out. 25°C (ambient ) ⎯8°C /⎯ →100°C (30 min) ⎯8°C /⎯ → 550°C (20 min) ⎯ min ⎯ ⎯ min ⎯ The hydration and oxidation reactions may be written as: SnCl 4 + H 2 O → SnO + 2 HCl + Cl 2 SnCl 2 + H 2 O → SnO + 2 HCl 2 SnO + O2 → 2 SnO2 38 . 3. Heating at 550 °C allows complete metal oxidation and formation of SnO2 and Sb2O5 crystals on the surface of Ti electrodes (Figure 3.2 Dipping and drying procedures Under an ambient condition.2).

Chapter 3: Preparation of Ti-based electrodes Sb2O3 ⎯430~⎯⎯→ Sb2O4 ⎯ 900°C 430 900°C Sb2O3 ⎯⎯~⎯⎯→ Sb2O5 Table 3. In the present research.4 Procedure of the Ti/SnO2-Sb-Al electrode preparation (Figure 3.5 M 450 ºC 30mins 450 ºC 30 min 550 ºC 120 min 3 15-25 mg/cm2 Comments Sn-Sb-Al = 100:7:1 3.6 Thermal decomposition conditions tested and selected.1 Platinum electrodes Platinum is a precious metal commonly used for electrochemical studies. Sn Heating temperature I Heating time Heating temperature II Heating time Heating temperature III Heating time Repeating Coating density 0. Pt electrodes were also tested for their effectiveness and 39 . Parameters of thermal plating 1 2 3 4 5 6 7 Components of plating solution Sn : Al = 100 : 0/1/20/50 Concentration of plating solution. 3.6.6 Other electrodes used for the experimental research 3.5.4).

2 Ti/RuO2 mesh electrodes used for electrochemical denitrification Traditional DSA electrodes used in the chlorine alkali industry were selected for the experiments of electrochemical denitrification. Ti/SnO2-Sb-Al. Goodfellow Cambridge) 0. The electrolyte was 0.Chapter 3: Preparation of Ti-based electrodes performance in electrochemical degradation of organic pollutants. TiO2 and ZrO2 by thermal decomposition.1 mm in thickness were cut into squares with a size of 2 × 2 cm2. In addition to the voltammetrical measurements in the electrolyte without organic substances. which was the same as the Ti-based electrodes. The Ti/RuO2-ZrO2 mesh electrodes were found to be of a high stability during the experimental studies. The tests were performed at room temperature in a three-electrode cell with stainless steel as the counter electrode and a saturated Ag/AgCl wire as the reference electrode.95%. were characterized by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). According to the manufacturer.3-C). The Pt plates (purity > 99. the electrode surface was coated with RuO2. China. The mesh electrodes were purchased from Beijing Chemical Equipment Company. Ti/RuO2 and Pt. 3. 5000 and 10000 mg/L. The LSV tests were conducted with a computercontrolled potentiostat (Radiometer Copenhagen/Dynamic-Eis Voltalab PGZ301). Beijing.1 Linear sweep voltammetry (LSV) The electrochemical properties of all three different electrodes (2 × 2 cm2).6. and the results were compared with those of Ti-based electrodes.7 Characterization of the electrodes 3. 3.7. Such a treatment on titanium surface has been commercially used to make DSA electrodes with much improved resistance. The electrodes were made of Ti mesh plates rectangular in shape with a dimension of 5×4 cm2 (Figure 4. 40 .25 M Na2SO4 that was the same as used in the organic electrolysis experiments. the LSV of the anodes were also determined with the addition of phenol and chlorophenol at various concentrations such as 1000.

3.2 to 2. Olympus) equipped with a digital camera (DP10. the advancing angle at the lower edge and the receding angle at the upper edge of a water drop on an inclined surface were measured.3 Surface morphology 3. which could result in an obvious rise in current. and photos were taken for comparison of the surface morphology.7. 2002). 3. 41 . 3. Olympus) that was connected to a PC. The total current still increased with the potential charged until the mass transfer of ions or molecule from the solution to the electrode became rate limiting in comparison to the charge transfer at the surface of the electrode.2 Surface contact angle measurement The surface property of the electrodes for chemical adsorption was analyzed through the contact angle measurement. The wetting angle of a water drop on a flat surface. The difference in contact angles between different electrodes suggests their different hydrophobic/hydrophilic surface features and chemical adsorption properties.7. including the wetting. The electrodes were observed directly without any special treatment. PCO imaging) connected through IEEE1394 to a PC and the digital image of the drop was analyzed. A high enough potential would be reached to reduce/oxidize the substrate in the electrolyte. During a LSV test. The contact angles of a drop of water on the electrode surface.7.1 Microscopic observations The electrodes at different stages of polishing and coating treatment and after various usage were regularly examined under an optical microscope (BX60. advancing and receding contact angles. were measured following the sessile drop method (Musselman and Chander. the change in current flowing through the electrodes in the cell was recorded as the potential on the working electrode increased linearly with time. The shape of the water drop was recorded by a CCD camera (PCO1200.1 V.Chapter 3: Preparation of Ti-based electrodes Most LSV experiments were performed at a scan rate of 50 mV/s over a potential range 0. The maximum current is known as the limiting current.

EDX . JSM5600V.6 eV of photons). A high energy (typically 10 keV) electron beam was employed to scan across the surface for SEM imaging. The Ti electrodes after different durations of electrochemical usage were inspected by the SEM to examine the deterioration of the coating surface.Chapter 3: Preparation of Ti-based electrodes 3.Energy Dispersive X-ray analysis further provided the proportions of coating materials on titanium plate. 3.7.7.4 Energy Dispersive X-ray (EDX) Analysis EDX was performed with a scanning electronic microscope (JEOL.3. 3.3.3. Japan). 42 .3 X-ray Photoelectron Spectroscope (XPS) X-ray Photoelectron Spectroscopy (XPS) was performed with an X-ray photoelectron spectroscope (Shimadzu ESCA-3400) using an Al Kα X-ray source (1486.7. No special pretreatment was required for the conductive metal samples. The full scan image provided the element information of the coating materials.2 Scanning electron microscopy (SEM) Scanning electron microscopy (SEM) (Leica stereoscan 440) was used to examine the coating film on an electrode surface in a greater detail.

16 A of current input 550ºC. Ti(OBu)4 Cathode deposition Ru as counter electrode Parallar placed for e-plating 20 minutes of e-plating 0. 90。C. Sb2O3 Sn:Sb:Al=100:7:1 butanol as solvent 0.5mol/L NaF . 2hr Chemical etching Ethanol. 120min Annealing Electrode Figure 3.Chapter 3: Preparation of Ti-based electrodes Electrode Physical polishment HCL.4 Flow chart of the Ti/SnO2-Sb-Al electrode preparation. 43 . Sb2O3 Ethanol as solvent 0. 30min Ultrasonic bath SnCl4. 120min Annealing SnCl4.5mol/L Thermal decomposition Dipping for solvent attachment Drying for solvent evaporation Baking at high temperature Repeating for 3 times 450ºC.

seawater accounts for around 20% of the sewage influent to the Shatin STW. It is expected to last for 25 years from the day of commencement in 1999.1). 4.1 Saline sludge centrate Sludge liquor was collected from a local municipal sewage treatment works. As a result.1.1.1. The landfill has a total design capacity of 60 million m3 solid wastes. The raw sludge centrate collected from the dewatering unit was dark-yellow in color with a NH4+-N content of around 500 mg/L (Table 4. the decay of animal bodies and residues 44 . Due to the usage of seawater for toilet flushing in Hong Kong. the largest solid waste disposal facility in Hong Kong (Figure 4.concentration of more than 5000 mg/L.2 Landfill leachate Raw leachate samples were collected from the West New Territories (WENT) Landfill Facility.Chapter 4: Experimental materials and methods Chapter 4 Experimental materials and methods 4. Sludge from both primary and secondary sedimentation tanks are mixed and treated by anaerobic digestion of around 10 days (Figure 4. Shatin Sewage Treatment Works (STW) in Hong Kong. the sludge liquor samples had a high salinity with a Cl. in which the conventional activated sludge process is used. As it is a major facility for disposal of slaughterhouse wastes.1. while the centrate is returned to the main stream of sewage flow for treatment.1 Wastewater samples 4.1). The digested sludge is then dewatered by centrifugation to a solid content of around 30%.1 Electrochemical denitrification 4.1.2).

Chapter 4: Experimental materials and methods 45 .

The EC reactor was a 1-L beaker filled with the waste liquid.70±0. two potentiostats as the DC power suppliers. Parameters NH4+-N COD TOC ClConductivity pH 4. Table 4.05±2.2).5 46 . followed by biological wastewater treatment with extended aeration of activated sludge for COD degradation.Chapter 4: Experimental materials and methods gives the leachate high ammonia and COD contents (Table 4. The mesh Ti/RuO2-ZrO2 electrode plates described previously with a dimension of 5×4 cm2 were immersed in the waste liquid.1 Basic water quality parameters of the sludge centrate samples. a pair of titanium electrode plates for electro-denitrification. Parameters NH4 -N BOD COD TOC ClConductivity pH + Unit mg/L mg/L mg/L mg/L mg/L ms Value 518±137 160±40 224±84 62±11 5278±422 13. The leachate has a chloride concentration of around 3000 mg/L.2 Basic water quality parameters of the landfill leachate samples.3).2 Electrochemical denitrification set-up The EC experiment system for denitrification from the sewage sludge liquor included an EC reactor on a magnetic stirrer.21 Table 4. Currently.1-8. hot steam air striping is used to remove ammonia-nitrogen from the leachate.5-3714 2800-3500 29. The gap distance between the two electrode plates could be varied Unit mg/L mg/L mg/L mg/L ms Value 3000-5000 13200-21280 2213.75 7.3 8.1. and sometimes a pair of needle iron electrodes for additional electro-flocculation (Figure 4.9-31.

Chapter 4: Experimental materials and methods Power supplier Needle iron electrode Electrode mesh Stirrer Figure 4.3 (B) Electrochemical denitrification set-up 47 .3 (A) Electrochemical denitrification system illustration Figure 4.

The two power sources. could charge the pair of Ti plates and the pair of iron needles separately.3 Experimental conditions 4. 8 and 15 mm. For each test run which lasted from 1 hr to more than 2 hrs depending on the current intensity.1.3 (C) Ti/RuO2-ZrO2 electrode mesh plates for different testing conditions.5. and the voltage (V). 3.1 Batch denitrification tests for the sludge liquor The EC treatment experiments were carried out mainly in batch mode.1.5 A. 50. 1.0 and 2. when both were used. 75. 100. For each electrode setting. resulting in different current intensities of 25. 125 mA/cm2 for EC denitrification. Three gap distances between the Ti plates. including 0. were tested. electrolysis experiments were conducted at different current input. 2. samples were withdrawn from the 48 .3. 1. The DC input from any of the power suppliers was adjustable by varying both the current (I).5.Chapter 4: Experimental materials and methods Figure 4.0. the power input to the Ti plates for denitrification was much greater than that to the Fe needle electrodes for dissolving iron and electro-flocculation. Because of different treatment purposes served. 4.

particularly on the removal of total inorganic nitrogen (TIN). NaCl was added into the raw leachate influent to increase the chloride content from about 3000 to over 4000 mg/L. Leachate was pumped into the EC reactor at four different flow rates.1. iron dissolved into the solution at a controlled rate by adjusting the current input. Fe2+ was expected to function as a flocculant for particulate organics in the sludge liquor.3 Continuous flow stirred tank reactor (CFSTR) for denitrification of landfill leachate EC denitrification tests also were conducted for landfill leachate using a CFSTR with continuous inflow and outflow.1.4 Electro-denitrification and electro-flocculation reactions. and 9 hrs. Three mesh electrode plates were immersed in the liquid with one anode facing two cathodes. The electrodes had a gap of 5 mm between them.1 Electro-chlorination reactions Electro-chlorination is believed to be essential to EC denitrification of the waste liquor. In addition to the nitrogen content. electro-chlorination 49 . 4. With the DC charged.3.3. Samples were withdrawn and analyzed for the results of EC denitrification from the landfill leachate. 4.2 Denitrification plus electro-flocculation for organic removal In combination with EC denitrification. which resulted in 4 different treatment times of 3. By the end of EC treatment. To enhance the EC process. 4. the sludge solution was flocculated for 30 min followed by sedimentation of 120 min. In the presence of Cl-.Chapter 4: Experimental materials and methods reactor at various time intervals for evaluation of the treatment result. and the sludge accumulated in sediment was measured.1. 4.4. and a high current intensity was charged at 125 mA/cm2. 7. the supernatant was analyzed for organic and SS reductions. electro-flocculation was tested for additional organic removal from the sludge centrate. The pair of iron needles placed 65 mm apart were charged at a low current. NH4+ and other impurities.1. The EC reactor was a 500-mL beaker filled with leachate 300 mL in working volume. 5.

electrolysis can be written (Parsons.4. 1959. 2003.3) The combined reaction of Cl.4) The principal chlorination reactions in the presence of NH4+ and the resulting denitrification reaction (Metcalf and Eddy 2003) are 2 NH 4 + 3HOCl → N 2 ↑ +3H 2 O + 5H + + 3Cl − Thus.36 2 H 2 O − 4e → O2 ↑ +4 H + Λ Λ Λ Λ Λ Λ Λ E 0 = 1.1.2 Electro-flocculation reactions 50 .1) (4. Roger.229 2 H + + 2e → H 2 ↑ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ E 0 = 0 Cl 2 + H 2 O → HOCl + H + + Cl − Bess. 1959): 2Cl − − 2e → Cl 2 ↑ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ E 0 = 1. 2003) as (4. Casson and − Cl + H + + H 2 O → HOCl + H 2 ↑ (4.Chapter 4: Experimental materials and methods for nitrogen removal is a complex process.2) (4. The following electrolysis reactions are important (Leonard.5) (4.6) 4. the overall reaction of EC denitrification can be written as Power 2 NH 4 ⎯⎯ → N 2 ↑ +3H 2 ↑ +2 H + ⎯ + + (4.

Chapter 4: Experimental materials and methods The pair of iron needles placed 65 mm apart were charged at a low current. With the DC charged, iron dissolved into the solution at a controlled rate by adjusting the current input. Fe2+ was expected to function as a flocculant for particulate organics in the sludge liquor, according to the following reactions.

