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    How Does Periodic Polarity Reversal Affect The Faradaic Efficiency and Electrode Fouling During Iron Electrocoagulation

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    CUEVA VASQUEZ BRYAN ALBERTO

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    Water Research 208 2021) 117497 Contents lists available nt ScienceDirect Water Research ELSEVIER journal homepage: www-elsevier comMlocate/watres: ® How does periodic polarity reversal affect the faradaic efficiency and sae electrode fouling during iron electrocoagulation? Héline Chow”, Markus Ingelsson”*', Edward P.L. Roberts”, Anh Le-Tuan Pham" {Deere of Cl nd sre Bering. very of Wate, Watrioa. Ovo ON N2L 301, Conan ° Deparment of hoi nd ean Eerie Cnr of Cele, Cay, abo T2W IN, Cana Beewoce oling Feral ieney Polity tees Lscuocongulation (EC is a promising elecuoctenieal water wentment technology. However, major challenge to susaning effective long-term EC operation fs conolling the precipitation of mateials on the electrodes, commeniy tefered to as fouling. Pesodiealy reversing eleeuode pola has been suggested as an isin fouling mitigation strategy and is often implemented in EC flelé applications. However, the wiley of this approach has not been investigate in etal nl study, de effet of polity reversal (PR) on the performance ‘OF EC slag lon eletodes was examined wader diferent water chemist conditions anda a ange of eves fequencis.Irwasobeerved hat the faadale efficiency in PRCEC was always ler than that ia the EC ystems operated with a diet cure (Le, DCEC). It was ao observed thatthe faradie efficiency progressively Aecrened asthe eurrent reversal fequency insensed, with the faa efency dropping a low as 10% when the PR interval was 05 min. Results fom fouling layer, uouopotensiomenic, and eyele volanetie in ‘eigatons indicated thatthe decrease in he fatale efiieny was cused by (i) Incense ele tod oulng by ton preiptates an (i) eleenochemical side rections at the eleetodeelectlyte interface. The extent ofthese fet was dependent on the soln chemists oxyanions an slide were fxn to be pavtelly deinen to the performace of PREC, causing severe elecvode fouling while decveasing the faradal efficiency, Fouling ‘ould be sltigated by increasing the solution convection rate, resulting ina sbear on theelactuode susace that emaved tn and other eletrochemealy reactive species fom the eletodes 1. Introduction 2009), Both fone forms of iron further reat with water co form (oxy hhyénoxides, which function as coagulants for contaminant removal (Dubravisk et al, 2015), Compared to chemical coagulation (CC) (Le, the addition of iron of aliminsns sl Hleetrocongulation (EC) Is an electrochemical water creatment technology tht has becom increasingly popular ving to its ability to efficiently remove various types of contaminants (M. Yousuf A. ols! ‘al, 2001). BG involves the application of electric current co corrode metal eleetrodes to produce coagulant (Yasri ctl, 2020). Steel elec trodes are commonly used in EC (Fe-EC) due to thelt low cost (Bandar ‘et al, 2020). The corrosion of a steel anode generates Fe® vin the following reaetion (Van Gentiehten eta, 2017) Poy eo Fe yg | 20 B= 044 V v5 SHE o Subsequently, some Fe? may be oxidized 10 Fe™* by disolved ox: ‘ygen. (While che direct electrochemical production of Fe is posible, previous studies have reported that almost all Fe ions produced in ECare Fe (Dubrawski eta, 20155 Lakshmanan et al. 2009; Moreno Cet al, * Coxresponding authors. ), EC offers several advantages Including reduced chemical sage du to the elimination of eounter los (Garcia Segura eta, 2017; ingelsson etal, 2020; M. Yousuf A. Molla cr al., 2001), improved coagulant mixing due to corrosion aver the tire electrode surface (as opposed to point-addition in Cc), contol lable coagulant production via the electrical current (which permits & high degree of automation), and reduced coagulant dosing ad sludge production owing to inereased coagulation efficiency (Garcia Segura eral. 2017; Ingelsson et a, 2020; M. Yousuf A. Molla ets, 2001; ML Yousuf A Mollet a, 2001), Additionally, EC does not require sup plemental neutralizing chemicals du to the production of OH” ions at the cathode mall adareses: edward sobetsucalgary.ca (EPL Robets), aah pham@uwatsio.ca (AL. Pham). * puthors asume eo Rit auorship hnups://doL.og/10.1016/}. wats 2021117497 Received 10 May 2021; Received a ese fm 26 July 2021; Accepted 27 July 2021 ‘Availabe online 2 Ags 2021 (0043-13547 2021 Ekeviet Lic, All ight sete 21,0 4-26 20H p+ Hag b = Its also worth mentioning that because of reaction 2), an alkaline boundary layer is developed at the cathode-electolyte interface sépanjeh Hojaghan et s., 2010). Simultaneously, the hydrolysis of and Fe°* jons generates H°, creating an aedie boundary layer at the anode (Yasri and Gunasckaran, 2017): Fe" 0.50; 4 2H,0 + Fe(OH), +H @ 083 V ws SHE, 2 ‘Therefore, the pHi profile within an EC reactors distine from that of ce, A significant opeaitonal challenge forthe fong-term operation of EC Is the build-up ofeleetode surface layers (refered (0 as ful) dana et al, 2020; Chow and Pham, 2021; tngelsson et al, 2020; Miller cet al, 2010; Timmes et al, 2010; Van Genuchten etal, 2016), which leads to diminished treatment performance, Specifically, it has been shown that the accumulation of a non-porous insulating surface layer Increases the resistance of the electrom-transfer processes at the electrode electrolyte interfaces, thereby inducing a passvating effect increasing the cel voltage, and consequently increasing operating costs CAmrose et a, 2014; Bandar et al, 2020; Chow and Pham, 20213 Ingelsson et al., 2020; Maller et al, 2019; Timmes et al, 2010) Furthermore, at sfiiently high overpotentils its possible to trigger ‘side reactions such as the electrochemical oxidation of water and Cl 2,050, +41! $de B= 123 V vs SHE ” 2C1 oC 420 6 V vs SHE ° ‘These side reaetions wil divert the current away from renetion (1), ‘reducing the coagulant production efficiency (Duibraviski ots, 2015), ‘while it as Deen shown that electrode surface layers can also e porous ‘and coudutive (and, therefore, will havea negligible effect on the cell, voltage) (Bndan ets], 20205 Sehnniki, 2002), a thick fouling layer ‘ay inhibit the transfer of coagulant fom the anode to che bulk sol tion, hence reducing, EC performance (Van Genuchten et al, 2016) ‘Additionally, the accumulation of materials on the surface of the elec trodes may increase the pressure érop through the EC cell, or plug the «ell fter prolonged operation. TTo overcome the operational Issues described above, electrode fouling layers aust be removed or avoided altogether. Methods sca as ‘mechanical cleaning (brushing/straping) or washing the electrodes with ‘acid have been proposed (Anirose etal, 2014; Bandar ets, 20205, Lakshmanan etal, 2009; Miller et al, 2019; Times etal, 2010) tis ‘also possible 10 avoid calcium: and magnesium containing scales by installing pretreatment nits—suich as ionexehange—to remove Cx** ‘and Mg? upstream ofthe EC reactor, While effective, these approaches require either reactor shutdown or additional infrastructure, whieh significantly increases che system's cost and complexity. Another method tht ns been proposed forthe mitigation of eletrode fling is polarity reversal (PR) (Eyvaz et al, 20095 Keshmirizadel etal, 20115 Mao et al, 2008 Yang etal, 2015). This technique involves intermit: tently reversing ce current direction such that the anode becomes the ‘cathode and vice versa. Each time the ewrent diection i switehed, the ‘evolution of Hag) (reaction (2)) at the cathode ean dislodge fouling layers that accumulated on the electrode in the previows current eyele (Gian et al, 20195 Timms etal, 2010), Om the anode (which served as the cathode prior to current switching) fouling layers ean be dislodged ‘due to the corrosion of the underlying eletrode (Bian etal, 2019), ‘Additionally, the inversion ofthe boundary Inyer pit at each electrode may dissolve fouling layers. For example, Ca- and M-containing min ferals precipitated in the cathode's alkaline pH environment may dissolve when the boundary layer becomes acide