Fe + 2 H + → Fe 2+ + H 2 ↑ ,
4 Fe 2+ + 8OH − + O2 + 2 H 2O → 4 Fe(OH ) 3 ↓

(4.7) (4.8)

4.1.5 Analytical methods 4.1.5.1 Chlorine compounds and chloride Chloramines NH2Cl, NHCl2 and NCl3 were determined for their concentrations by the titration method in accordance with the Standard Methods (1998) Section 4500-Cl F, DPD ferrous titrimetric method. Chlorine concentration was determined by the portable datalogging spectrophotometer (DR/2010, HACH) at 530 nm following Section 4500-Cl G: DPD Colorimetric Method in the Standard Methods (1998). Chloride concentration was measured with the same equipment at 550 nm following the methods defined by the manufacturer. 4.1.5.2 Nitrogen (NH3-N, NO2--N, NO3--N) concentrations Total inorganic nitrogen (TIN) in different forms was analyzed. The analytical procedures of NH3-N, NO2--N, and NO3--N followed Section 4500-NH3 D: AmmoniaSelective Electrode Method, Section 4500-NO2- B: Colorimetric Method, and Section 4500-NO3- B: Ultraviolet Spectrophotometric Screening Method in the Standard Methods (1998), respectively. Ammonium nitrogen was analyzed by the electricalchemical method using an ammonia-selective electrode (95-12, Orion) with an electrometer (920A, Orion). An UV-visible spectrometer (Lambda 12, Perkin Elmer, 1cm path length) was used for NO3- and NO2- measurements following the Standard Methods (1998). 4.1.5.3 Trihalomathane (THM) formation potential measurement

51

Chapter 4: Experimental materials and methods

Figure 4.5 Portable datalogging spectrophotometer (DR/2010, HACH)

Figure 4.6 UV/Visible spectrometer (Lambda 12, Perkin Elmer)

52

Chapter 4: Experimental materials and methods Formation of trihalomathanes (THM) after the EC treatment in a sample was assessed following the extraction with pentane. A Hewlett Packard (HP) 6890 series gas chromatograph (GC) equipped with an Agilent J&W DB-5 capillary column (30.0 m × 320 μm × 1.0 mm nominal), an auto-sampler, and a linearized Electron Capture Detector (ECD) was employed for the THM analysis (Figure 4.10). The flow rate was adjusted to 1.1 mL/min with ultra-high pure (UHP) nitrogen as the carrier gas. The initial oven temperature was set at 35 oC and held for 5 min. The temperature was then gradually increased to 70 oC at a rate of 10 oC/min and further increased to 200
o

C at a rate of 20 oC/min. The total running time for the temperature program was 15 C (Li and Chu, 2003).

min. The equipment was ready for the next run when the column cooled down to 35
o

4.1.5.4 Other water quality parameters The input of DC current and voltage could be read directly from the power suppliers. All analyses of conventional water quality parameters, such as the biochemical oxygen demand (BOD), chemical oxygen demand (COD) and the suspended solids (SS), were performed following the Standard Methods (1998). COD measurement followed the Standard Methods (1998), Closed Reflux Method in Section 5310-B, high temperature combustion method. SS was determined according to Section 2540-D, total suspended solids dried at 103-105◦C. BOD was measured by the OxiTop®BOD measuring devices. Total organic carbon (TOC) was measured by a TOC analyzer (TOC-5000A, Shimadzu) using the combustion-infrared method, which followed Section 5310 B: High Temperature Combustion Method in the Standard Methods (1998). The solution pH was measured by a pH meter (420A, Orion), and the turbidity was monitored by a Turbidimeter (2100N, HACH) according to Section 2130 B, Nephelometric Method in the Standard Methods (1998). In addition, A jartest device (PB700, Phipps & Bird) with a flat paddle mixer (3.8×1.25 cm2) was employed for the flocculation test. 4.1.5.5 Current efficiency of EC denitrification

53

Shimadzu).Chapter 4: Experimental materials and methods Figure 4. Turbidimeter (2100N. HACH) 54 . Figure 4.7 TOC analyzer (TOC-5000A.8.

and the total organic carbon (TOC) concentration was about 280. However. a longer ultrasonication time of 60 min was needed for complete chlorophenol dissolution.3 Solutions of the intermediate organics of EC phenol degradation Solutions of a number of pure aromatic components and aliphatic acids were prepared for the EC oxidation experiments. 1991) by 3 F ΔN 14 I t η= (4.1.Chapter 4: Experimental materials and methods The current efficiency of electrolysis for denitrification can be estimated (Prentice. The stock phenol solution was prepared by dissolving 0.5 g of the phenol (Aldrich) into 250 ml DI water.2.9) where: ∆N is the amount of TIN removed from 1 L of the sludge liquor within a treatment time of t at the current I. a stock phenol solution at a higher concentration of 2000 mg/L was also prepared occasionally. 4. which had a TOC concentration of about 383 mg/L.2.1 Wastewater samples 4. and F is the Faraday constant (96.2 Chlorophenol solution Chlorophenol wastewater was prepared in the same way as described above for the phenol wastewater. The aromatic 55 . The stock phenol solution had a concentration of 500 mg/L. The stock chlorophenol solution had a concentration of 500 mg/L.1.2 Electrochemical degradation of aromatic organic pollutants 4.2. 4.16 mg/L.2.1 Phenol solution Chemical reagent was used to make artificial wastewater for the EC treatment experiments. Additionally. These organic chemicals were expected to be the intermediate products of phenol and chlorophenol electrolysis.1. The solution was placed in an ultrasonic bath for 30 min for complete phenol dissolution.500 coulombs). 4.

All above chemical solutions. Each had a cover cap with two open slits for assembling the electrodes. stainless steel plates of the same size (2 × 2 cm2) were used as the counter cathodes. oxoglutaric acid (Aldrich). maleic acid (Aldrich).2. benzoquinone (Aldrich).2. Together with the working anodes. three different types of the anodes. if not used immediately. fumaric acid (Aldrich).2. molonic acid (BDH).2 Experimental set-up and operational conditions 4. As described previously. The stock solutions of these pure chemicals had a concentration of 200 mg/L. oxalic acid (BDH). were stored in refrigerator at 4 °C before the EC degradation experiments. 4.Chapter 4: Experimental materials and methods chemical solutions included hydroquinone (Aldrich). catechol (Aldrich). Ti/SnO2-Sb-Al. were investigated through the experimental tests. Ti/RuO2 and Pt. The two electrodes in each EC cell were 56 . axetic acid (Aldrich) and formic acid (Aldrich).1 Experimental set-up Phenol and chlorophenol degradation experiments were conducted in batch electrolysis cells using 100-ml glass beakers. succinic acid (Aldrich). The organic acids included muconic acid (IL).

A consistent DC current. A DC potentiostat was used as the power supply with a voltage output up to 35 V.10 Gas chromatograph – mass spectrum (GC-MS) for THM analysis (HP 6890 ) 4. 60 ml of a chemical solution at a predetermined concentration was placed in the EC cell.g.3 Analytical methods 57 .25 M Na2SO4 as the supporting electrolyte. Through the electrolysis process. Figure 4. and the temperature stayed at around 25oC without special control. 4. The solution contained 0. between the electrodes. 0.Chapter 4: Experimental materials and methods placed facing each other 8 mm apart. the cell voltage and solution pH were recorded. For example. Samples were withdrawn from the solutions at various intervals for chemical analysis of the phenol or chlorophenol. 20 mA/cm2.. e. The EC cells were placed on a magnetic stirrer for continuous mixing.2 Operation and sampling For a test.08 A. phenol had an initial concentration of 100 mg/L.. e. the total organic carbon (TOC).2. was charged to the electrode pair.2. resulting in a certain current intensity.g. and intermediate products in the electrolyzed liquids.

chlorophenol and the intermediate organics of the EC degradation process. For analysis of aliphatic acids the column Atlantis dC18 5 μm (3.Chapter 4: Experimental materials and methods 4. Waters) was chosen.75 adjusted by H3PO4 was used as the mobile phase at a flow rate of 0. hydroquinone and catechol and aliphatic acids of oxoglutaria acid. maleic acid.1 High performance liquid chromatography (HPLC) for organic analysis High performance liquid chromatography (HPLC) was used to determine the concentrations of phenol. a capillary column in Symmetry C18 5 μm (3. Before each analysis.5 ml/min under room temperature.5 ml/min.9 × 150 mm.9 × 150 mm. malonic acid. fumaric acid. the sample was filtered through a 0. succinic acid. For analysis of phenol and other aromatic compounds.11 High performance liquid chromatography (HPLC) (Waters 2695 2996) rate of 0. Methanol/water = 1/1 (V/V) was used as the mobile phase at a flow Figure 4.25 mM) solution with a pH = 2. Waters) was used. The intermediates included aromatic compounds of benzoquinone.3. The HPLC (Waters 2695) was equipped with a UV detector (Waters 2996) used at working wavelengths from 190 to 400 nm. oxalic acid and acetic acid. NaH2PO4 (0.45-μm 58 .

661 acetic acid 5.166 maleic acid 6.00 2.409 0.002 0.000 1.00 10.00 9.010 AU 0.13.008 succinic acid 9.00 11.Chapter 4: Experimental materials and methods membrane filter (Millex-LCR) in the ambient environment.00 Minutes 8.00 14. Two examples of HPLC analysis of the aromatic compounds and aliphatic acids are given in Figures 4.12and 4.006 0.00 15.721 0.00 7.00 5.467 0.004 0.016 malonic acid 4.014 oxalic acid 2.13 HPLC analysis of aliphatic acids 59 .00 13.00 4.00 3.583 fumaric acid 0.00 12.00 6.012 0. Figure 4.12 HPLC analysis of the four 4 types of aromatic compounds formic acid 3. 00 Figure 4.956 oxoglutaric acid 4. The sample injection volume was 10 μl.158 8.

14 Characterization of different anodes treatment time of t. Similarly.2 Current efficiency and TOC removal efficiency Current efficiencies were calculated for phenol and chlorophenol destruction and TOC removal by the EC process. 60 . The efficiency was used to evaluate the performance and energy effectiveness of different electrodes for electrolysis of toxic organics.10) where C1. I is the current input and Q hence is the total charge input within time t.TOC2 is the TOC change during a time period of t at a current of I. the current efficiency for TOC removal can be calculated by TOC1 − TOC 2 TOC1 − TOC 2 = × 100 I ×t Q η= (4.Chapter 4: Experimental materials and methods 4.3.C2 refers to the concentration change of phenol or chlorophenol after a TOC Liquor GC-MS HPLC Current C-V SEM Electrode XPS/EXD Contact angle Figure 4.11) where TOC1. The current efficiency for chemical destruction can be obtained from C1 − C 2 C1 − C 2 = × 100 I ×t Q η= (4.

can be estimated. The kinetic equation may be transformed to ⎛C ln⎜ 0 ⎜C ⎝ t ⎞ ⎟ = kt ⎟ ⎠ (4.3 Rate constants for EC oxidation of organic chemicals Organic decreased in concentration during the electrolysis process. 61 . Samples were withdrawn from the electrolyzed solution at various time intervals to obtain a series of the chemical concentrations. phenol. and their degradation intermediates.Chapter 4: Experimental materials and methods 4.13) The chemical usually had an initial concentration of 100 mg/L. The destruction of a pure organic by the EC treatment with different anodes was found to generally follow a first order kinetics.3. and k is the rate constant of the first order oxidation process. t. chlorophenol. From a linear regression of ln( C0 Ct ) vs. the rate constant for EC destruction of a specific organic.12) where C is the chemical concentration after an electrolysis duration of t. Hence. the reduction in the chemical concentration can be described by dC = − kC dt (4.

Removing the ammonia input from either the sludge liquor or leachate by a separate treatment will improve the performance and increase the capacity of the mainstream wastewater treatment process for nutrient removal (Jetten et al. laboratory experiments were carried out to investigate the effectiveness of EC treatment for denitrification and organic removals. In the present study. the sludge liquor from the dewatering unit is returned to the inlet of the treatment system. in which electro-chlorination and the subsequent ammonia oxidization are expected. 62 . The high salinity content in the sludge liquor and landfill leachate of Hong Kong will improve the performance and efficiency of the EC process for nitrogen removal. accounting for about 1% of the influent. The ammonia loading from the sludge liquor contributes to 10-20% of the influent nitrogen loading (Janus et al. Landfill leachate (in Hong Kong) usually has a NH4+-N concentration of more than 3000 mg/L together with about the same amount of refractory organic pollutants. Although the flow rate of the sludge liquor is low. it contains a high nitrogen content of more than 500 mg/L NH4+-N. An EC system is simple and robust in structure and operation..Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification Chapter 5 Nitrogen removal from wastewater by electrochemical denitrification 5. 1997). 1997). Leachate from landfills is a complex and high strength wastewater.. which is rather difficult and expensive to treat by conventional means. During EC treatment the sample water will be forced through a reactor of electrolysis. Inflow of raw leachate into a municipal wastewater treatment plant would considerably increase the loading of the treatment facility. Pre-treatment of landfill leachate is normally required before its flow into a municipal wastewater works.1 General characteristics of the waste liquor samples and EC treatment In wastewater treatment plants. Electrochemical (EC) treatment can be considered for effective treatment of the sludge liquor and landfill leachate.

Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification
5.2 Electrochemical denitrification of sludge centrate liquor

5.2.1 Electrochemical denitrification The EC treatment was demonstrated to be highly effective for denitrification of the saline sludge liquor. Nitrogen measured as total inorganic nitrogen (TIN) was removed continuously from the sludge centrate samples by electrolysis. With a sufficient duration of the EC treatment, complete denitrification could be achieved (Figure. 5.1). An increase in the current intensity resulted in a faster rate of TIN reduction. For example, at a current intensity of 50 mA/cm2 for sludge liquor with an initial NH4+-N of more than 350 mg/L, denitrification could be completed within 150 min. This treatment time was shortened to around 60 min at an elevated current intensity of 125 mA/cm2. Thus, higher current input favoured the kinetics of EC denitrification. As anticipated, electrolysis of the ammonia solution formed intermediate products of chloramines prior to the completion of denitrification. However, there did not appear to be significant accumulation of chloramines, including NH2Cl, NHCl2 and NCl3, during the EC treatment (Figure 5.2). NH2Cl-N could reach a concentration of around 20 mg/L, which disappeared from the solution by the end of EC denitrification. Formation of NO3- and NO2- were hardly detectable during the EC process. Thus, NH4+ was the predominant TIN species throughout the EC treatment.
400 350 50 mA/cm2 75 mA/cm2 100 mA/cm2 125 mA/cm2

TIN concentration (mg/L).

300 250 200 150 100 50 0 0 40 80 Time (min)

120

160

Fig. 5.1 TIN removal as a function of the contact time and current intensity with a gap distance of 8 mm between the electrodes.

63

Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification Chloride in the sludge liquor was electrolysed to chlorine, which was believed to be essential to EC denitrification. While both free chlorine and combined chlorine were present in the solution, free chlorine accounted for the major fraction of total chlorine in the reactor (Figure 5.2). The combined chlorine of NH2Cl and NHCl2 was found in a low and rather stable concentration level. Upon complete NH4+-N removal, the combined chlorine was gradually eliminated, while free chlorine was found to increase with time by continuous electrolysis. The importance of chloride to EC denitrification was also demonstrated with a model wastewater which was a (NH4)2SO4 solution containing 500 NH4+-N mg/L. Without salt (Cl-) addition, electrolysis of the model solution did not result in any effective nitrogen removal. While Cl- was dosed into the solution at a level of 4000
400 350 300 250
N (mg/L)
NH4-N NHCl2 NO3pH NH2Cl NCl3 NO2-

8 7.5 7 6.5 6 5.5 5 0 15 30 45 T ime (min) 60 75
pH

200 150 100 50 0

400 350 300
Cl (mg/L)

Free-Cl2 NH2Cl NHCl2 NCl3 T otal Cl2

250 200 150 100 50 0 0 15 30 45 T ime (min) 60 75

Figure 5.2 (a) Nitrogen removal as a function of treatment time and (b) chlorine compounds during the EC process at a current intensity of 125 mA/cm2 with an electrode gap of 3 mm.

64

Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification mg/L, the same denitrification result that was obtained for the actual sludge centrate was reproduced. Thus, electro-chlorination can be considered as the major mechanism responsible for EC denitrification of the saline sludge liquor (Stoner and Cahen, 1982; Casson and Bess, 2003). 5.2.2 Electro-chlorination for denitrification of the sludge centrate Electro-chlorination is believed to be essential to EC denitrification of the saline sludge liquor. In simplified terms, the overall reaction of EC denitrification is:
Power 2 NH 4 ⎯⎯ → N 2 ↑ +3H 2 ↑ +2 H + ⎯

+

(5.1)

Electrolysis of NH4+ would lead to an accumulation of H+ ions and thus a continuous decrease of the solution pH, which was observed during the EC process (Figure 5.2a). After the completion of nitrogen removal, with continuous chlorine production, the following electrolysis reaction would become dominant: 2 Cl − + 2 H 2 O → Cl 2 ↑ + 2 OH

+ H2 ↑

(5.2)

Thus, a turn point of the pH value was expected, after which the pH would increase with time. This change in solution pH was also demonstrated by the test results (Figure 5.2a). One of the major concerns in use of EC treatment methods is the formation of chlorination by-products (CBPs). As an indicator, trihalomethanes (THMs) were used for assessing the potential CBPs problem in EC denitrification of the sludge liquor. The total THMs in the treated sludge liquor was found to range only from 200 to 300

μg/L. The low THMs formation during the electro-chlorination was likely due to the
short contact time of 1 hr or so used. Since the sludge liquor will be returned to the main stream of sewage flow, the low level of THMs in the denitrified liquor will be degraded by the downstream biological treatment. Hence, it is predictable that the accumulation of THMs and other CBPs during EC denitrification will be insignificant, which is not supposed to cause any deterioration in the effluent quality of wastewater treatment. 5.2.3 Power consumption and current efficiency

65

In the EC treatment. in addition to NH4+ electrolysis to nitrogen gas. for the same gap distance between the electrodes. As shown in Figure 5. current input was also consumed for electrolysis reactions of H2O. as well as for heat generation. when the gap was reduced to only 3 mm. the gap distance between the electrodes and treatment time regulate the effectiveness and performance of EC denitrification.and other compounds. an increase in the current input would accelerate the nitrogen removal process by electrolysis. Instead. a too high current input would decrease the current efficiency (Figure 5. More electricity was likely wasted for heat generation as the gap distance increased. Among the 3 distances examined. 66 . The gap distance of the electrodes had more profound effect on the current efficiency for EC denitrification. the current efficiency dropped more dramatically to around 40%. as evidenced by the temperature rise observed. However.3. Cl.3 Current efficiency as a function of current input for different electrode gaps in EC denitrification. a gap of 8 mm gave the best current efficiency as high as 65% or more. although a higher current favoured the nitrogen removal kinetics. a higher current intensity might not improve the efficiency of the current used for denitrification. Increasing the gap to 15 mm resulted in a large reduction of the current efficiency to around 55%. Bubbles trapped between the narrow gap could have a negative effect on the EC nitrogen removal 100 Current efficiency (%) 80 60 40 20 0 40 60 80 100 120 140 3mm 8mm 15mm Current intensity (mA/cm2) Figure 5. It is apparent that the fraction of current used for denitrification did not increase with the current intensity.3). However.Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification For a given EC system. parameters such as the current intensity.