following PR. Aldhougl PR can potentially prevent electrode fouling, its effect on the overall performance of EC renanins poorly understood, and con: flictng results have been reported inthe literature (Feieo el, 2015 Ingelson et a, 20205 Miller eta, 20195 Timmes et al., 2010; Yang War Ree 208 (2028) 117697 sal, 2015). For example, a recent study reported the build-up of thick electrode fouling layers in an Fe EC system in which the electtode po larity was periodically reversed (ile et al,, 2019). This result rises ‘questions about the ability of PR to mitigate electrode fouling. As another example, while high eoagulant production efficiencies were reported in some PR-EC studies (Qzyonar and Karagozogl, 20154 Yang eral, 2015), several other studies, including outs, have demonstrated that coagulant production efficiency in PREC decreased with increasing PR frequeney, and can be significantly lower than the efficiency in EC systems operated with a direct current (h, DC-EC) (Fekewe et al, 20165 Miler et al, 20195 Yang etal, 2015; Chow and Phas, 2021). While efflelent anodle dssolutlon does not guarantee successful contaminant removal, ics pre-requisite for effective EC operation. Therefore, the ‘optim PR frequency should ensee high coagulant prodicton while voiding electrode fouling. However, a wide range of oprimim PR in tervals (0.515 mia) have been reported, presumably due to differences im the electrode material and water composition employed in past studies (Grated aid Smoczyiskl, 19855 Heldmann and Calmano, 2008; Maer etal, 20195 Shao qin etal, 20145 Timmies eta, 2010). ‘The purpose of this study wins to investigate if PR is an effective method to mitigate fouling and sustain effective anodic metal disso tion in EC. Building upon our previous study (Chow snd Pham, 2021), whieh investigated the effets of current density and polarity reversal ‘ime on the coagulant production in PR-EC, this eurrent study forused specifically on the effects of water chemistry and flow dynamics in PREC that employs Fe electrodes. We hypothesize that water chemistry plays significant role in Fe PREG, since the corosion and fouling of Fe efectrodesare strongly influenced by various ions such as Ct~ (which ean Induce piting corrosion and prevent passivation) alsin ira) fal, 2008; Van Gemsichten et a, 20175 Xu etal, 2015), S042 and PO.” (which have een shown to inhibit Fe corrosion and increase overpotentials\Lakshmipathiraj et al, 2008 Refaey, 2005; Van Gen lichen aly 2017), CR2*, Mg, and dissolved sien Cwiel ean accelerate electrode fouling)(Ha0varu et al, 2020). To test this hy- pothesis, a series of batch and continous flow experiments were can ducted to quantify the faradaic efficiency and the amount of Fouling on the electrodes. In addition, chronopotentiometry and cyclic voltamme- try were employed to identify the elecrochemicsl processes occurring during PREC. 2, Materials and methods 21, Maverils All chemicals were of reagent grade and were used without futher purification. The electrodes were Fe rods (4.8 mm diameter, 9896 purity) obtained from Metal Supermarkets, or steel plates (1 emt» 1 em, 9986 purty, ASTM A109 steel) obtained from MeMaster-Car. Although these materials were of different grade, suull impurities Ihave been shown to have negligible effect on faradaiceicleney in Fe EC (Miller etal, 2019) Four types of synthetic water samples were used to study the effect of solution chemistry on faradaie efficiency and fouling: 1» NaCl in deionized water 1©ag804 in defonized water ‘Synthetic grouncueater (SGW) « Synthetie produced water (SPW), emlating the chemical profile of These solutions were chosen for their increasing complexity and varying effects on EC performance. For example, the SGW and SPW solutions contained Dulfers (eg, HCO ), whieh have previously been reported to affect EC performance by creating a passive layer at the electrode surfaces whieh prevents the release of Fe(H/AH) (Van Ges uch eta, 2017) In the NaCl solution, the faradaic efficiency ean be ‘expected to be high because Cl can help dissolve the electrode surface layers and facilitate pitting (Arroyo etal, 2009). In contrast, 80. has been shown to promote Fe passivation (Van Gesuchten tal, 2017). the SGW solution, Ca? and Mg?* are expected to contribute to the fouling of the cathode in DC-EC (Doggaz etal, 2019), and on both ‘electrodes in PREC (Chow and Pham, 2021). Lastly, the SPW contains HS”, whieh can be electochemiealy oxidized into elemental sulfur (8°), ‘and/or can react with Fe to generate sparingly soluble iron sulfide ainerals (FeS) (Chow an Pham, 2019). The ionie compositions of the tested solutions are presented in “Inble 1. The chemicals used to prepare the solutions were NaySiO3 (or NasSi0se9H0), NaHSeH,0, MgGls (Or MgClze6H20), CaCl, NazSOx INaHOOs, NaNO, NaiPOyeH20 (Or NasPO4e12H,0), ad NACI. The PH ‘of the solutions was adjusted to their intial pH sing 1 MHC, All so lutions were prepared sing 18.2 Mftecm water. 2.2. Coagulant production experiments ‘The effects of polarity reversal time (PRT) and water chemistry on faradaic efficiency and electrode fouling were examined using a single ‘pass continuous flow reactor (V = 200 ml) that was operated for 6k (ig. 18). The reaetion solution was supplied ro the reaetor by a per static pamp at a flow rate of 10 ni. min, resting in a recention tne ‘of 20 min. Within the reactor, the solution was continuously mixed by a magnetic stir bar. The reactor was covered with li with openings that held the Fe rods and for solution sampling. The Ferods were spaced 2 em. ‘spar, and were submerged ro @ depth of 6 em, resulting in an active surface area oF7.6 emi? 0.1 em. Inadlition a reference electrode (3 M NaCl Ag/AgCl, 0.209 V versus SHE) was placed 0.25 em from one of the ‘other to electrodes, Before each experiment, the electrodes were son ieated in 1 M HC! for approximately 1 min, polished with 1500 grit sandpaper, and rinsed with deionized water. ‘The reactor was controlled by a potentostat (VSP, Biologie Science Instruments), which applied a constant current of J= 0.1 A (i= 13 mA ‘ny ®)- Experiments were conducted ether in the DC mode, of in the PR mode with PRTS of 0.5, 1 or 2auin, ACt— 3 ana 6 hy, Sm Liquid sanples ‘wore withdenwn from the tenctor, and were digested in a solution consisting of 3 wt 96 HNOs and S wt, % HCL Subsequently, che digested solution was subjected to inductively coupled plasm-optical emission specitoscopy CICP-O88) analysis, To examine dhe electrons surtace morphology and elemental composition, the electrodes were removed fromthe reactor nt the end ofthe experiments, air dried, nd analyzed using an FEL Quanta FEG 250 Environmental Scanning Microscope (CESEMD) that was coupled with an Inca energy dispersive Xray (EDX) speettonieer ‘The ICP-OBS analysis described above provides the total amount of ‘Table 1 Chnroceristis of et sitions? NSO, Syotieie Goud symbole Podued Wace sow? Nox (a8) 53 Hoos = 1,700 Poche) 25 sess m2 8 (as "Concentration of solutes ace i mg/L, pan etal 2016) chow and Pham, 2019) War Ree 208 (2028) 117697 Fe released into the bulk solution, To measure the amount of Fe ac uated inthe fouling layer on the electrodes, a separate set of expe tients were conducted in which the reactor was operated in. the batch mode for 1h. Subsequently, the rods were removed, ther surface layers were digested by submerging the rods into acid, and the amount of Fe in the digestate was quantified by 1CP-OES, It is acknowledged that this approach only proved a semi- quantitative estimate ofthe amount of Fe he fouling layer, since the underlying rod could also have been dis solved. To account for the Fe that was released from the underying rod, ‘contol experiment was performed wherein a new rod (Le, foul free rod) was submerged in the acid for the same duration, and the aniount Fe dissolved In this experiment was subkracted from that released inthe digestion of the rod and the associated fouling layer. 