The EC process did not appear to be highly effective for the removal of organic materials from the sludge liquor. 1989).4 TIN removed as a function of power consumption for different electrode gaps at the same current intensity of 75 mA/cm2. 5. 350 300 250 200 150 100 50 0 0 5 10 D=3 mm D=8 mm D=15 mm 15 20 Power consumption (kWh/L) Figure 5. For a batch operation of NH4+ electrolysis. the amount of nitrogen removal from the sludge liquor depended directly on the power input into the EC treatment system.5). Thus. EC oxidisation was not expected to be highly efficient for large organic molecules and 67 .4 Electro-flocculation for organic removal 400 TIN concentration (mg/L). It has the potential to be developed as a robust and cost-effectiveness technology for separate treatment of saline sludge liquor. although a certain extent of reduction in the organic content was observed (Figure 5. Possible short circuit between the electrodes would considerably lower the current efficiency for NH4+ electrolysis.4).2. This value is rather comparable with other denitrification processes (William.Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification process. In addition. However. EC denitrification is simple in structure and easy in operation. an appropriate gap distance between the electrodes should be adopted in the EC system to ensure a high current efficiency for denitrification. Some organic molecules could likely be oxidised by EC reactions or the oxidizing products of the EC process. It could be estimated that the power consumption rate for nitrogen removal from the sludge liquor was about 23 kWh/kg N under the optimum operation conditions. The power efficiency for denitrification was also affected by the current density and the gap distance of electrodes (Figure 5.

5). With the electro-flocculation examined in this study. Fe2+ and its hydrolysis products are excellent flocculants. Fe2+ compounds produced by the EC process functioned as a flocculant to promote flocculation of organic materials. They are capable to destabilise the colloidal solution of large organic molecules.12 TOC mg/L 44. chemical flocculation would require more facilities and operation attention. electrodenitrification together with electro-flocculation appears to be the best treatment approach for nitrogen removal and organic reduction of sludge liquor. Table 5.1). Electroflocculation did not have any adversary effect on EC denitrification. In actually application.22 441 Turbidity NTU 17. Figure 5.2 COD mg /L 100 44 SS mg/L 6. particulate organics and other impurities.Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification particulate organics. Large flocs formed by electro-flocculation were effectively removed in the subsequent sedimentation. Therefore.4 17. Electrolysis with the iron electrodes would dissolve Fe2+ into the sludge solution.1 Effect of electro-flocculation on the sludge liquor treatment.5).18 0. Electroflocculation No Yes NH4+-N mg/L 0. However. With the EC system. electro-flocculation without EC denitrification only removed a part of organic and SS and had no function of nitrogen removal (Figure 5. Chemical flocculation using FeCl3 in combination with EC denitrification had a similar treatment result as the coupled process of EC denitrification and electroflocculation.5).57 68 . over-dosage of Fe2+ by the EC reaction did not result in more organic and SS reductions from the sludge liquor. In the present tests. Instead.1. however.89 Sludge mg/L 0. The electrolysed effluent after flocculation and sedimentation was transparent and colourless with a rather low turbidity (Table 5. the rate of Fe2+ dissolving into the sludge liquor from the iron anode could be well controlled by regulating the current input. In comparison.5).8 0. chemical flocculation lowered the solution pH to around 3 and produced more sludge sediment (Figure 5. It should be noted. while sludge production was largely increased. the combined action of electro-denitrification with electro-flocculation had better treatment results in organic and SS removals (Figure 5. organic removal of the sludge liquor was improved considerably (Table 5.74 2.

5 Comparison in removals of TOC.3 Electrochemical denitrification of landfill leachate 69 . (B) ECdenitrification only. COD and SS. 5. sludge production and TIN degradation for conditions of (A) EC-denitrification + EC-flocculation. (C) EC-flocculation only and (D) EC-denitrification + chemical flocculation.Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification 700 TIN concentration (mg/L) 600 500 400 300 200 100 0 20 A C B D 60 0 50 40 60 T ime (min) 80 100 TOC (mg/L) 40 30 20 10 0 100 0 80 A B C D 20 40 60 80 A B C D 100 T ime (min) SS (mg/L) 60 40 20 0 3000 0 2500 20 40 T ime (min) 60 80 100 Sludge (mg/L) 2000 1500 1000 500 0 0 20 40 T ime (min) 60 80 100 A B C D Figure 5.

5. Figure 5.6).was consumed during the electrolysis process for nitrogen removal from the leachate. Nitrogen measured as TIN was removed continuously from an initial concentration of more than 1600 mg/L by 3 hrs of electrolysis.6 TIN removal as a function of the electrolysis time for different chloride concentrations in EC denitrification of the landfill leachate.1 Batch EC leachate treatment tests The electrochemical treatment was also demonstrated to be highly effective for denitrification and organic removal of the landfill leachate. 70 Cl. with a sufficient duration of the EC treatment. About 30% of Cl. the time required for complete EC denitrification was shortened from 3 hrs or longer to 2 hrs. complete denitrification could be achieved (Figure.(NaCl) 2500 2000 1500 1500 1000 1000 500 500 0 0 1 2 3 4 0 Time (h) Figure 5.1-A Untreated leachate (left) and EC treated leachate (right). Adding NaCl into the solution could increase the rate of denitrification. 3000 3000 N 2500 2000 ClN (NaCl) Cl. As the initial Cl.Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification 5. In batch tests.(mg/L) N(mg/L) .3.content was increased from around 2200 to about 2700 mg/L.

the influent had a nitrogen concentration of 3500 mg/L. 71 Cl. while both wastewater samples had a similar level of chloride ions.3. A longer duration of treatment in hydraulic retention time (HRT) would achieve a higher level of nitrogen removal. salt addition was necessary for EC nitrogen removal from the landfill leachate.7 TIN removal and chloride concentration as a function of the contact time (HRT) in the CFSTR for EC denitrification.(mg/L) N (mg/L) . the electro-chlorination and ammonia oxidation reactions were about to stop. 5.7. This was shown to be rather unfavourable to the reaction kinetics of EC denitrification. the nitrogen concentration decreased to 1800 mg/L. To achieve 100% EC nitrogen removal. As a large amount of chloride ions were consumed by electrolysis. a much longer time was needed for the leachate. When chloride concentration in solution was reduced to 300 mg/L or below. the chloride concentration could drop to a rather low level. The chloride concentration was about 3500 mg/L (fresh leachate sample while different from batch tests). The ammonia concentration in the leachate was 6-10 times higher than that in the sludge centrate. Five hours of 4000 4000 3000 3000 2000 2000 Influent NH4+-N Effluent NH4+-N 1000 Influent ClEffluent Cl- 1000 0 1 2 3 4 5 6 0 Retention time (h) Figure 5.Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification The landfill leachate was different from the sludge liquor. With the pretreatment retention time of 2 hrs. As illustrated in figure 5. Therefore.2 EC denitrification during the continuous flow process CFSTR was also tested for EC nitrogen removal from landfill leachate.

For the batch reactor.8). Both batch and continuous CFSTR operations could be used for EC denitrification of landfill leachate. A treatment of 4 hrs had only 80% nitrogen removal.9).8 Current efficiency and TIN degradation as the functions of reaction time in batch operation. 72 . 5. while the current efficiency was around 50% (Figure 5. the TIN removal percentage increased consistently with the batch treatment time or HRT of electrolysis in the CFSTR (Figure 5. the TIN removal could reach 95%. For the CFSTR. In addition to ammonia electrolysis. it was difficult to decide the optimum treatment duration. In comparison.11). As anticipated. the EC process was highly effective for discoloring of the leachate. With this HRT. the current efficiency for nitrogen removal showed a trend of decrease with the time. This was likely brought about by electro-chlorination and related organic oxidation reactions. EC reaction would cause destruction of large and colored organic molecules.Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification HRT by electrolysis in the CFSTR achieved complete denitrification.9). 100 90 80 100 90 80 70 60 50 40 30 20 Current efficenency (%) 70 60 50 40 30 20 10 0 1 2 3 4 5 6 TIN degradation (%) Current efficency TIN degradation 10 0 Time (hr) Figure 5. while a chloride concentration at about 2500 mg/L could be maintained in the EC reactor. the optimal HRT could be defined as 4 hrs. while the current efficiency was already lower than 40% (Figure 5. the CFSTR mode appeared to perform better than the batch treatment. however. The original dark brown liquor was changed gradually into a light yellow water by electrolysis (Figure 5. The decoloring function should be favorable to the subsequent biological treatment of landfill leachate. However.8.

The power consumption for nitrogen removal increased nearly linearly with an ever decreasing nitrogen concentration during the EC process (Figure 5. such as for separate treatment of saline sludge liquor and landfill leachate. 5. The EC process was highly effective in decoloring the landfill leachate. the EC process has the potential to be developed as a cost-effective alternative for nitrogen removal and organic degradation in high strength wastewater treatment. which would lead to easy downstream treatment.Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification 5.3 Power consumption and current efficiency The amount of nitrogen removal from the landfill leachate depended on the power input into the EC treatment system. which increased the organic removal from less than 30% to more than 70%. The power consumption rate for nitrogen removal from the landfill leachate was apparently higher than that from the sludge centrate liquor (about 23 kWh/kg N). 73 . The current density and the gap distance of the electrodes also affected the power efficiency for denitrification. The EC system also performed well in denitrification of landfill leachate. for both batch operation and CFSTR. With a HRT of 5 hrs in CFSTR. complete TIN removal of more 3000 mg/L of ammonia nitrogen could be achieved. Electro-chlorination was considered to be the major mechanism for EC denitrification. The power consumption rate was rather high when the bulk solution had a high nitrogen concentration.4 Summary The laboratory experimental results indicate that the EC process is highly effective for denitrification of the saline sludge liquor with a NH4+-N of around 500 mg/L.3. The power consumption rate for nitrogen removal of the sludge liquor was around 23 kWh/kg N. Complete nitrogen removal could be achieved within a contact time of 1 hr or so. there was not significant accumulation of chloramines during the EC reactions. Additional electro-flocculation with a pair of iron needle electrodes could enhance the flocculation and subsequent sedimentation of colloidal organics in the sludge liquor. The best current efficiency for nitrogen removal was obtained with a gap distance between the electrodes at 8 mm. Nonetheless. the power consumption rates were similar during EC denitrification. However.10). followed by the gap of 15 mm and then 3 mm. In general.

4000 3000 Continnous Semi-batch N (mg/L) 2000 1000 0 0 20 40 60 80 Power consumption (kWh/kg-N) Figure 5.Chapter 5: Nitrogen removal from wastewater by electrochemical denitrification 100 90 80 100 90 80 70 60 50 40 30 20 Current efficency (%) 70 60 50 40 30 20 10 0 1 2 3 4 5 6 TIN degradation (%) Current efficiency TIN degradation 10 0 Time (hr) Figure 5.11 TIN as a function of the power consumption.9 Current efficiency and TIN degradation as the functions of reaction time in continuous. 74 .

The four electrodes had an even greater difference in organic mineralization measured by the TOC reduction (Figures 6. At the same current input rate to the Ti/RuO2 anode. respectively.1. showed rather different effectiveness for EC phenol degradation (Figures 6. Phenol was destructed nearly completely from the initial 100 mg/L after 3 hrs by the Ti/SnO2-Sb-Al anode and 5 hrs by the Pt anode (Figures 6.1 and 6.1 and 6. 75 . However.3).3). only 42% phenol removal was achieved after 6 hrs of electrolysis. Ti/SnO2-Sb-Al. Ti/IrO2 and Pt. the Pt and Ti/RuO2 anodes reached just 36% and 12% TOC removals. Complete organic removal was achieved after 5 hrs on the Ti/SnO2-Sb-Al anode. followed by the noble Pt anode and then the conventional DSA of Ti/RuO2 and Ti/IrO2 anodes. in comparison to less than 50% by the Ti/IrO2 electrode (Figure 6. almost 95 % of TOC was removed after 12 hrs with the Ti/SnO2-Sb-Al anode.1 Phenol degradation and TOC removal The four different anodes.1 Performance of selected anodes in EC phenol degradation 6. under the same electrolysis conditions at a current density of 20 mA/cm2. Ti/RuO2. For the phenol solution with an initial concentration of 500 mg/L. From an initial concentration of 500 mg/L. phenol was degraded almost completely after 10 hrs by the Ti/SnO2-Sb-Al electrode.1).4).2 and 6. The best treatment result was obtained with the Ti/SnO2-Sb-Al anode. the TOC removals were only 28-30% for the Ti/IrO2 and Ti/RuO2 electrodes under the same electrolysis conditions at a current density of 20 mA/cm2.Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products Chapter 6 Electrochemical degradation kinetics of phenol and its intermediate products 6. However.

1 Phenol destruction on the three types of anodes 350 300 250 14 12 10 Sn Ir Ru TOC (mg/L) 200 150 100 6 4 50 2 0 0 2 4 6 8 10 12 Reaction time (hr) Figure 6.Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products 500 Ti/SnO2-Sb-Al Ti/IrO2 400 Ti/RuO Figure 6.2 TOC and solution pH during EC phenol degradation 76 pH 8 Voltage (V) 8 .1 500mg/L phenol incineration on 3 kinds of2 anode 12 10 Phenol concentration (mg/L) 300 200 6 100 4 0 0 2 4 6 8 10 12 2 Reaction time (hr) Figure 6.

the pH decreased continuously to around 4..5 to around 4. Compared to these anodes. 77 . This reached the lowest pH point which followed by an increase.2). the pH increased gradually to 5. Comninellis. 6. 1994. the conductivity of the coating film was apparently incomparable to pure metals such as Ti and Pt.4) indicated the slow degradation and hence accumulation of intermediate organic acids in the systems.1). In the Ti/SnO2-Sb-Al system.Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products The Ti/SnO2-Sb-Al cell had a voltage input of about 4. Grimm et al. The solution pH changed probably with the intermediate production during the electrolysis process (Figure 6. On the contrary. while about 55 % of phenol disappeared (Figures 6. 2003. Feng and Li. Houk et al.2). Continuous pH decrease in the solutions electrolyzed by the electrodes Ti/IrO2 and Ti/RuO2 (figure 6. 1991. 6. the pH dropped initially from 5. The drop in pH was apparently caused by the formation of acidic substances from the phenol destruction. 6. while a great TOC content remained in the solution. the Ti/SnO2-Sb-Al anode required a much less charge consumption to achieve complete phenol and TOC removals. Aliphatic acids were believed to be one of the main intermediates produced by phenol electrolysis (Comninellis and Pulgarin. However.0 while the phenol was being oxidized. Li et al.2. 2005). There was a pronounced drop of pH in the first 2 hours of electrolysis.2 V. 1998. Comninellis 1994. which was somewhat higher than those of the Pt and Ti/RuO2 cells (Figure 6. the Ti/SnO2-Sb-Al anode is considered to have a catalytic capacity toward the destruction of aromatic compounds and degradation of organic pollutants (Kotz et al. in the Pt and Ti/RuO2 systems during 6 hrs of electrolysis (figure 6.. Although its conductivity could be greatly increased by doping of Sb. Pure SnO2 is a kind of typical n-type semiconductor.2 The solution pH during the EC process The residual TOC in the solutions after EC phenol destruction suggests the formation and accumulation of organic intermediate products. 1991. TOC reduction was much slower than phenol destruction particularly on the Pt and Ti/RuO2 anodes..4).. Thereafter.1. because of a greater efficiency phenol and TOC reduction on the Ti/SnO2-Sb-Al anode than that on the other three anodes. 2000).1. A slightly increase trend appeared during next 10 hrs.0 with no sign of increase.4 as TOC mineralization approached its completion.

Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products 14 100 Sn Pt Ru 12 Phenol concentration (mg/L) 80 10 60 8 40 6 20 4 0 0 1 2 3 4 5 6 2 Reaction time (hr) Figure 6.3 Phenol removals by the three types of anodes 14 80 12 TOC (mg/L) 60 10 Sn Pt Ru 8 40 6 20 4 0 0 1 2 3 4 5 6 2 Reaction time (hr) Figure 6. time during phenol degradation 78 pH Voltage (V) .4 TOC and solution pH vs.

Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products 6.6).3 Current efficiency and TOC removal efficiency Electrode Ti/SnO2-Sb-Al had an average current efficiency of around 50% for phenol oxidation from 500 mg/L at a current input of 20 mA/cm2. which is produced by phenol oxidation (Comninellis and Pulgarin. It is generally believed that the light yellow color is caused by benzoquinone. 1991). Benzoquinone and hydroquinone are known as an active redox couple in equilibrium in an aqueous solution (Rieger. However. 6.1 Direct products of phenol oxidation The phenol solutions exhibited color changes during the electrolysis processes. the liquid turned to light yellow first. Electrode Ti/SnO2-Sb-Al was two to three times greater than the other electrodes. however. they accumulated to a higher concentration level and for a much longer time in the solutions treated by the Ti/RuO2 and Pt anodes.1. For the Pt and Ti/RuO2 cells. The HPLC results indicate the transformation of the phenol by electrolysis to benzoquinone. 1987). The value of the current efficiency for phenol destruction decreased as the phenol concentration became lower (Figure 6.7). The color did not fade even after 6 hrs of electrolysis. In the anode Ti/SnO2-Sb-Al cells. which began to fade after 3 hrs when the phenol concentration was reduced to zero.2. hydroquinone and catechol (Figure 6.5). Current efficiency on TOC destruction during the final 3 hrs of electrolysis faster than the first 3 hrs on electrode Ti/SnO2-Sb-Al. the solution turned to yellow and became darker with the EC process. the current efficiency of electrode Ti/SnO2-Sb-Al anode was significantly greater than the Pt and Ti/RuO2 anodes for TOC removal (Figure 6. With an initial phenol concentration of 100 mg/L. much lower current efficiencies of about 7% were recorded. The total detectable amount of aromatic compounds was about 5 mg/L in the cell of Pt and 20 mg/L in the cell of Ti/RuO2 based on the carbon content. These aromatic compounds had no detectable accumulation in the solution electrolyzed by the Ti/SnO2-Sb-Al anode for 6 hrs.2 Intermediate products and reaction routes for different electrodes 6. On the electrodes of Pt and Ti/RuO2. Benzoquinone was found in 79 . which means the major intermediate compounds in the solution has replaced phenol and the degradation rate was accelerated by the catalytic effect of this anode.

20 Ti/SnO2-Sb-Al Pt Ti/RuO2 15 10 5 0 1 2 Reaction time (hr) 3 4 5 6 Figure 6.Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products 25 Current efficiency on phenol degradation (mg/L C) .5 Current efficiency on phenol removal 7 Current efficiency on TOC removal (mg/LC) 6 Ti/SnO2-Sb-Al Pt Ti/RuO2 5 4 3 2 1 0 1 2 3 4 5 6 Reaction time (hr) Figure 6.6 Current efficiency on TOC removal 80 .

7 HPLC analysis of the intermediates of EC phenol degradation on the three anodes 81 .Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products 50 Phenol incineration on Ti/SnO2-Sb-Al anode Phenol oncineration on Pt anode Phenol incineration on Ti/RuO2 anode 40 Concentration-C (mg/L) 30 Hydroquinoe 1.4-benzoquinone Catechol 20 10 0 Muconic acid Oxoglutaric acid Maleic acid Fumaric acid Succinic acid 4 Concentrration-C (mg/L) 3 2 1 0 Pyruvic acid Malonic acid Oxalic acid Acetic acid Formic acid 10 Concentrration-C (mg/L) 8 6 4 2 0 0 60 120 180 240 300 360 0 60 120 180 240 300 360 0 60 120 180 240 300 360 Retention time (min) Retention time (min) Retention time (min) Figure 6.2-benzoquinone 1.

and Ti/RuO2 (right) B B B B 82 .C aliphatic acids Concentration .Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products 100 80 Phenol Aromatic intermediates 6.C (mg/L) 60 40 20 0 0 60 120 180 240 300 360 Time (min) Figure 6. 5. 4 .C aliphatic acids 3. 1 . Pt (middle). 2.8 TOC components of the intermediates of EC phenol degradation by the three anodes Ti/SnO2-Sb-Al (left).

9 Degradation of pure intermediate chemicals on the three anodes 83 .Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products Hydroquinone 60 Catechol Oxoglutaric acid Concentration (mg/L) 40 Ti/SnO2-Sb-Al 20 Pt Ti/RuO2 50 0 Fumaric acid Maleic acid Succinic acid 40 Concentration (mg/L) 30 20 10 50 0 malonic acid Acetic acid Oxalic acid 40 Concentration (mg/L) 30 20 10 0 0 60 120 180 240 300 360 0 60 120 180 240 300 360 0 60 120 180 240 300 360 Time (min) Time (min) Time (min) Figure 6.

2 Aliphatic acids from phenol oxidation A number of carboxylic acids with 2 to 6 carbon atoms were identified by HPLC as the intermediates of phenol degradation in the electrolyzed solutions. 6. This was in line with a higher concentration of phenol and other aromatic intermediates totally 75 mg/L remaining in the solution electrolyzed by the Ti/RuO2 anode (Figure 6. 1994. In the Ti/SnO2-Sb-Al system only a light yellow color was observed for a period of time during the EC process..8). 6. The color was probably caused by the polymeric compounds produced by the EC oxidation of phenol (Gattrell and Kirk. a yellow to brown color built up in the solutions that were treated by the Ti/RuO2 and Pt anodes. Generally speaking. The acids were the intermediate products after aromatic ring cleavage. there were considerable differences in the formation and degradation of the intermediate organic acids between the three EC systems of different anodes. However. maleic acid and acetic acid accumulated in the solution as aromatic compounds were degraded by electrolysis. oxalic acid and formic acid gradually increased with the EC process. The products of polymerization consist of hydroquinone-benzoquinone monomeric units that 84 . which was less the concentration of 12 mg/L in the cell of Pt (Figure 6. the overall degradation rate of the intermediate organics by the Pt and Ti/RuO2 anodes was much slower than that with the Ti/SnO2-Sb-Al anode under the same experimental conditions. HPLC results did not suggest the substances that would cause the color appearance. maleic acid. 2005). 1993. For the Pt cells. The total amount of aliphatic acids was 6 mg/L based on the sum of carbon.2. For the Ti/RuO2 system. oxoglutaric acid.Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products the Pt cells and both hydroquinone and benzoquinone lefted in the Ti/RuO2 cells (Figure 6. The color disappeared well before the TOC had been completely removed.7).. Li et al. oxoglutaric acid and oxalic acid were the most dominant organic acids. Rajeshwar et al. as indicated by the HPLC analysis of individual intermediates. which was in agreement with the TOC measurement. All acids were reduced to zero in concentration after 6 hrs.8).3 Polymeric compounds produced during the EC process As described above.2. For the Ti/SnO2-SbAl cells.

2. acetic acid and formaic acid. 1986. These intermediates substituted the organic carbons of the parent substrate. 1. However.5 EC destruction of the intermediate products of phenol electrolysis The oxidation kinetics of the above intermediates of phenol electrolysis were examined individually with pure chemicals as the parent substrates. the 85 . they were apparently included in the TOC measurement (Figure 6. or might be reversed. TOC2 included five long carbon chain acids in muconic acid.4 Grouping of intermediate organic compounds The organic components analyzed by HPLC were combined into a few groups for comparison (Figure 6. oxalic acid. fumaric acid. however. It was a gradual substitute process that simple organics replaced complex organics. and even less than 10% of TOC transformation on the Ti/RuO2 anode. the EC destruction process of a pure intermediate was traced by HPLC for solution analysis (Figure 6.4-benzoquinone and catechol. The change in the concentrations of different TOC groups showed the organic degradation steps from larger molecules to smaller molecules. organic acids and unknown organics that could be polymeric materials. oxoglutaric acid. These amorphous polymers are formed by a radical reaction mechanism by phenate anions (Mengoli and Musiani. According to the curve of concentration reduction.. 6. With the decrease of phenol. Similar to phenol oxidation. 6.8). TOC1 referred to the sum of four aromatic compounds of hydroquinone. This comparison suggested that the acid oxidation would be the rate-limiting step for complete TOC removal by electrolysis with the Pt anode. Rodgers et al.2.Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products generally exhibit a dark brown color (Feng et al. the same treatment duration time only could transfer phenol into carboxylic acids on the Pt anode. maleic acid and succinic acid. The color compounds could not be detected by the present HPLC analysis.4). 6.2.2-benzoquinone. Electrolysis of 6 hrs was enough for all intermediate species to be oxidized by the Ti/SnO2-Sb-Al anode. 1995). there were accumulations of benzoic compounds. TOC3 was the sum of five short carbon chain acids of malonic acid.. 1. while both ring cleavage and acid oxidation were difficult for the Ti/RuO2 anode. 1999).9).

As to the carboxylic acids.Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products Table 6. For the EC destruction of aromatic compounds. In addition.011 0.0006 0. EC treatment was confirmed to be more effective for 86 .0015 0.0019 0.0015 0.032 0. However.002 0.000003 0. on any specific anode.14 0.001 0. Nearly all of the chemicals were tested and the Ti/SnO2-Sb-Al anode delivered the fastest EC destruction rate.000007 first-order rate constant could be estimated for the EC destruction reaction of a specific intermediate compound (Table 6. the Ti/SnO2-Sb-Al anode was about a half to one order of magnitude faster than the Pt anode and around one to two orders of magnitude faster than the Ti/RuO2 anode.1).024 0.0004 0. the organic destruction by the EC oxidation was faster for large molecules than for smaller ones (Table 6.033 0.0099 0.00004 0.019 0.0041 0.000009 0.032 0.00002 Pt Ti/RuO2 0.025 0.1 Kinetic rate constants for EC oxidation of different intermediates by the three types of anodes (min-1) Ti/SnO2-Sb-Al Phenol Hydroquinone Benzoquinone Catechol Oxoglutaric acid Maleic acid Fumaric acid Succinic acid Malonic acid Oxalic acid Acetic acid 0.028 0.0049 0. oxidation of the aliphatic acids.026 0.0046 0. followed by the Pt anode and then the Ti/RuO2.028 0. It is apparent that there was no pronounced rate-limiting step in complete phenol degradation by the Ti/SnO2-Sb-Al anode. rather than destruction of the aromatic compounds or ring cleavage apparently was the rate-limiting step in EC phenol degradation on the Pt anode.1).008 0. the destruction rate constants on the Ti/SnO2-Sb-Al anode were about one to two orders of magnitude higher that those on the Pt anode and around two to four orders of magnitude higher than those on the Ti/RuO2 anode.026 0.0023 0.0055 0.0067 0.0002 0. These results further confirmed the generally high effectiveness of the Ti/SnO2-Sb-Al anode to oxidation of any type of organic compounds. Both the destruction of aromatic rings and oxidation of carboxylic acids were rate limiting processes to phenol mineralization on the Ti/RuO2 anode.

6. 2005). are in general agreement with the reaction pathway of EC phenol degradation outlined above.. In addition. Houk et al. 1991). 1999. Once the ring cleavage takes place.. Feng and Li..3. maleic acid would first be oxidized to oxalic acid. 1999. the pathway should include the polymer formation from aromatic compounds via phenoxy radicals that attack either benzoquinone or hydroquinone. 2003.2 Aromatic ring cleavage vs. Gattrell and Kirk. the slow degradation rate of intermediate acids led to an accumulation of H+ and continuous drop of the solution pH. Polymerization is hardly a reversible reaction. Rodgers et al. Feng and Li. 1998). Johnson et al.1 Major phenol electrolysis reactions The pathway of phenol degradation by EC oxidation has been the topic of many investigations (Comninellis and Pulgarin. The oxidation proceeds further to break down the C = C bond and decarboxylation to form smaller acids. 1999). Through a series of reactions an organic acid will be oxidized completely with continuous electrolysis. 2005). 1998. which can be degraded with ring breakage to various carboxylic acids. 6. For instance. and in the formation of intermediates. polymerization The present experimental findings in the removal of phenol and TOC.. It is generally considered that phenol oxidation begins with an electron transfer that leads to phenoxy radical reactions (Lund and Baizer. and the polymers are more recalcitrant to EC degradation than phenol. 1991. the subsequent degradation will quickly convert the aliphatic compounds through ethers and simple alcohols. 1984. Furthermore. For benzoquinone and 87 . Tahar and Savall.3.. 2003. 1993. and eventually mineralize to acetic acid. 1991. or be reduced to succinic acid at the cathode followed by oxidation at the anode to malonic acid and then to acetic acid. Radical reactions result in the formation of benzoquinone and hydroquinone.3 EC phenol degradation pathways on different types of electrodes 6. Li et al.. formic acid and carbon dioxide (Devlin and Harris. (Comninellis and Pulgarin. Li et al. and finally to CO2 (Houk et al.Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products treatment of large organic compounds than smaller organic molecules. in the phenol degradation tests by the Pt and Ti/RuO2 anodes.

if the ring breaks rather slowly. If the aromatic ring cleavage takes place rapidly. The electrodes shared largely a similar reaction pathway.3 Pathways of EC phenol degradation The present HPLC analysis revealed more complete intermediate products and their abundances during the EC phenol degradation process. The existence of ·OH radicals definitely strengthens the oxidation capability of the Ti/SnO2-Sb-Al anode for ring cleavage and organic degradation. However. while succinic acid and formic acid formed the intermediates of electrode Ti/RuO2. the ring cleavage could form aliphatic acids of different molecular weights with one to six carbons. Such as the degradation of oxoglutaric acid.11 and 6. compared to the Ti/RuO2 and Pt anodes. ring cleavage and polymerization are two parallel processes that occur simultaneously. there might be some variations in the routes of the pathways. In contrast. 1995). Hence. 6. small acid could be produced directly from either ring cleavage of aromatic compounds or from destruction of larger organic acids. Different electrodes with different surface properties performed rather differently in the electrolysis of phenol and its intermediates. succinic acid and oxalic acid composed the intermediates in the cell of Pt. oxalic acid was the intermediate on Ti/SnO2-Sb-Al anode. Comninellis (1994) has detected the accumulation of ·OH radicals on the surface of anode SnO2 and no ·OH appearance on anode RuO2. Small organic acids were already detected in the early phase of electrolysis. the Ti/SnO2-Sb-Al anode imposed a catalytic capability for organic oxidation. In such a system. For electrodes Ti/RuO2 and Ti/SnO2-Sb-Al.Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products hydroquinone. the EC phenol degradation pathways were proposed for the three electrodes (Figures 6. which is the case with the Ti/SnO2-Sb-Al anode. In particular. According to the electrolysis performance and intermediate abundances during the process.12).10. then polymerization becomes more significant.3. 6. then there is little accumulation of benzoquinone and insignificant formation of polymeric compounds. which is in fact the case with the Ti/RuO2 and Pt anodes. Hence. dimerization and polymerization are not the major reactions in comparison to ring oxidation (Chu . The surface characteristics of an anode could to a certain 88 . the difference in oxidation strength appears to be the key for the different levels of the formation and accumulation of polymer products in the electrolyzed solutions. The results suggest that phenol oxidation might not follow a simple series of reactions.

Ti/IrO2 and Pt anodes. However. 6. There could be some variations in the routes of the pathways of phenol degradation by different anodes. The Ti/SnO2Sb-Al anode had a high current efficiency for phenol destruction and TOC removal. 1. 89 . Ti/IrO2 and Pt anodes. 1. oxalic acid. but accumulated in the cells of Ti/RuO2. malonic acid.2-benzoquinone. Ti/IrO2 and Pt anodes. Based on the electrochemical performance and the abundances of the intermediate chemicals during the EC process. The intermediates according to HPLC analysis included aromatic compounds of hydroquinone. which decreased the EC organic degradation effectiveness.4-benzoquinone and catechol and aliphatic acids of muconic acid. were subsequently oxidized rapidly by the Ti/SnO2Sb-Al anode. which was 2-3 times higher than the current efficiencies of Ti/RuO2.4 Summary Phenol could be readily mineralized by electrolysis at the Ti/SnO2-Sb-Al anode. fumaric acid. phenol degradation was considerably slower at the Ti/RuO2.Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products extent regulate the predominant routes of phenol degradation as well as to determine the reaction kinetics. maleic acid. the modified reaction pathways of phenol degradation on the different electrodes were proposed. it is difficult to identify a single chemical reaction as a rate-limiting step for EC phenol degradation at any electrodes. It is suggested that ring cleavage was critical to phenol oxidation. succinic acid. The intermediate products of EC phenol degradation. there were apparently dark-colored polymeric products formed at the Ti/RuO2. The surface characteristic of the anode could to a certain extent regulate the predominant routes of phenol oxidation as well as to determine the reaction kinetics. In addition. including benzoquinone and organic acids. Ti/IrO2 and Pt. oxoglutaric acid. EC tests with pure intermediate chemicals also demonstrated that different electrodes performed rather differently in organic destruction. pyruvic acid. actic acid and formic acid. Ring breakage resulted in the formation of intermediate organic acids with different molecular weights. Nonetheless.

Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products OH [O] OH [O] OH O [O] O Phenol Hydro quinone OH OH O [O] [O] OH OH O Benzoquinone O Polymeric products Catechol I COOH COOH Benzoquinone O Muconic acid II COOH COOH O 2 COOH COOH CO 2 Oxalic acid Oxoglutaric acid III COOH COOH COOH HOOC Maleic acid Fumaric acid COOH 2 COOH CO 2 H 2O Oxalic acid COOH COOH C O2 COOH COOH Succinic acid Malonic acid COOH CO 2 COOH CO 2 H 2O Figure 6. 90 .12 Proposed phenol degradation pathway at anode Ti/SnO2-Sb-Al.

Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products OH [O] OH [O] OH O [O] O Phenol Hydroquinone OH OH O [O] [O] OH OH O Benzoquinone O Polymeric products Catechol I COOH COOH Benzoquinone O Muconic acid II COOH COOH O COOH HCOOH COOH Succinic acid 2 COOH CO2 COOH H2 O Oxoglutaric acid COOH 2 COOH Oxalic acid HCOOH CO2 H2O Oxalic acid COOH III COOH COOH COOH 2 COOH COOH CO2 H2O Maleic acid Succinic acid COOH Oxalic acid H2O 2HCOOH COOH CO2 Oxalic acid COOH COOH 2HCOOH HOOC COOH CO2 H2 O Fumaric acid COOH Oxalic acid COOH 2 CO2 COOH H2 O COOH Succinic acid Oxalic acid Figure 6.13 Proposed phenol degradation pathway at anode Pt. 91 .

Chapter 6: Electrochemical degradation kinetics of phenol and its intermediate products OH [O] OH [O] OH O [O] O Phenol Hydroquinone OH OH O [O] [O] OH OH O Benzoquinone O Polymeric products Catechol I COOH COOH Benzoquinone O Muconic acid II COOH COOH O COOH HCOOH COOH Oxoglutaric acid III COOH Succinic acid COOH COOH COOH HOOC COOH Maleic acid Fumaric acid Succinic acid COOH 2HCOOH COOH CO 2 H 2O Figure 6.14 Proposed phenol degradation at anode Ti/RnO2. 92 .

Chapter 7: Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms Chapter 7 Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms 7.1 LSV and oxidation potentials The electrochemical properties of the four kinds of electrodes were analyzed by the voltammetric technique. The measurements were conducted in 0. 93 .25 M Na2SO4 with and without phenol addition at different concentrations.1 Characterization of the electrodes by linear sweep voltammetry (LSV) 7. The LSV was performed Figure 7.1 Phenol oxidation on the three types of anodes.1.

7.1 Two electrochemical reactions: phenol oxidation and oxygen evolution There were two electrochemical reactions expected at an anode during the LSV scanning process.1. on which the current density 1. However. The LSV results would suggest the potentials of phenol oxidation at the surface of different anodes.1. Oxygen evolution potential was advanced than the phenol oxidation potential. 94 .9 V and 1. Figure 7. Occurrence of a reaction at a certain voltage would result in a sudden current density increase as a response which was caused by the electron transfer.1 V potential values could be found on electrode Ti/RuO2. For example. phenol oxidation and oxygen evolution from water electrolysis. the sudden LSV increases in the current corresponded to the two electrochemical reactions at the voltage of 0. which would hinder the phenol oxidation peak.1 mA/cm2.2 Phenol oxidation at electrode Ti/SnO2-Sb-Al with different phenol concentrations.2 to 2. Similar phenomena could be observed at the Pt electrode. only water oxidation peaks at 1.1 V.8 V respectively (Figure 7. The peak of phenol oxidation potential was less positive than the oxygen evolution potential of water electrolysis.1).Chapter 7: Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms at a scan rate of 50 mv/s and the potential ranged from 0. as observed on electrode Ti/SnO2-Sb-Al.

In contrast.1.1. The peak current increased significantly from 0.2). oxygen evolution took place rapidly at a lower potential on the Pt and Ti/RuO2 anodes. In comparison.000 mg/L.1.1 Anode Ti/SnO2-Sb-Al Addition of phenol into the electrolyte resulted in new shoulders or peaks along the LSV curves of the Ti/SnO2-Sb-Al anode (Figure 7.5 V for different concentrations. with respective values of around 1. Ti/SnO2-Sb-Al anode had a considerably higher oxygen evolution potential of 1.4).2. The Ti/SnO2-Sb-Al anode apparently was able to oxidize phenol directly on the electrode surface.2 LSV of the electrodes in the electrolyte without phenol The LSV curves in the pure electrolyte show that the Pt and Ti/RuO2 anodes had a lower oxygen evolution potential.2. A phenol concentration of 10. the reference (Figure 7. the reference of the saturated Ag/AgCl electrode (Figures 7.1 mA/cm2 with the increase in phenol concentration from 1000 to 10. While the impute potential ranged below 1.2 LSV curves in the solutions with phenol addition 7.1.Chapter 7: Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms 7.6 V for oxygen evolution was not expected at the Ti/SnO2-Sb-Al anode.8 V vs.1 V vs. This would facilitate the generation and accumulation of ·OH radical at the electrode surface.3 and 1. 7.2 Anode Pt 95 .2 mA/cm2 to 3. Hence these peaks suggest direct anodic oxidation of phenol during the LSV tests. which was unfavorable to the accumulation of ·OH radicals. The high overpotential of oxygen at the Ti/SnO2-Sb-Al anode suggests that the reaction forming molecular oxygen was probably restrained.000 mg/L accelerated the oxidation rate comparing with the concentration of 1000 mg/L. The peaks were located at about 1.3 and 7. 2000. 7. 2002).1. Tanaka et al. It is believed that oxygen molecules are formed by radical reactions involving the ·OH free radical generated electrochemically (Polcaro et al.1.1.2).

Chapter 7: Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms Figure 7.4 Phenol oxidation at electrode Ti/RuO2 for different concentrations.3 Phenol oxidation at electrode Pt for different concentrations. 96 . Figure 7.

There were no peaks or shoulders found in the LSV curves with the phenol concentration increasing. On the other hand. Hence.4 Effect of phenol concentration on the LSV curves In general. Simond and Comninellis. Ti/SnO2-Sb-Al anode had a greater reactivity towards direct phenol oxidation on its surface. however. though its reactivity for direct phenol oxidation was not as good as its conductivity.2 mA/cm2. the starting background current density in the LSV curve at the Ti/RuO2 anode was about 0. Increasing the phenol concentration to 10.2. 1997).2 mA/cm2. The result suggests that the possible phenol oxidation potential at the Ti/RuO2 anode was higher than the potential of water oxidation at 1. In comparison.2. The corresponding phenol oxidation potential at Pt was somewhat lower than the potential on the Ti/SnO2-Sb-Al anode.Chapter 7: Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms For the Pt anode. however. organic concentration also could shift 97 . Ti/RuO2 anode apparently have more active sites on the surface which favors current transfer.. and additionally. 7. concentration affects the mass transfer process from the bulk solution to the anode surface. the oxidation rate was not as faster as that at the Ti/SnO2-Sb-Al anode. water discharge. an increase in phenol concentration introduced more electrons into EC reaction on the Ti/SnO2-Sb-Al anode surface which reached a current density of 3. oxygen evolution was the dominant EC reaction and only an insignificant fraction of charge impute would be utilized for phenol oxidation.1 V (Arikawa et al. Phenol also could be oxidized directly at the Pt surface. current peaks were observed in the LSV curves with phenol addition and increased with phenol concentration.3 Anode Ti/RuO2 With the Ti/RuO2 anode.1. The response of the limiting current might be related to the mass transfer of the organic from bulk solution to the anode surface. phenol addition into the electrolyte did not cause significant changes in the LSV measurement.1. direct phenol oxidation at the Ti/RuO2 anode was much more difficult than that on the Ti/SnO2-Sb-Al anode and the Pt anode as well. This shows a better conductivity to the Ti/RuO2 anode. which hindered direct phenol oxidation on the Ti/RuO2 anode surface. 1998. 7. Hence. In other words.1 V higher than the other two anode types.000 mg/L led to a raise of the current density up to 1.

which 1. electron transfer and mass transfer refered to the two alternatives limiting steps. and also exhibited their different catalytic capability toward phenol oxidation (Figures 7.Chapter 7: Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms the oxidation potential of the substance compound. Due to the catalytic effect of anode Ti/SnO2-Sb-Al.3. 7. the oxidation reaction carried out by electrodes Ti/SnO2-Sb-Al and Pt were easier than that by Ti/RuO2. Voltage impute at 0.2. The comparison among voltammetric sweep figures of electrodes Ti/SnO2-Sb-Al. According to energy requirement. Pt and Ti/RuO2 illustrated their different electrochemical properties. and 7.8 V may cause phenol oxidation. while the concentration effects during electrolysis should not be overlooked. the energy hump (ΔG) for phenol oxidation reaction was lowered.3 Effect of the solution pH on the phenol oxidation over-potential 98 . To the different phases of electrochemical phenol oxidation. 7. an increase in phenol concentration may advance the onset phenol oxidation potential. Hence in the voltammetric sweep.4).8 V is enough to led water discharge and oxygen evolution.1.

and the process may be simplified to three steps (Figure 7.6. 99 . the potential got 0. which includes two reactions.1 V increasing with the solution pH dropping.2 Electrochemical phenol oxidation mechanisms The EC organic degradation process includes mass transfer steps and electrochemical reaction steps (Za. 7. The oxidation of phenol was accompanied with the loss of protons.1 ma/cm2 increasing of limiting current. as suggested by the LSV results. With decreasing of pH. there was a slight shift towards the lower potential of the onset of oxidation reactions. and 7. A pH change could to a certain extent influence the thermodynamics of phenol oxidation reactions. ③. from bulk to electrode surface.Chapter 7: Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms The dependence of oxidation potential on pH was demonstrated by the cyclic voltammograms at electrodes Ti/SnO2-Sb-Al. (2) Electrochemical reaction. Pt and Ti/RuO2 (Figure 7. To the electrode Ti/SnO2-Sb-Al. (3) Mass transfer steps shown as ④and ⑤. and have maximum 0. ①and ②.5.7). 2002). 7.8): (1) Mass transfer.

. Reaction ② is the generation and accumulation of hydroxyl radicals at the electrode surface. 2000. This is expected to be the case for phenol oxidation on the Ti/SnO2-Sb-Al anode. The adsorption behavior of a chemical solute could be related to the adsorption free energy of water molecules on the surface with no respect to specific chemicals (Za. 2002. the chemical concentration in the solution and the surface hydrophilicity of the anode. and the two EC reactions for ·OH radical generation (Polcaro et al.1 EC phenol oxidation process and mass transfer Reaction ① is the mass transfer to the surface of an electrode. 2002). Tanka et al.2.Chapter 7: Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms 7. 2004). 100 . The rate of ·OH radical generation and the amount of ·OH accumulation are determined by the surface property of the electrode. This is a reaction accompanied by the increase in chemical concentration at the anode surface and the decrease of its concentration in the bulk solution. which also is affected by temperature. the adsorption of the organic matter onto the electrode surface. Chen.. A good hydrophilic surface favors chemical adsorption and increase the amount of substances involved in EC reaction.

This also favors a more covalent character of the metal-oxygen bond than for other dn cations (Rodrigues and Olivi. Additionally. 1997. The anode surface property also affects the route of reactions and the reaction kinetics as illustrated in Chapter 6 for different anodes. the d10 electronic configuration plays a prominent role in allowing a wide band gap to be stabilized. Tanaka et al. the EC oxidation reactions are simple and direct as follows: MOx + H 2 O → MOx (⋅OH ) + H + + e − MOx (⋅OH ) + R → MOx + RO + 1 / 2O2 ↑ + H + + e − (7.. and the conductivity of SnO2 coating increased due to the presence of oxygen vacancies and free electrons. 2003. to the cations Sn4+ and Sb5+. this decreases the need of oxygen atom in the metal oxide crystal lattice.. partially substitutes the place of Sn4+ with Sb5+.1) (7.2 EC phenol degradation steps Reaction ③ is the electrochemical oxidation of the organic on the anode surface. during reaction ③ . 2002). Free radical chain reactions would result in a series of organic degradation reactions as demonstrated in Chapter 6. and RO is the oxide of the organic matter.2. On the electrode Ti/SnO2-Sb-Al. H2O / OH- Ti ─ Titanium plate MOx ─ Metal oxide coating film R ─ Organic matters RO ─ Oxidation product of organic R 7. In doped coating.2) where MOx refers to metal oxide. Meanwhile. 1997. 2004). Choisenet et al. hydroxyl radicals are adsorbed by the metal oxides on the electrode surface (Simond et al.8 EC phenol oxidation process...Chapter 7: Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms The electrode with a higher overpotential of oxygen evolution would lead to more ·OH radical production from water electrolysis. On the other hand. 101 . R ① ② ③ ⑤ ④ Ti MOx O2 RO Figure 7. a hydrophilic polar surface would allow continuously accumulation of ·OH radical production on the surface. R is the organic matter. CorreaLozano et al.

Additional step is the oxygen evolution. The selectivity of dn electronic configuration of metal oxide made phenol oxidation on Ti/RuO2 anode more complex (Rodrigues and Olivi. oxygen evolution took place at a rapid rate at a lower potential on the Ti/RuO2 anodes. In contrast.4 and 7. According to the analysis of electrode electrochemical behaviors. There were considerable differences between anodes Ti/Sn-Sb-Al.3. including the intermediates and end products.3 Oxygen evolution Reaction ④ and ⑤ are another mass transfer step. First. nonselective oxidant of free radicals.5).Chapter 7: Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms Oxidation reactions on electrode Ti/RuO2. In comparison to the conventional Pt and Ti/RuO2 anodes.2. during reaction ③ are illustrated in following equations (7. The surface properties of the electrodes appeared to affect the reactions involving in EC organic degradation.. MOx + H 2 O → MOx (⋅OH ) + H + + e − MOx (⋅OH ) → MOx +1 + H + + e − MO x +1 + R → MO x + RO + 1 / 2O2 ↑ (7. as well as the generation of other byproducts.5) where MOx+1 refers to a higher valent metal oxide. Choisenet et al. the desorption and releasing of electrolyzed products. 7. 2003. 7. Organic matter could be readily destructed by the high-energy. 2004). Organic oxidation products that are difficult to be desorpted cause the contamination of Pt. 7.4) (7. anode Ti/SnO2-Sb-Al had an obvious catalytic capability toward phenol oxidation.3) (7.3 Summary Electrochemical oxidation with the catalytic electrode Ti/SnO2-Sb-Al was demonstrated as an effective alternative to degradation of toxic and refractory organic pollutants. its high overpotential of oxygen evolution would allow more production and accumulation of hydroxyl radicals near the anode surface under a higher potential condition. which was unfavorable to the 102 . Pt and Ti/RuO2 at each step during the phenol degradation process. The three types of electrodes performed rather differently during LSV tests. there could be two main reasons for the high effectiveness of the Ti/SnO2-Sb-Al anode in phenol.

Second. power could be utilized for direct oxidation of chemical compounds on the anode.Chapter 7: Surface and electrochemical properties of the electrodes and EC phenol degradation mechanisms generation of hydroxyl radicals. 103 . the peaks in the LSV curves of the Ti/SnO2Sb-Al anode in phenol solution indicates direct organic oxidation at the anode surface. Thus. which was much difficult to be achieved with the Pt and Ti/RuO2 anodes.