29. Chronopotentiotetry and cyclic voltammetry A series of eheonoporentiomertie and eyeie voltammotrie expert ronts were condiicted to gain further insights into the electrochemical processes occuring in DC-EC and PR-EC. These experiments employed & 1 emt = 1 em stel plate (Le, the working electrode) housed in @ 3D: printed polycarbonate reactor (V = 100 mil) such that only one side of the eleetrode was exposed to the solution (Pig. 1b). Before each exper iment, the working electrode was polished with 800 and 1500 grt sandpaper (1214 black fee, Norton) until the surface was smooth and reflective. The reactor also housed a platinum counter electrode and @ duble junction Ag/Agclat. KCI reference electrode (Pine Research) “The reference electrode was placed inn separate compartment that was connected to the reactor by a capillary (inner diameter = 1 mm). The capillary tip was positioned ~1 ma from the stel electrode. A pote: tiostat (Autolab Metrolum) was used to control te potential or current of the working electrode. The resetor was also designed to allow control of| te convection rareby recirculating the solution using a peristaltic pump (Cole Parmer Masterfex). Te flow inlet was strategically placed adja cent to the working electrode, allowing recycled water to enter the reactor parallel to the electrode surface, Consequently, this setup permitted the hydrodynamic shear on the electrode tobe increased by increasing the flow rate, Tis Feature was incorporated to study the ef fect of forced convection om fatadaic efficiency and electrochemical processes occurring a the electrade-electrlyte interface. In the absence of low recirculation, convection still occurred due to uid density di ferences, whieh is referred to as natural convection condivions i is sy. Chronopotentiomenry was conducted employing { —13 mA em”, withthe current ireetion switching every PRT = 0.5 and 2 min. The duration of all experiments was 40 min, coresponcing to 40 and 10 complete eycles of PR for each PRT, respectively. The sort experimental time was deenied sufficient to observe the electrochemical phenomena occurring during PR-EC operation, and the trends observed were assumed to continue under longer experimental durations. In addition, DC BC experiments were conducted for 20 min (corresponding ro anodic operation duration inthe PR-EC experiments). In each experiment, the solution (NaCl, NajS0,, SGW, oF SPW) vias circulated through the reactor at low rate of 0 mL mia, 175 a min-*, and 770 a. mis, tnd the potential of the working electrode was monitored over time. ka Addition, the amounts of Fe released into the bulk solution and Fe accumulated in the fouling layer of the working electrode were reasited by digesting the entie working solution and the fosling layers nwt. 96 HNOsand 3 we. % HCL Following digestion, the samples were ‘quantified on ICP-OES. Cyclic voltammetry was conducted using voltage window of -3.25, V 10 41.75 V vs, SHE at 20 mV s~* for 10 scans, This procedare was similar to PR, but with gradually changing the potential and measuring the current response, as opposed to reversing the polarity instant racously while operating galvanostatically. Consequently, this method facilitated the observation of the corrosion/pitting potentials, the Dssivation charseterstes, and the aceurrence of side reretons cae: - ere Bie So Se War Ree 208 (2028) 117697 (b) ‘counter Fig. 1. The expeinentalresetrs employed inthis stud Performing 10 couseeutive sans permitted the observation of how the ‘currence of electrochemical reactions changed with incrensing scan ‘number, analogous co increasing the operating time in PREC. 2.4, Farudaic effclency ‘The applied current governs the electrochemical reaction rates atthe lectrodes. Therefore, the amount of anodic metal dissolution can be predicted by Farnday’s Law (Ea, (1) Theoretical mass of congulant metal dissolved © F where I (A) Is curren, (9) is electrolysis time, M isthe atomic mass of| the metal (M = 55.485 g mol? for Fe, is eleewon transfer number (2-2 for Fe), and Fis Faraday’s constant (96,48 Cmol, tn thisstudy, Ps Pa - Nacl Na2SO4| | mmm 3 hr z 100 100 mmm 6 hr a “0 Ew ra i 20 ° ° FS ho Fe ho eee ee . sw E 100 100 Ee 0 3 é Ew © 3 Zo © > 20 ° ° ig. 2. Theeffets of PRT and water chemisy on faadaleefficeney Expesents were coudueted employing 2 curtent density of 13 A eat * Thesoutlons were ‘eitlated single-pass though the teactor at lo rte of 10 mn resulting in esdeace cae of 20 ai, Experiments weve conducted in iplictes, ad average values along With one stand! devon (Le, etre) ae presented the feradnic efficiency was calculated as the rtio ofthe measured to the theoretically predicted (electrochemical produced by Faraday's law) (Geom Eo. (6) mass of Fe dissolved Oveerved Coagulant Frade etfiieny ( x 100% ” Theoretical Coaglant mat ‘where m ()s the experimentally measured mass of Fe relensd into the bulk solution. 