Chlorophenol is much more toxic than phenol. were examined for their performance and effectiveness in chlorophenol electrolysis. Ti/SnO2-Sb-Al. Three types of electrodes.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways Chapter 8 Electrochemical degradation of chlorophenol: Kinetics and pathways 8. Ti/RuO2 and Pt. The degradation pathways were proposed based on the HPLC analysis of the intermediate products for different electrodes. 104 Voltage (V) Ti/SnO2-Sb-Al 8 . The experimental procedures were similar to the phenol degradation study. The electrochemical properties of the electrodes were 12 100 10 MCP concentration (mg/L) 80 60 Pt Ti/RuO2 6 40 20 4 0 0 1 2 3 4 5 6 2 Reaction tiem (hr) Figure 8.1 EC chlorophenol oxidation Mono-chlorophenol-2 (MCP) was selected as another model organic compound for treatment by the electrochemical method.1 MCP destruction by the three types of anodes.

followed by the noble Pt anode and then the conventional Ti/RuO2 anode.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways characterized.1).2 TOC removal at the three types of anodes. However. In comparison under the same operation conditions. Chlorophenol was destructed nearly completely from an initial concentration of 100 mg/L after 4 hrs by the Ti/SnO2-SbAl anode.1). Ti/SnO2-Sb-Al.1. the rate of chlorophenol destruction was comparable to that of phenol destruction. 55% chlorophenol was oxidized by the Pt anode and only 10% chlorophenol was destructed by the Ti/RuO2 anode (Figure 8. The three electrodes had an greater difference in organic mineralization as 50 14 40 12 10 TOC (mg/L) 30 Pt Ti/RuO2 8 20 6 10 4 0 0 1 2 3 4 5 6 2 Reaction time (hr) Figure 8. chlorophenol destruction took place at an even slower rate than that observed previously for phenol destruction. The reduction rate in chlorophenol concentration was particularly fast in the first half hour. The best treatment result was obtained with the Ti/SnO2-Sb-Al anode. 8. showed rather different effectiveness for EC chlorophenol degradation (Figure 8. 105 pH Ti/SnO2-Sb-Al .1 Chlorophenol oxidation and TOC removal by electrolysis The three different anodes. Ti/RuO2 and Pt. and the results were compared with what obtained from the phenol electrolysis study. on the Pt and Ti/RuO2 anodes. To the Ti/SnO2-Sb-Al anode.

In the Ti/SnO2-Sb-Al system. Comninellis. 1991. 1998. 8.2 with no sign of increase. respectively. while a high TOC content remained in the solutions. 8. 1994. the pH decreased continuously to around 4. Li et al.5 to around 3. under the same electrolysis conditions at a current density of 20 mA/cm2.3 Current efficiency The current efficiency indicates both the performance of the EC process and the specificity of the surface reactions involved.3 as TOC mineralization approached completion.1.. electrodes Pt and Ti/RuO2 appeared to be worsein performance for treating chlorophenol than phenol degradation tests. The drop in pH was apparently caused by the formation of aliphatic acidic substances from the chlorophenol destruction. A much lower current efficiency of chlorophenol treatment was recorded for both Pt and Ti/RuO2 electrodes under the same EC conditions (Figure 8.2). particularly at the Pt and Ti/RuO2 anodes. 2005). just 30% and 10% TOC removals were deliverded by the Pt and Ti/RuO2 anodes. The efficiency decreased to around 10% by the end of the EC process with an everdecreasing chlorophenol concentration in the electrolyzed solution. the pH increased gradually to 5. However. in the Pt and Ti/RuO2 cells during 6 hrs of electrolysis. Complete organic oxidation was achieved after 5 hrs at the Ti/SnO2-Sb-Al anode.6 while the chlorophenol was being oxidized. the Ti/SnO2-Sb-Al anode had a current efficiency of more than 50% for TOC destruction. aliphatic acids were believed to be the main intermediates produced by EC degradation of chlorophenol (Comninellis and Pulgarin.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways indicated by the TOC removal (Figure 8. Electrode Ti/SnO2-Sb-Al appeared to be highly effective for complete degradation of chlorophenol. Houk et al. TOC reduction was worse than chlorophenol destruction.1.4). On the other hand. On the contrary.2). For a current input at 20 mA/cm2.2 The solution pH during electrolysis The residual TOC in the solutions after EC chlorophenol destruction suggests the formation and accumulation of organic intermediate products. Thereafter.. 2003. The Pt anode had a current 106 . Similar to phenol electrolysis. Feng and Li. The solution pH changed correspondingly with the components of intermediates at the electrolysis process (Figure 8. the pH dropped initially from 5.

40 mA/cm2 Cl.3).3. when 95% chlorophenol was destructured. while the Ti/RuO2 had an efficiency of only about 5%.60 mA/cm2 30 25 30 Current efficiency (%) 20 Cl (mg/L) 20 15 10 10 5 0 0 1 2 3 4 5 6 0 Reaction time (hr) Figure 8. On the other hand. For the Ti/SnO2-Sb-Al anode. as the overpotential of chlorine evolution is slightly lower than oxygen evolution. An increase in current density was able to accelerate the reaction rates. Different from phenol electrolysis. However. as described previously. a higher current input might result in more power contribution to heat generation and oxygen evolution. continuous chloride release of from the chemical substance was identified by the solution analysis in the cell of electrode Ti/SnO2-Sb-Al.20 mA/cm2 Cl. the current efficiency based on TOC for EC chlorophenol treatment decreased slightly as the current density increased (Figure 8. As exhibited in Figure 8.3 TOC degradation as a function of charge input at different current density 107 - . Chlorine production would work on the oxidation of chlorophenol and its intermediates. and definetly faster than phenol degradation which 40 20 mA/cm2 40 mA/cm2 60 mA/cm2 Cl. Chloride ions in the solution would in turn lead to chloride electrolysis and chlorine evolution. chlorophenol degradation on the Ti/SnO2-Sb-Al anode had double engine forces. dechlorination was supposed to one of the important steps in chlorophenol oxidation. After 2 hrs of the electrolysis. chlorine is an effective oxidant.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways efficiency of around 8% throughout the test period. the chloride concentration reached the maximum point. Therefore.

hydroquinone. 1991).5 and 8. It is generally considered that phenol is the major intermediate product of chlorophenol oxidation (Comninellis and Pulgarin.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways was pushed by one engine. chloride release was detected at a much slower rate in the chlorophenol solutions electrolyzed by the Pt and Ti/RuO2 anode. they accumulated at a higher concentration level and for a much longer time in the solutions treated by the Ti/RuO2 and Pt anodes. benzoquinone. about 4 mg/L substances left in the cell of Ti/RuO2 while 3 mg/L in the Pt cell.1 HPLC analysis of intermediate compounds The intermediates of chlorophenol electrolysis were analyzed by HPLC by the solutions treated by different electrodes (Figures 8. Also.6). During the EC treatment process with different electrodes. Chlorophenol degradation also produced the same aromatic intermediates as phenol electrolysis (Figure 8. the concentrations of chlorohydriquinone. 2-benzoquinone. There was more chlorohydroquinone found in the Pt cells and both hydroquinone and benzoquinone were found in the Ti/RuO2 systems (Figure 8. the chlorophenol solutions did not exhibit obvious color changes as observed for phenol electrolysis. 4-benzoquinone.5). Chlrohydroquinone was apparently the main product in the Pt and Ti/RuO2 cells. Eight kinds of aromatic compounds and chlorophenol were identified. 4-chlorocatechol. 1. 4-chlorocatechol. The aromatic intermediates included chlorohydroquinone. 1. which led to a considerable slow rate of chlorophenol destruction and organic degradation. 8.5). It was apparent that dechlorination was a important limiting step in the electrolysis of chlorophenol by electrodes Pt and Ti/RuO2.2. These eight aromatic compounds summed to 2 mg/L (based on C) in the Ti/SnO2-Sb-Al cells (Figure 8. Most of the aromatic compounds were completed removed by the end of electrolysis 108 . and these substances in number was more than what encountered during the phenol degradation tests. This was probably due to the decoloring effect of hypochlorite that was formed by chloride electrolysis following EC dechlorination and chlorophenol oxidation. phenol. 3-chlorocatechol were not less than phenol in considerable quantity in the electrolyzed solutions. However. However.5) after 6 hrs treatment. On the contrary.2 Intermediates and pathways of EC chlorophenol degradation 8. 3-chlorocatechol.

Similar to EC phenol degradation. fumaric acid. acetic acid and formic acid. maleic acid.6). The result of chlorophenol degradation further validated the higher catalytic activity of anode Ti/SnO2-Sb-Al toward organic mineralization.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways 60 50 Ti/SnO2-Sb-Al Pt Ti/RuO2 Current efficiency (%) 40 30 20 10 0 0 1 2 3 4 5 6 Reaction time (hr) Figure 8. All types of aliphatic acids could be fully oxidized by the Ti/SnO2-SbAl anode.4 MCP degradation as a function of the reaction time for different anodes. The intermediate carboxylic acids included muconic acid. Only in the Ti/SnO2-Sb-Al cell muconic acid was completely oxidized. both destruction of chlorophenol and degradation of its intermediates were slower by an order of magnitude or more comparing to the tests with the Ti/SnO2-Sb-Al anode.2. Muconic acid was the major intermediate in any of the electrolysis cell. in the Ti/SnO2-Sb-Al system. 8. while a large amount of them were left in the other two cells. Also for the other two electrodes. which resulted in complete TOC removal. malonic acid. a number of aliphatic acids were found during chlorophenol electrolysis with the three different electrodes (Figure 8. succinic acid.2 Grouping of the intermediate organic compounds 109 . oxoglutaric acid.

g. benzoquinone. e.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways The overall organic compounds were grouped into three parts. 4-benzoquinone). the sum of 8 kinds of aromatic compounds (chlorohydriquinone. 8. almost all organic species were mineralized on the Ti/SnO2-Sb-Al anode. 2-benzoquinone. The summation of organic carbons in these chemicals demonstrates the change of total organic content from the parent substrate. 3-chlorocatechol.2. organic acids and polymeric products. and the sum of 8 specis aliphatic acids (muconic acid. Within three hours of electrolysis. succinic acid. The situation in the Ti/RuO2 cell was even worse with a 28% chlorophenol destruction and a 5% overall TOC removal (Figure 8. However. Y-axis refers to the sum of organic carbon concentrations that were calculated from the results of HPLC analysis (Figure 8. maleic acid. both ring cleavage and organic acid oxidation were apparently the rate limiting steps for complete chlorophenol degradation. 4-chlorocatechol. the parent substrate chlorophenol. oxoglutaric acid. and the second is the releasing of chlorine.7). As to the reductive 110 . hydroquinone. With the destruction of chlorophenol during the EC process. The dechlorination reaction could take place in two ways according to the direction of electron transfer. there were accumulations in benzoic compounds. Till the end of the 6-hr electrolysis tests. reductive dechlorination and oxidative dechlorination. the reaction is reductive dechlorination. If chlorine is the electron donor. 99% chlorophenol was destructed and 80% TOC was removed at the Ti/SnO2-Sb-Al anode. phenol. There was no obvious rate-limiting step in chlorophenol degradation at the Ti/SnO2-Sb-Al anode. The oxidative reaction of a chlorinated aromatic compound has two effects: the first is the oxidation of the aromatic ring. On anode Ti/RuO2. 1. fumaric acid. In comparison. malonic acid. 1. However. only 25% organic removal was achieved on the Pt anode.7). acetic acid and formic acid). more than 50% TOC was still left in the Pt cells and about 80% TOC was left in the Ti/RuO2 cell. oxidation of the organic acids appeared to be the limiting step for the Pt anode. contrarily the process is oxidative dechlorination.3 Transformation and degradation of chlorophenol during electrolysis As suggested previously. dechlorination is a crucial step in EC chlorophenol oxidation.

2-benzoquinone 1.4-benzoquinone Catechol Phenol 2 1 0 0 60 120 180 240 300 360 0 60 120 180 240 300 360 0 60 120 180 240 300 360 Reaction tieme (min) Reaction time (min) Reaction time (min) Figure 8.5 HPLC analysis of intermediates of EC MCP degradation on the three anodes (aromatic compounds).C (mg/L) 15 10 5 20 0 Concentration .C (mg/L) 15 Chlorohydroquinone 3-chlorocatechol 4-chlorocatechol 10 5 0 3 Concentration . 111 .Chapter 8: Chlorophenol incineration: kinetics and pathway 20 Hydroquinone 1.C (mg/L) Hydroquinone 1.2-benzoquinone 1.4-benzoquinone Catechol Phenol Chlorohydroquinone 3-chlorocatechol 4-chlorocatechol Ti/SnO2-Sb-Al Pt Ti/RuO2 Concentration .

Chapter 8: Chlorophenol incineration: kinetics and pathway 30 Ti/SnO2-Sb-Al 25 Concentration . 112 .C (mg/L) 8 Muconic acid Oxoglutaric acid Fumaric acid Maleic acid Succinic acid 6 4 2 0 20 Malonic acid Acetic acid Formic acid 15 Concentration .C (mg/L) 10 5 0 0 60 120 180 240 300 360 0 60 120 180 240 300 360 0 60 120 180 240 300 360 Reaction time (min) Reaction time (min) Reaction time (min) Figure 8.6 HPLC analysis of intermediates of EC MCP degradation on the three anodes (aliphatic acids).C (mg/L) 20 Muconic acid Oxoglutaric acid Fumaric acid Maleic acid Succinic acid Malonic acid Acetic acid Formic acid Pt Ti/RuO2 15 10 5 0 12 10 Concentation .

Chapter 8: Chlorophenol incineration: kinetics and pathway 60 Chlorophenol-C Quinones-C Acids-C 50 Concentration -C (mg/L) 40 30 20 10 0 0 60 120 180 240 300 360 Reaction time (min) Figure 8. 113 . and Ti/RuO2 (right).7 TOC components of intermediates of EC MCP degradation by the three anodes: Ti/SnO2-Sb-Al (left). Pt (middle).

5% 0.8% 360 55% 1.1% 0.5% 0.7% OH Cl OH OH Cl OH Cl Polymers Catechol Benzoquinone B OH OH O Acids Table 2: Chlorophenol percentage Time Sn Pt Ru 30 1.3% 0. 114 .Chapter 8: Chlorophenol incineration: kinetics and pathway OH [O] OH Cl [O] OH OH O [O] O OH Hydroquinone Chlorophenol Phenol Table 1: Phenol percentage OH OH OH O Benzoquinone O O [O] [O] A Time Sn Pt Ru 30 0.9% Chlorohydroquinone 3-Chlorocatechol 4-Chlorocatechol Figure 8.8 Proposed MCP electrolysis pathways for the three anodes.5% 16% 0.7% 360 0 0.

Dechlorination could take place during chlorophenol destruction. the subsequent ring cleavage.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways dechlorination.4 Basic pathways of EC chlorophenol degradation Figure 8. There were little chlorinated aliphatic acids detected in the electrolyzed solutions. The degradation of chlorophenol may consist of two different phases. 8.9 LSV of anode Ti/SnO2-Sb-Al in MCP solution. The first one was dechlorination for a chlorinated chemical compound. 115 . It appeared that most dechlorination took place before the ring breakage.2. sometimes even after ring cleavage. The reactions included the oxidation of hydroxyl groups and double bonds in the phenolic ring. However. which was comparable to the process of EC phenol degradation. and the oxidation and mineralization of the aliphatic acids. it might also take place for different chlorinated intermediates. the chloride ions are released from the chemical. The other phase of chlorophenol degradation would be the further oxidation of dechlorinated organic compounds.

8). As to the part of acid destruction. which transformed a large portion of chlorophenol into phenol accompanied by releasing a chlorine form the ring.1 LSV of the electrodes in chlorophenol solutions Figure 8.3. the pathways for chlorophenol mineralization by electrolysis were proposed for the different electrodes (Figures 8. Both oxidative dechlorination and reductive dechlorination could take place during the EC process.10 LSV of anode Pt in the MCP solution. The majority of dechlorination apparently was advanced than ring cleavage. In a simplified expression.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways According to the above analysis and the results of EC phenol degradation study.3 Voltammetric study of the anodes in monochlorophenol solutions 8. 116 . the degradation of chlorophenol by electrolysis could be summarized as: [O ] MCP ⎯⎯→ [O ] [O ] Phenol ⎯⎯→ aromatic − compounds ⎯⎯→ aliphatic − acids [ O ] ⎯⎯→ CO2 + H 2 O [O ] chloride − aromatic − compounds ⎯⎯→ aliphatic − acids 8. the pathways were similar to phenol listed in Chapter 6. The following oxidation pathways of the organic intermediates after dechlorination should be similar to those proposed for EC phenol oxidation.

0.9). Hence these peaks suggest direct anodic oxidation reaction during the LSV tests.1.4 V for different chlorophenol concentrations.000 mg/L. Chlorophenol also could be oxidized directly at the Pt surface.1. Respecting to the peak current.11 LSV of anode Ti/RuO2 in the MCP solution. Similar to the phenol study. 117 . addition of chlorophenol into the electrolyte resulted in new shoulders or peaks in the LSV curve of the Ti/SnO2-Sb-Al anode (Figure 8. without chlorophenol produced a rather smooth LSV curve (Figures 8. significant oxygen evolution was not expected from the Ti/SnO2-Sb-Al anode. current peaks were observed in the LSV curves with MCP addition.2 to 6 mA/cm2 as the chlorophenol concentration increased from 1. The Ti/SnO2-Sb-Al anode apparently was able to oxidize chlorophenol directly on the electrode surface. the oxidation Figure 8.10).25 M Na2SO4 solution.9).6 V. In the potential range below 1. On the Pt anode. However. and increased with the chlorophenol concentration (Figure 8.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways Measurements of the electrodes began from the pure electrolyte.000 to 10. The peak current increased significantly from 1. A higher chlorophenol concentration accelerated the oxidation reaction rate at the anode surface. the voltage was located within 1.