2. Results and discussion, Sud, The effect of PR on congulane production Inthe continuons-flow system (Pg. 1a, the fara efictencles in PREC were always lower than those in DC-EC (Pig. 2. Notably, the faradae efficiency progressively decreased as PRT decrease fom 2 min 00.5 niin, The extent to which PRT influenced faradaie efficiency was ‘dependent on the solution chemisty. For example, the lowest faradaic ‘effcieney observed with the NaCl solution was 80%, while che lowest faradnie efciency in other solutions ranged between 5 and 50%. tn the PREG experiments with SPW, the faradaic efficiency was < 209% a all PRIS. War Ree 208 (2028) 117697 Possible explanations for the diminished faradaic efficiency in PREC. include: © Fens precipitated on the electrode surfaces instead of migrating into the bulk solution—it was visually observed that more ma: teriols accumlated of the electrodes in PREC than in DC-EC, especialy in experiments with a PRT of 0.5 min. (Gi) There are electrochemical side reactions that diverted the current away ftom resetion (1. ‘To decermine the contibution ofthe fest mechanism fo the rede: Udon n he faradalc efficiency, adiconal experiments were conducted to ‘quantify the amount of Fe accumulated inthe electrode fouling layers. ‘These experiments also eniployed the reactor presented in Fig. 1, except that the resctor was operated in a batch mode to enable the closing of Fe mass balance (which will be discussed further in Seton 5.2), Asshown in Fg. 5, the amount of Fe in te fouling layer inreased as PRI’ decreased, consistent with the decreasing faradale efficiency trend described above. The amounts of Fein the fxg ayer the SPW experiments were 2-5 tines greater than those in the other expe ‘ments. This is atrbutable tothe reaction between Fe(lt) and HS", which is known to be much faster than the hydrolysis and oxidation of Fe(I}) pice Nact|2° Na,SO, & Pus 5 Be to § 2 Eos 5 = oo 20 18 10 os Iron in Fouling Layer (mg/cm?) i 2. The effects of water chemistry and PRT on the amount of Fe accumulated in the elecuode fouling lye. Expeinents weve conducted eniployag the atch reactor setup that was operated fr 1h. The corespoding fadaie efficiency Values are lepoited in Fgute S. Experiments wete condicted in wipliates, aod average vals along with one stand! deviaon (i, itr bat) ae presented Gao et al, 20189 Fel: HS FeS +H ® This reaction produced sparingly soluble FeS minerals whose pres ‘ence on the electrade surface is corroborated by a cle signal of Sin the EDS spectrum (Figure S1 in the Supporting Information), and by the ‘observation that the electrodes timed black Ce, the typical color of Fes minerals). The biild-p of Fe inthe fouling layer in the SPW and SGW ‘experiments could also have been caused by Ca- and Mg;contaning tinerals, which covered the surface ofthe electrodes (Figure S1) and trapped more Fe in the fouling layer (ler eta, 2019). Ga- and Mg-containing minerals, such as CaCO, Mg(OH)a, and CaMg(CO3)z, ca precipitate under alkaline conditions developed in the boundary layer of the cate (Lei et, 20195 Weg la 2013) Because Doth electrodes in PR-EC intermtoutly served as te cathode asthe polarity alternated, ‘Ca: and Mg:containing minerals were sen to be present on both elec: trodes (Figure $1). On the contrary, the higher farndaic efficiency and lower Fe amount in the electrode fouling layers observed in the exper iments with the NaCl solution is attributable tothe ability of Cl ta Inhibit electrode passivation via piting corrosion (Arroyo el, 2009). (Although SGW and SPW also