12 Current density as a function of the scan rate square root 118 . Ti/SnO2-Sb-Al anode had a greater reactivity towards direct chlorophenol oxidation on its surface.11). 1997).8 mA/cm2.000 mg/L led to a raise of the current density up to 1. lower than the potential at the Ti/SnO2-Sb-Al anode.000 mg/L at Pt was 1. chlorophenol addition into the electrolyte caused little change in the LSV curves.0 V. With the Ti/RuO2 anode. Increasing the chlorophenol concentration to 10. Only an insignificant fraction of charge input could be used for chlorophenol oxidation. 1998. Hence. direct chlorophenol oxidation on anode Ti/RuO2 was much more difficult than that on the Ti/SnO2-Sb-Al anode. There were no peaks and shoulders found in the LSV curves as the chlorophenol concentration increased (Figure 8. however. In comparison. Oxygen evolution was the 25 20 Current dencity (mA/cm ) 1000 mg/L MCP 5000 mg/L MCP 10000 mg/L MCP 2 15 10 5 0 6 8 10 12 14 16 18 20 22 24 Scan rate square root Figure 8. which has been demonstrated by the LSV tests for phenol solutions. In other words. The corresponding chlorophenol oxidation potential with 10. an increase in chlorophenol concentration brought more electron transfer into EC reaction at the Ti/SnO2-Sb-Al anode surface. Simond.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways rate was not as faster as that at the Ti/SnO2-Sb-Al anode. The result suggests that the potential of possible chlorophenol oxidation at the Ti/RuO2 anode was higher than the potential of water electrolysis (Arikawa.

This suggests that the EC decomposition of chlorophenol was probably controlled by the mass transfer of the chemical from the aqueous phase to the anode surface.4 EC Chlorophenol degradation pathways 8. This was indicated by the peaks of current density in the LSV curve for the addition of chlorophenol in the electrolyte. 8. Electrolysis of chlorophenol allowed a new current peak during the LSV test. Figure 8. A higher concentration would allow a faster mass transfer rate to the anode interface. rather than electron transfer at the anode. However. an increase in the scan rate square root would cause a linear increase as a response in the oxidation peak current density. power could be utilized for direct degradation of chlorophenol on the anode.2 Peak current densities versus CV scan rate The mass transfer behavior of chlorophenol onto the electrode surface also could be investigated by means of cyclic voltammetry (CV). 8. In other words. Another 119 . with an increase in the chemical concentration. Chemical mass diffusion.3. In general. Thus. appeared to be the rate-limiting step for chlorophenol electrolysis during the LSV process.4. the rate of EC reaction catalyzed by the active Ti/SnO2-Sb-Al surface was faster than the rate of substrate transfer to the anode surface. which would facilitate the oxidation reaction.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways dominant electrochemical reaction that allowed little increase in potential and hence hindered the direct chlorophenol oxidation on the Ti/RuO2 anode surface. A higher chlorophenol concentration resulted in a faster oxidation reaction on the anode surface. Three different chlorophenol concentrations were tested for the correlation. A faster LSV scan rate could result in more current flow for chlorophenol oxidation. the current density increased at a much faster rate with the LSV scan rate.12 illustrates the peak current density as a function square root of the scan rate for the oxidation of chlorophenol at the anode Ti/SnO2-Sb-Al.1 Electrolysis mechanisms Electrode Ti/SnO2-Sb-Al had a much better performance in electrochemical chlorophenol degradation likely due to two main reasons. The first was the direct chemical oxidation on the anode surface.

4 and 1. The LSV curves in the pure electrolyte showed that the Pt and Ti/RuO2 anodes had a lower oxygen evolution potential. A higher chlorophenol concentration caused the increase of the peak current density on the Ti/SnO2-Sb-Al anode. In comparison. The high overpotential of the Ti/SnO2-Sb-Al anode suggests that the radical reaction forming molecular oxygen was probably restrained. oxygen evolution took place at a rapid rate at a lower potential on the Pt and Ti/RuO2 anodes. Only in the cell of Ti/SnO2-Sb-Al. It is believed that oxygen molecules are formed by radical reactions involving the ·OH radical generated electrochemically. This is why a faster reaction kinetics and a greater current efficiency were obtained in the early phase of EC chlorophenol treatment than the later phase when the organic concentration became lower. the Ti/SnO2-Sb-Al had a higher overpotential of oxygen evolution than the other two anodes. with respective values of around 1. The accumulation of chlorohydroquinone in the cell of Ti/RuO2 was not as higher as that in the Pt cell.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways reason could be the generation of hydroxyl radicals from water electrolysis during the EC process.4.2 Analysis of chlorophenol degradation pathways Among the intermediates. there was no significant accumulation of aromatic compounds throughout the 6 hours 120 .1 V vs. In contrast. Ti/SnO2-Sb-Al anode had a considerably higher oxygen evolution potential of 1. This would facilitate the generation and accumulation of ·OH radical at the electrode surface under a higher potential condition. Chlorophenol and other organics could be easily destructed by the high-energy free radicals in the vicinity of the anode. 8. which was unfavorable to the production and accumulation of ·OH radicals. Different from the situation with the Ti/SnO2-Sb-Al anode for which dechlorination advanced than ring cleavage.8 V vs. suggesting a faster chlorophenol oxidation on the anode. the concentration of chlorohydroquinone was much higher than others in the solution electrolyzed by anode Pt. Chemical concentration did show a great effect on the effectiveness of the EC treatment process. EC chlorophenol degradation would take place at a faster rate for a higher substrate concentration. the reference of the saturated Ag/AgCl electrode. About half of dechlorination took place before ring cleavage and half after ring cleavage (Figure 8. the majority of dechlorination apparently took place after ring cleavage on the Pt anode. the reference.8). According to the LSV experiments.

which gave a partial TOC reduction. and the anode hardly showed any catalytic effect toward the oxidation of chlorophenol and its intermediate products. The Ti/SnO2-Sb-Al anode was highly effective for the oxidation of chlorophenol and its intermediates. the non-selective catalytic activity of the anode was demonstrated as all acids were mineralized effectively. which were reduced to zero by the end of EC treatment. there was transformation of aliphatic acids. In the cells of the other two electrodes. Further degradation of aromatic intermediates produced different kinds of aliphatic acids (Figure 8.5). In the cell of Ti/SnO2-Sb-Al. there was a trend of accumulation of the organic acids. The Pt anode was less effective for chlorophenol degradation. 8% for anode Pt and 5% for anode Ti/RuO2.5 Summary The results of chlorophenol degradation on the three different electrodes were similar to those obtained from the phenol degradation study. In the cell of Ti/SnO2-Sb-Al. Dechlorination was a critical step in chlorophenol degradation.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways of electrolysis. in the Ti/RuO2 cell the decrease of intermediate organics was hardly detected (Figure 8. degradation of the organic acids was actually slower than the destruction of aromatic compounds. The amount of intermediates in the Pt cell decreased at a slow rate. a 6-carbon acid. which comprised a large fraction of the TOC. These results further confirmed that the degradation rates of aliphatic acids on anodes Pt and Ti/RuO2 were much slower compared with that on the anode Ti/SnO2-Sb-Al. Muconic acid. Its long carbon chain apparently increased the difficulty of its degradation. However. For the Pt cell. which could be mostly achieved before aromatic ring cleavage. The Ti/RuO2 electrode was the least effective anode for chlorophenol treatment with an insignificant TOC removal after 6 hours of electrolysis under the same EC conditions. In the Ti/RuO2 cell. Dechlorination was not difficult for the Ti/SnO2-Sb-Al electrode. 8. organic reduction was quite minimal. Complete TOC removal from 100 mg/L could be achieved after 6 hours of electrolysis. In contrast. was the major product of oxidation of aromatic ring cleavage. similar to the phenol treatment test. Its concentrations in all three cells of the electrodes were much higher than other intermediates.6). dechlorination was more 121 . The current efficiencies in the early phase chlorophenol electrolysis were 55% for anode Ti/SnO2-Sb-Al.

maleic acid. and Pt. but accumulated in the cells of Ti/RuO2. 1. phenol. 4-benzoquinone and aliphatic acids of muconic acid. The aromatic intermediates were subsequently oxidized rapidly by the Ti/SnO2-Sb-Al anode. After dechlorination. The experimental results further indicate that the Ti/SnO2-Sb-Al electrode has a non-selective catalytic capability toward organic oxidation. 2-benzoquinone. succinic acid. which is highly suitable for treatment of toxic organic pollutants. pyruvic acid. hydroquinone. oxoglutaric acid. fumaric acid. benzoquinone. 122 . The intermediates according to HPLC analysis included aromatic compounds of chlorohydriquinone. 3-chlorocatechol. actic acid and formic acid. oxalic acid. There were more chlorohydroquinone found in the Pt cells and both hydroquinone and benzoquinone were found at a high level in the Ti/RuO2 systems. 1. 4-chlorocatechol. the organic degradation pathways were comparable to those obtained for EC phenol degradation.Chapter 8: Electrochemical degradation of chlorophenol: Kinetics and pathways difficult on the Pt anode and much more difficult on the Ti/RuO2 anode. malonic acid.

Moreover.1 Coating density The preparation method determined the coating thickness on the electrode.Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes Chapter 9 Discussion: Comparison of the surface morphology and properties between different electrodes 9. 2.1.1 Comparison of surface properties of different electrodes 9. Secondly. catalytical property. The optimal range of coating weight was defined by several parameters.1. coating materials and also the preparation methodology.2 Deactivation of electrode Ti/SnO2-Sb-Al 9. the naked titanium metal substrate uncovered by the coating layer will soon be oxidized under anodic ambient. the porous structure and the creaks of the coating film would allow the penetration of active oxygen atoms through the coating layer to reach Ti surface.1.1 The mechanism of deactivation Electrode deactivation may be caused two reasons. The oxidation of titanium substrate lowered the electrode’s catalytical activity and shortened its service life. Firstly. The coating weight density was about 4 mg/cm2 on the electrode Ti/SnO2-Sb-Al. Sol-gel attachment and thermal decomposition were selected for adhesion of coating materials and formation of the 123 . 9. A sufficient thickness of coating could effectively protect the substrate base and prohibit titanium dioxide formation. such as the substrate. the formation of titanium dioxide and the peeling away of the coating layer. peeling away of the active coating film was another reason which caused deactivation.

which caused the loss of catalytic coating and made the titanium metal. The Ti electrode surface was not as smooth as Pt plate (Figure 9.1.3 Deactivation of electrode Ti/SnO2-Sb-Al The first step was the generation of bubble-like points. A B Figure 9.1.1 A). 9. However there were mud cracks formed on the electrode coating surface.1 B).2. many of small bubble points generated from the original smooth surface. the latter one appeared smoother with the coating film. Comparing to a coated Ti/SnO2-Sb-Al electrode (Figure 9. Small cracks could be easily peeled off. Figure 9.Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes active compounds. Figure 9.2 B).2 C. The unevaporated solvent of precursor salts might be oxidized by the penetrating oxygen atom. The Ti electrode after coating was shown in Figure 9. forming these bubble like points in Figure 9. comparison between untreated and treated surfaces. exposed to the oxidation atmosphere.2 provided a clear morphology of the electrode surface by SEM.2 D.2 D. All those holes were filled with coating materials and the plate became smoother.2 Images of the titanium plates The fresh titanium plate after etching showed a rough surface. More and more cracks generated from these 124 .2.1 Titanium plate under microscope 9.2 A was a vision of the titanium plate surface after etching. In Figure 9. and the Ti surface area was effectively. a lackluster gray color under a microscope at 500× (Figure 9.

coating materials peeled off from the electrode surface (Figure 9. the deactivation of the Ti/SnO2Sb-Al anode underwent through a three-step process. A B C D E F Figure 9.2 F). 125 . which accelerated the penetration of oxygen atom.2 E). The incomplete evaporation of sol-gel solvent could be the major reason. The cracks split the coating surface into small pieces. accompanied by the shear of disturbing. The formation of carbon dioxide might cause the formation of new cracks on the electrode surface and finally led the peeling of the coating materials.Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes sports on the electrode’s coating surface during electrolysis (Figure 9.2 SEM images of the electrode in different service stages. In general.

1. Sn3d5/2 Figure 9. The major dopant element Sb also could be found by XPS even though the amount was quite small with a low peak.1 XPS analysis Figure 9. though accompanied with other values (Safonova. In general. different peaks of Sn showed its different locations. Oxygen was another nonmetal component with the metal elements. which had the highest response peak during the full scan process.3 shows the full scan results of the electrode Ti/SnO2-Sb-Al from zero to 1100 ev for testing the component of the coating materials and their locations. 2000.Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes 9. Figure 9. Amanullah.3. 1998).3 A typical full-width XPS spectrum of the Ti/SnO2-Sb-Al electrode Sn3d3/2 O1s Sb3d3/2 C1s 9.2 EDX analysis 126 . The valence of Sn located at the highest point also was confirmed as 4+.1.3.3 provided an overview of the coating materials on electrode Ti/SnO2-Sb-Al. and O also could be detected. C. On the electrode surface.3 Coating surface components 9. Simultaneously. Aluminium could not be detected. the major metal component was Sn.1. Elements Sb.

The EDX scan was carried out based on the scan of SEM in the part through the red line.4 and 9.4 EDX analysis of electrode Ti/RuO2.89 1.79 7.73 71.67 0.34 0.77 20.53 4.52 3. SEM-EDX combination graphs afforded a 3-dimensional view of the electrode surface.Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes Electrodes Ti/SnO2-Sb-Al and Ti/RuO2 were tested and the results are shown in Figures 9. EDX scan also provided full information of the components of surface coating materials.18 8.77 Figure 9. 127 .90 48.5.20 Atomic% 12.92 3. The surface of electrode Ti/SnO2-Sb-Al Element CK OK Cl K Ti K Ru L Sn L Sb L Totals Weight% 2.83 5.37 3.

Sn. Table 9. On the electrode Ti/SnO2-Sb-Al. 9. The coating materials had four kinds of metal elements on the electrode Ti/RuO2.1.5° 128 . The right column of Figure 9.75° 81. The high concentration of element Sn apparently increased the catalytic activity of the electrode. which recorded the state of drops when they kept stable on the surface of different electrodes. The high hydrophilicity of electrode Ti/SnO2-Sb-Al greatly decreased the surface tension of the water drop. Electrode Ti/SnO2-Sb-Al differed greatly from the other two electrodes of the advancing angle and receding angles. and a low receding angle even less than 10°.6 was another method for contact angle measurement. respectively.75°.75° and 81.5°. which is far larger than any element in electrode Ti/RuO2.5° θa 31. Ti. The advancing angle and receding angel of three electrodes were listed in Table 9. A plate shape of water drop also has a low value of the advancing angle of 31.1 Contact angle (advancing and receding contact angle) measurement.10%. The water drops on the electrodes Ti/RuO2 and Pt showed a similar shape. and Sb.75° 69. Electrode Ti/RuO2 and Pt. Higher hydropilicity surface could greatly decrease the contact angle while drops were imbibed of the surface. There was not much difference between their contact angles. the water drop has shown a flat shape with a contact angle of 17°. The major components of coated electrode Ti/SnO2-Sb-Al was Sn.1. with the atomic percentage as high as 17.6).4 Contact angle and hydrophilicity Contact angles were measured with digital photos (Figure 9. The total amount of atomic metal (MT) percentage was 15.Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes appeared uniform with many evenly distributed small cracks. The low hydropolicity of electrode Ti/RuO2 and Pt may prohibit the transformation of organic molecules from water phase to the solid surface. 67° and 72°. Ru. have the advancing contact angles of 69. with a similar shape of water drop attached on the surface. and the atomic oxygen percentage was 71. θ Ti/SnO2-Sb-Al Ti/RuO2 Pt 17° 67° 72° θr 8° 27. respectively.25° 28.21%.34%.

129 . two aromatic compounds and two aliphatic acids were selected as model substrates for the adsoption tests.90 17. Here.35 Atomic% 81.78 34.5 EDX analysis of electrode Ti/SnO2-Sb-Al.21 Figure 9.1.5 Organic adsorption onto the electrodes The adsorption capability comparison between the three kinds of electrodes is listed in Table 9.25 20.Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes Element OK Al K Sn L Totals Weight% 13. 9.88 0.32 0.2.

Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes I II Sn Pt Ru Figure 9.6 Contact angle measurement. 130 .

45 2. Also. appeared to have a great resistance to contamination.1 EC degradation of organic matter On phenol degradation from the initial 100 mg/L.55 0. chlorophenol was destructed nearly completely after 4 hrs by the Ti/SnO2-Sb-Al anode from the initial 100 mg/L.52 mg/m2 0.08 Maleic acid mg/L 2. respectively. However. lowest adsorption to aromatic acids prohibited further degradation of intermediates. and just 30% and 10% TOC removals were produced by the Pt and Ti/RuO2 anodes.2 Comparison of different electrodes for organic electrolysis 9. Electrode Ti/RuO2.Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes Electrode Ti/SnO2-Sb-Al showed better adsorption of aromatic compounds than Ti/RuO2 but worse than Pt. only 42% phenol removal was achieved after 6 hrs of electrolysis. Phenol mg/L Sn Ru Pt 1. which would limit further oxidation reactions on the electrode surface. 55% chlorophenol was oxidized by the Pt anode and only 10% chlorophenol was destructed by the Ti/RuO2 anode.04 0. electrode Ti/SnO2-Sb-Al took 3 hrs to achieve complete destruction and 5 hrs by the Pt anode.49 0.05 1.56 0.75 mg/m2 0. Metal Pt has a high specific adsorption of aromatic compounds.94 Benzoquinone mg/L 1. 131 . just 36% and 12% TOC removals were reached by the Pt and Ti/RuO2 anodes.98 Fumaric acid mg/L 2. Table 9. respectively.61 0.15 3. Complete TOC removal was achieved after 5 hrs on the Ti/SnO2-Sb-Al anode.94 0.30 mg/m2 0. Complete TOC removal was achieved after 5 hrs on the Ti/SnO2Sb-Al anode.2 The quantities of organics adsorbed on different electrodes. The order of organic removal efficiency is: Ti/SnO2Sb-Al > Pt > Ti/RuO2.93 mg/m2 0. In comparison under the same current input condition.10 0.28 0.2. The same order of chlorophenol organic removal capability is: Ti/SnO2-Sb-Al > Pt > Ti/RuO2. At the same current input rate to the Ti/RuO2 anode. Adsorption maybe also correlated to the contamination of electrode.0 0.13 9.25 1.2 7.25 0.18 0.

It is apparent that dechlorination was an important limiting step in the electrolysis of chlorophenol by electrodes Pt and Ti/RuO2.2 Organic degradation pathways In a simple way. the reference. the chloride concentration reached the maximum. The Ti/SnO2-Sb-Al anode had a considerably higher oxygen evolution potential of 1. The chemical aliphatic acid degradation on electrode Pt was almost zero except oxalic acid. which led to much slower chlorophenol destruction and organic degradation. the reference of the saturated Ag/AgCl electrode. The major components are aliphatic acids after 6 hrs of electrolysis. Complete mineralization is impossible on plate Pt. On chlorophenol degradation. Phenol could also be oxidized directly at the Pt surface.8 V vs.5 V for different phenol concentrations to the Ti/SnO2-Sb-Al anode. the phenol degradation routes could be written as: 1O ] 2O 3O Phenol ⎯[⎯→ Aromatic − Compounds ⎯[⎯]→ Aliphatic − Acids ⎯[⎯]→ CO2 ⎯ ⎯ ⎯ Electrode Ti/SnO2-Sb-Al is effective in any step of oxidation [O]. the peaks of direct anodic oxidation of phenol were located at about 1. with respective values of around 1. dechlorination is another step that showed the great difference for the three anodes. Plate Pt is effective in the first two steps of oxidation and stop at aliphatic acid oxidation. This would facilitate the generation and accumulation of ·OH radicals at the electrode surface under a higher potential condition. and 1/3 to plate Pt. The corresponding phenol oxidation potential at Pt 132 .2.3 Surface electrochemical properties Oxygen evolution potential may be closely correlated to the ·OH radical formation and the electrolysis oxidation process. The Pt and Ti/RuO2 anodes had a lower oxygen evolution potential. Chloride release was detected at a much slower rate in the chlorophenol solutions electrolyzed by the Pt and Ti/RuO2 anodes. Phenol degradation on electrode Ti/RuO2. which was unfavorable to the production of ·OH radicals.1 V vs.1.2. the rate of oxidation was much slower than that at the Ti/SnO2-Sb-Al anode. when 95% chlorophenol was destructured. and there is no limiting step from phenol to the final carbon dioxide. However.Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes 9. During the LSV tests. 9. with smaller peaks observed in the LSV curves. the whole process rate is 1/8 to the electrode Ti/SnO2-Sb-Al. After 2 hrs of electrolysis on Ti/SnO2-Sb-Al.4 and 1.1.

the doping element Ti and Sn are 5.Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes was somewhat lower than the potential on the Ti/SnO2-Sb-Al anode. The atomic concentration of Ru in the coating of Ti/RuO2 is 3. organic solution electrolysis allowed a new current peak during the EC test.1 V vs. Except oxygen evolution. This was indicated by the peaks of current density in the LSV curve for the addition of organic matter in the electrolyte. The first was the direct chemical oxidation on the anode surface.52% 133 . Oxygen evolution was the dominant electrochemical reaction that allowed little increase in potential and hence hindered direct phenol oxidation on the Ti/RuO2 anode surface. The element analysis of surface coating layer illustrate that electrode Ti/SnO2Sb-Al has 17. According to the LSV experiments. Another reason could be the generation of hydroxyl radicals from water electrolysis during the EC process. the reference.92%. oxygen evolution took place at a rapid rate at a lower potential on the Pt and Ti/RuO2 anodes. Pt and Ti/RuO2 anodes had lower oxygen evolution potentials. Similar results could be found on chlorophenol degradation. Organics could be easily destructed by the high-energy free radicals in the vicinity of the anode. In the pure electrolyte water discharge showed that the Ti/SnO2-Sb-Al anode had a considerably higher oxygen evolution potential of 1. Direct phenol oxidation on the Ti/RuO2 anode was much more difficult. It is believed that oxygen molecules are formed by radical reactions involving the ·OH radical generated electrochemically. Additionally. organic matter degradation was limited by the limiting activator metal atoms. In contrast.4 EC oxidation mechanisms Electrode Ti/SnO2-Sb-Al had a much better performance in electrochemical organic degradation likely due to two main reasons. the reference of the saturated Ag/AgCl electrode.4 and 1.21% atomic percentage of Sn. the Ti/SnO2-Sb-Al had a higher overpotential of oxygen evolution than electrodes Pt and Ti/RuO2. which was unfavorable to the production and accumulation of ·OH radicals.8 V vs. 9. The high overpotential of the Ti/SnO2-Sb-Al anode suggests that the radical reaction forming molecular oxygen was probably restrained.2. The higher proportion of active atomic would increase the catalytic activity of the coating film. This would facilitate the generation and accumulation of ·OH radical at the electrode surface under a higher potential condition. Power could be utilized for direct degradation of substrates on the anode. with respective values of around 1.

89%.2 Investigation of EC organic oxidation mechanisms The EC oxidation mechanism was only discussed from electrochemical properties. Pt fouling is the limiting of its application and its cost as well. even can not sustain several times of LSV scanningf. respectively. Electrode Ti/RuO2 has a long service life for its application in alkali industry.2.3. 9. Further discussion from the aspect of energy should be carried out. Higher concentration prohibits the transformation of oxygen from the outside into the crystal lattice of metal oxide.3 Future work 9. electrochemical reaction direction and the components of surface coating materials. the percentage of oxygen of the coating layer is another limiting issue. A slow deactivation process is accompanied by a slow increase of voltage on electrode Ti/SnO2-Sb-Al. which helps the accumulation of ·OH on the electrode in favor of organic matter oxidation. On the other hand. which is the deathful shortcoming of this electrode. and the cycle for electrode replacement is normally ten years. Electrolysis is a power consumption process and the electrochemical reaction 134 . and adjusting the method for internal layer preparation might also advance its service life.3.88%. More development work should be focused on extension of its service life. about 10% higher than electrode Ti/RuO2. A well prepared electrode could support continuous 16 hrs of electrolysis.Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes and 3. Introducing another metal element might increase the stability.1 Improvement of the electrode preparation techniques Electrode Ti/SnO2-Sb-Al is good at toxic organic removal while is poor at its service life. 9. Anode Ti/SnO2-Sb-Al has a higher percentage of 81. Pt is easily be contaminated by substrate matters and their intermediates. 9.5 Stability of the electrodes Electrode Ti/SnO2-Sb-Al has far better performance than the other two electrodes for organic degradation.

The structure of metal oxide crystal lattice and the transformation of electrons and holes involve energy. 135 .s.Chapter 9: Discussion: Comparison of the surface morphology and properties between different electrodes accompanied by the energy transfer. Hydrophilicity discussion is incomplete and also should be advanced by energy calculation. Surface materials are also related to the energy matter.

For the saline sludge with a NH4+-N of around 500 mg/L. The rate of EC denitrification increased with the current intensity applied. 136 . The best current efficiency for nitrogen removal was obtained with a gap distance between the electrodes at 8 mm. The power consumption rates were similar at around 30kWh/kg-N for both the batch reactor and CFSTR for nitrogen removal from the landfill leachate. Additional electro-flocculation with a pair of iron needle electrodes could increase the organic removal by sedimentation from less than 30% to more than 70%. Therefore. and the power consumption rate for nitrogen removal of the sludge liquor was around 23 kWh/kg N.Chapter 10: Conclusion Chapter 10 Conclusions 10. The experimental results demonstrate that the EC process is highly effective for denitrification of the high-strength wastewaters. Electro-chlorination is considered to be the major mechanism for EC denitrification. there was no significant accumulation of chloramines during the EC reactions. The formation of chlorination by-products (CBPs) appeared to be minimal as the total trihalomethanes (THM) were below 300 μg/L. complete nitrogen removal could be achieved within a contact time of 1 hr. the EC process including both electro-denitrification and electro-flocculation can be developed as a cost-effective treatment method for saline sludge liquor and landfill leachate. Nonetheless. nitrogen could be removed from an initial ammonia concentration of more than 1600 mg/L by 3 hrs of electrolysis. For the landfill leachate with a chloride content of about 2500 mg/L.1 Electrochemical treatment of saline sludge centrate and landfill leachate for denitrification and organic removal A lab-scale electrochemical (EC) system with Ti-based electrode plates was used for treatment of saline sludge liquor from a sewage treatment works and raw leachate from a landfill.

Ti/IrO2 and Pt anodes. For the other two cells with the Pt and Ti/RuO2 anodes. but accumulated in the cells of Ti/RuO2 and Pt anodes. just 36% and 12% TOC removals were reached by the Pt and Ti/RuO2 anodes. The EC treatment experiments were conducted for phenol and chlorophenol using the Ti/SnO2-Sb-Al electrode. were oxidized rapidly by the Ti/SnO2-Sb-Al anode. Phenol with an initial concentration of 100 mg/L could be readily destructed on the Ti/SnO2-Sb-Al anode.2 Degradation of phenol and chlorophenol by electrolysis with the Ti/SnO2Sb-Al and other electrodes A double-layer coating technique was employed to make catalytic active anodes in Ti/SnO2-Sb-Al for electrochemical oxidation of toxic organic pollutants. and those acids were reduced to zero in concentration after 6 hrs. organic acids accumulated in the solutions. Ti/RuO2 or Ti/IrO2. For organic removal. under the same electrolysis conditions at a current density of 20 mA/cm2. Similarly. there was apparent formation of colored polymeric compounds during phenol electrolysis. the best treatment performance was obtained with electrode Ti/SnO2-Sb-Al. In addition. For organic reduction. while the TOC removals were only 30% and 10% for the Pt and Ti/RuO2 anodes. The HPLC results show almost no considerable accumulation of aromatic compounds in the solution electrolyzed by anode Ti/SnO2-Sb-Al.Chapter 10: Conclusion 10. Oxoglutaric acid and oxalic acid were the most dominant acids in the Ti/SnO2-Sb-Al cell. including aromatic compounds and aliphatic acids. however. Aliphatic acids were the predominant intermediates produced by EC phenol oxidation and also the subsequent benzoquinone oxidation. followed by Pt and then Ti/RuO2. while more benzoquinone were found in the Pt cell and both hydroquinone and benzoquinone accumulated in the cell of Ti/RuO2. respectively. however. respectively. during the same electrolysis period. however. The chloride ions in solution 137 . The intermediate products of EC phenol degradation. in the electrolysis of chlorophenol. complete TOC removal was achieved after 5 hrs on the Ti/SnO2-Sb-Al anode. in comparison with the performance of other electrodes including Pt. However. Complete chlorophenol destruction from a concentration of 100 mg/L could be achieved after 4 hrs of electrolysis by the Ti/SnO2-Sb-Al anode. only 55% and 10% of chlorophenol could be destructed by the Pt and Ti/RuO2 anodes. its degradation was considerably slower at the Ti/RuO2. 100% TOC reduction could be achieved on the Ti/SnO2-Sb-Al anode.

In contrast. its high overpotential of oxygen evolution would allow more production and accumulation of hydroxyl radicals near the anode surface under a higher potential condition. including chlorohydroquinone and chlorocatechol.1V for the Pt and 1. It is argued that under the electro-catalytic condition at the Ti/SnO2-Sb-Al anode. However. Maleic acid formed from ring cleavage could be oxidized directly to oxalic acid that can be readily mineralized by EC oxidation. there could be two main reasons for the high effectiveness of the Ti/SnO2-Sb-Al anode in phenol and chlorophenol degradation. The accumulation of intermediate aromatic compounds. Addition of phenol in the testing electrolyte resulted in new peaks in the LSV curves for anode Ti/SnO2-Sb-Al. However. Based on the EC degradation performance and HPLC results modified pathways of EC phenol degradation at different types of electrodes were proposed. Organic matter could be readily destructed by the high-energy. for the Pt and Ti/RuO2 anodes. The surface property of the electrodes appeared to affect the reactions involved in EC organic degradation.Chapter 10: Conclusion from dechlorination of chlorophenol apparently increased the rate of chlorophenol electrolysis compared to the tests of phenol degradation. In comparison to the conventional Pt and Ti/RuO2 anodes. would lead to the formation of more stable polymeric chemical compounds. ring breakage became more difficult. There were more chlorinated aromatic intermediates detected by HPLC. the aromatic ring cleavage takes place rapidly. nonselective oxidant of free radicals. First. which suggests direct phenol oxidation on the anode surface.3 Surface properties of electrode Ti/SnO2-Sb-Al and their effects on EC organic degradation Different electrodes were characterized for their electrochemical behaviors and surface properties. which were considerably higher than 1. phenol addition did not change their voltammograms significantly. 10. most of chlorophenol was destructed into phenol which was further oxidized.3V for the Ti/RuO2 anodes. However. The three types of electrodes performed rather differently during LSV tests.9V for the Ti/SnO2Sb-Al anode. which was unfavorable to the 138 . such as hydroquinone and benzoquinone. The overpotential of oxygen evolution was 1. oxygen evolution took place at a rapid rate at a lower potential on the Pt and Ti/RuO2 anodes. at the Ti/RuO2 and Pt anodes without significant catalytic functions.

were less favorable for use in the EC treatment of organic pollutants. 139 . Second. The higher proportion of active metal atomic would increase the catalytic activity of the coating film toward organic oxidation. However. because their lack of the electro-catalytic capacity and the production of some intermediates that were more refractory to EC and additional treatment. specific anode surface treatment such as the SnO2-Sb-Al coating provided the anode with an apparent catalytic function for rapid organic degradation. which was much difficult to be achieved with the Pt and Ti/RuO2 anodes. Thus. such as Ti/RuO2 and Pt.Chapter 10: Conclusion generation of hydroxyl radicals. Better adsorption of the organic on the anode surface would improve electron transfer for direct organic oxidation and allow a more effective indirect oxidation by hydroxyl radicals generated on the anode surface. The effective EC organic oxidation was probably brought about by both direct electron transfer of the organic on the anode surface and the attack of hydroxyl radicals generated from anodic water electrolysis. some anode materials. the surface properties. The element analysis of surface coating layer illustrate that electrode Ti/SnO2-Sb-Al had 17.2% atomic Sn. In addition. The Ti/SnO2-Sb-Al electrode appeared to have a high affinity with organic substances than electrode Ti/RuO2. In brief. power could be utilized for direct oxidation of chemical compounds on the anode. the peaks in the LSV curves of the Ti/SnO2Sb-Al anode in phenol solution indicated direct organic oxidation on the anode surface. hydrophobicity and chemical adsorption potential. such as morphology. could also affect various reaction steps of EC organic degradation.

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