contained CI, te depassivaton eect oF ‘Cl- must have heen outcompeted by ions that can inhibit corrosion (Le, ‘S042, NO} ~ sillete and phosphate). SGW and SPW also contained Ca and Mg, which ean further foul the eleetrode surfaces via the mechanism discussed above). War Ree 208 (2028) 117697 3.2, Hlectrochemical phenomena atthe electrode electrolyte interface The fannie fficonis in PR-EC experiments were sil ower than 100% eve afer accounting for the Fein the fling ayer gu 2), sugesing that there must have een side reactions (he, hypothesis i) presented abore), Posie side reaction ince the oxidation of water tnd Cl (Ley reactions (4) and (6), the oxidation of Fell) to FD ttoverserenctions (9) mnt (10), andthe oxidation of Hayy to HO ttevrse reaction (2). Hag is prodveed fom encan 2 inthe prior current cycle when the eecrode served as the eathod) Since the nieasred anodic potential was alays < 01 Vv. SHE nt no pre sented) the oxidation of water and lca be rd out contrast, the ontdation of Fel) and Haip are thernodynanically poste becase magne O41 ¥, Fi won ecnra~ 0.5 10-0.6V (when DH 7-10), Bic raga toa™ 8S to-1.0V hen pH = 9-14, and Ey, resource -0-200-085¥ (hen pit = 814 (iss eal, 199%; Geni tals 2006; Beverskog and Purgdomeneth, 1996e; Boverskog and Puigdomenee, 19960) F20; +26 2H! + HO = 2Fe(OH), o Bfe,0, 26 4 2H! 2Fe,0, + HO a0) To gain farther insights into the eleewochemical phenomena that were responsible for the redirection ofthe faradaic current it PR-EC, & series of chronopotentiometric and cyclic voltametric experiments were conducted. AS mentioned in section 2, these experiments wete pet formed using the sual reactor (Fig. 1b) to enable the investigation of the effeet of hydrodynamie shear on the faradaie efficiency and the processes occurring at the electrode electrolyte interface. The rests 4060 80 Time [s] Fig. 4. Chionopotentiometry with supesinposed scans for PR-EC with PRTS convection (b, d). The working elecuode's anodic and eathodie potentials ax lectede tepoarization pelos le highlighted in yellow. (Fo inepretationo of this anise) 100 120 a (a) Natural Convection (b) Forced Convection PRT = 0.5 min a 2 a1 1 Zo — zs 82 Be 3 o 65 = 2 2 eS d) H 5) g 2 PRT =2 min = 0 2 40 60 80 Time [s] 100 120 5 mia (2b) and 2 min (e-) in 1.25 g L* NaCl with natal (ae) and freed J ploted roger. Experimental conditions: = 13 mA eat *, 40 min electli 3 the references 0 color ia tls gure legend the vader is efened othe web Wesson from the PREC chronopotentiometric experiments with natural con vection (Le. & low rate of © ml min through the reactor) revealed that following each PR event, the Fe working electrode underwent period of repolarization before its potential reached a steady state value (ig. 4, 83, 4, and $5) The repolarization duration was dependent on the PRT and the solution chemistry. For example, in the NaCl experi mens, the average anodic repolarization tines with PRTS of 0.5 min and 2 min were around 6 s aud 10 s respectively, whereas the cathodic "epolarizntion times were 7 sand 20 (the areas highlighted in yellow in ig. 4aand 4c), Similarly, the repolarization duration inthe NagSO. and 'SGW electrolytes also decreased as PRT increased (Figures S38, S3c, S48, ‘and S4c). In contrast, the potential of the Fe working electrode in the ‘SPW expetiments never reached steal state Figures Sa and S5D). Ths Indias that the repolarization processes in this ease were slow, with & longer timessale than the PRTs in each ease, Further sty is needed to Investigate this behavior; however, the dynamics may be associated fects of the passivating sulfate ions and the depassivating chloride fons present in this system. ‘The repolarization tines ofthe Fe working electrode were shortened, ‘upon the intraduction of forced convection by means of recirculating the solution through the reactor (alow rate 0f175 ax min (Pig. #b, #4 ‘Sab, 83d, S4b, $4, Sob and S5d). For example, the anodic and cathodic repolarization times were reduced to < 1 sand 2.5, respectively, upon the introduetion of low. Notably, the anodic overpotentials inthe NaCl NaS, and SGW experiments decreased by 0.5 1 V. In the absence of flow, the anodic potentials in the NagS0O. electrolyte were above +2 V (us. SHE, Figures $3a and 53). These potential values were suiiently high to trigger the oxidation of HO (Van Genuchiten et aly 2017, ‘resulting in the formation of gas bubbles on the working electrode Under forced convection, the anodic potential in the NaSO, electrolyte ‘dropped to below +1 V (Ws, SHE) and the production of gas bubbles was War Ree 208 (2028) 117697 no longer observable. ‘There are several possible reasons forthe presence of aa electrode repolarization period following each current switching event. First, electrode repolarization ean be the result of the recharging ofthe elec trode double layer, However, this is unlikely the main reason, since the time required to charge the electrochemical double layer in EC i spi cally 1 ~20 ms (ingessou e al, 2020), whereas the repolarization times observed hrerein were greater than 2s. Furthermore, there a5 n0 evi fence of significant electrochemical double layer capacitance in the polarization eyelie voltammetry curve (Figure 6), Second, electrode repolarization could be deco the aversion of the boundary ler pi, leading to a shift in the equilibrium potential of eleetrochemical re actions, For example, & higher potential at the beginning of exch tathodie polarization could be due to the reduction of water (he, te action (2)) being thermodynamically more favorsble in an acidic boundary layer (tis acidic boundary layer was established inthe pre ceding current cycle wiien the electrode functioned as an anode), Note thar the anodic repolarization Is unlikely due to the electrochemical Aisolution of, since eaetion 1) does not involve H* and, therefore, |s nor influenced by the pH change in the boundary layer. As such, ‘anodic repolarization could have been caused by reactions Involving electrochemically reactive species inthe electrode boundary layer. Its hypothesized that only afer these species were consumed did reaction D start. This hypothesis is in agreement with the observation that proportionally longer anodic repolarization times were associated with lower faradac efficiencies. For example the anodic polarization time in the NaCl solution constituted approximately 8% and 20% of the total polarity eyele forthe 2 min and 0.5 min PRTS, respectively Cis. and 40). Under these PRT, the faradaie efficiencies were 80% and 55% (Wig. 5). Note that the Fe in the fouling layers were included in the calculations ofthese faradai efficiencies, so any efficiencies < 100% Faradaic Efciency (*4) oo eee 75min = 75 mimin"t wa 0 ® ® © © « “ » 2 ° ° eae & 9 . or a gw 120 Ss 120 iS sam a Pa 0 Zs ® Zo « go ° : & 2 2 ° ° Fig. 5. Theetfcr of ow on fzadneeffitency. Experiments were conducted in upleates, and average values long with one standard deviation (Le, e104 bat) ae pesented, Fe in the solution and Fe in the fonling ayes were include in the fae efcencies. 1H ciow wah Ware Reser 209 (2021) 117407 could not have been caused by fouling in these experiments. The inac ‘The hypothesis that side reections redirecting the faradai current tivation of faradaic Fe°--Fe#” dissolution duting electrode repolatizn. during the eleewode repolarization is further corroborated by the tion has been hypothesized previously (Croerud and Smoczyiski, inereasing faradaic efficiency under forced convection (Fig. 0). Speci 1986), but has not been investigated in dell Teall, under a flow rate of 175 mi min the feradaiceficencies in the fa) Natural Convection —_(b) Forced Convectior ‘sos Socom ey on ner on a non os Potential V v8 SHE] Potential (V vs SHE) Fig. 6. Cylevoltanmettc experinents under natural (left) and forced (ight) convection, 10 forwatd scans (Le, cathode ~ anole potential) were superimpose Inthe iguies. Regions of passivation and possible side reactions a highlighted i yellow. (Fr laerpettion of the ferences to color ia thie Figure legend, he eae is refried fo the web version ofthis arte.) NaCl experiments were 96% (PRT = 2 min) and 9596 (PRT = 0.5 mi,

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