Chemosphere 46 (2002) 905–912

Degradation of azo dye Procion Red MX-5B by
photocatalytic oxidation
C.M. So a, M.Y. Cheng a, J.C. Yu b, P.K. Wong



Department of Biology, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong
Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong

Received 15 November 2000; received in revised form 11 June 2001; accepted 11 June 2001

The photocatalytic oxidation (PCO) of a monoazo dye Procion Red MX-5B under various physico-chemical conditions was investigated. Degradation of the dye by PCO was enhanced by augmentation in UV intensity, titanium
dioxide and hydrogen peroxide concentrations but was inhibited by increase in initial dye concentration. The PCO
process was affected by pH in a peculiar way. In the presence of 100 mg/l of TiO2 and the absence of H2 O2 , the highest
reaction rate was observed when the initial pH was 10. With 500 mg/l of TiO2 and 10 mM of H2 O2 , the reaction was the
fastest at initial pH of 3–5. The optimal conditions for the degradation of the dye, at an UV intensity of 17 mW=cm2 ,
were determined to be: TiO2 concentration, 500 mg/l; initial H2 O2 concentration, 10 mM; initial pH, 5.0. Monitoring of
TOC loss showed that the dye was mineralized by 90% within 80 min under these conditions. Nevertheless, the persistence of a low level of TOC indicated that mineralization was not complete and dead-end product(s) which was
(were) resistant to PCO might have accumulated. Ó 2002 Elsevier Science Ltd. All rights reserved.
Keywords: PCO; Mineralization; Titanium dioxide; UV

1. Introduction
Dye-laden wastewaters discharged by dyeing and
textile industries pollute natural waters and lower their
value in use. Azo dyes, which contain one or more azo
bonds (AN@NA), are among the most widely used
synthetic dyes and usually become major pollutants in
these wastewaters. It has been documented that some
azo dyes are toxic (Meyer, 1981) and even mutagenic
(Chung et al., 1981) to living organisms in aquatic environments. In addition, the stability of their molecular
structures renders them resistant to biological and even
chemical degradation (Dai et al., 1995, 1996a,b). Due to


Corresponding author. Tel.: +852-2609-6383; fax: +8522603-5767.
E-mail address: (P.K. Wong).

their toxicity and recalcitrance, these dyes can be hazardous to the environment though present at low concentrations.
Recently, numerous studies on the application of
photocatalytic oxidation (PCO) for the removal of azo
dyes (Hustert and Zepp, 1992; Davis et al., 1994; Goncalves et al., 1999; Hu and Wang, 1999; Tanaka et al.,
2000) and other organic pollutants (Mills et al., 1993;
Herrmann, 1999) in aqueous solutions have been reported. The process commonly involves irradiation by
UV ðk < 400 nmÞ in the presence of a semiconductor
catalyst like titanium dioxide (TiO2 ). Upon absorption
of light energy equal to or larger than the band gap
energy, a valence band electron of the semiconductor
can be excited to the conduction band (e
CB ), leaving a
positive hole in the valence band ðhþ
TiO2 þ hv ! e
CB þ hVB

0045-6535/02/$ - see front matter Ó 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 1 ) 0 0 1 5 3 - 9


1995). Neither forced aeration nor stirring of the dye solution was conducted in all experiments. which is also a potent oxidizer: þ  hþ VB þ H2 O ! OH þ H þ   hVB þ OH ! OH ð2Þ ð3Þ On the other hand. number 18200). The top of the glass column was open to the atmosphere. The Chinese University of Hong Kong and used as received without further purification. The chemical structure of Procion Red MX-5B. both TiO2 and H2 O2 are inexpensive and TiO2 is reusable. Furthermore. In the present study.2.. Construction of the photoreactor All photocatalytic experiments were carried out in a reactor depicted in Fig. H2 O2 (35% w/v) was from Riedel-de Ha€en (Seelze. The dye was from the Biology Department. Germany). Poulios and Aetopoulou. Frankfurt.5 mm thick was used as a container for the dye solution. and with a wall 1. 2. Third.. 2. 25 mm external diameter. All experiments were conducted in deionized water (<5 lS=cmÞ. The effects of various physico-chemical conditions on the degradation of the dye by PCO were studied and mineralization of the dye was monitored. Second.. The dye is highly water-soluble and can be used for dyeing cellulose. 1998. The monoazo dye Procion Red MX-5B. Materials and methods 2. Poulios and Tsachpinis. was manufactured by Imperial Chemicals Industries (ICI). 1. 1993). The glass column was surrounded by eight UV lights with a maximum emis- Fig. can oxidize these dyes to CO2 and mineral ions (Tan et al.M. PCO also appears to be a better treatment method for azo dye-containing wastes than conventional biological processes.1. such a PCO process can be accelerated by hydrogen peroxide ðH2 O2 Þ as demonstrated in some studies (Malato et al. Chemical reagents  e CB þ O2 ! O2 ð4Þ In addition. 2. they can be destroyed by PCO within hours (Mills et al. One efficient electron acceptor is molecular oxygen ðO2 Þ. Germany).906 C. During the reaction. or react with electron donors like water or hydroxide ions to form hydroxyl radical ð OHÞ. azo dyes can be readily transformed to aromatic amines which are usually more toxic than the parental dyes (Tan et al. 1 (Society of Dyers and Colorists. 2. on the contrary.. it can act as a conduction-band electron acceptor like O2 and form  OH subsequently   H2 O2 þ e CB ! OH þ OH ð7Þ Such a UV-TiO2 -based PCO system exhibits some attractive characteristics. 1999). 1999. Top view of the photoreactor. 1999). While these compound are highly recalcitrant to biodegradation (Dai et al. H2 O2 can produce  OH by reacting with O 2 or by direct photolysis:   H2 O 2 þ O  2 ! OH þ OH þ O2  H2 O2 þ hv ! 2 OH ð5Þ ð6Þ Besides. during the anaerobic digestion stage of the conventional sewage treatment process. which forms a superoxide anion radical after capturing the electron Fig. PCO. . TiO2 was obtained from the Degussa Company (P 25. nylon. also called Reactive Red 2 (C.I. It was constituted of a glass column surrounded by eight UV lights and enclosed in a stainless steel shield. So et al. / Chemosphere 46 (2002) 905–912 The positive hole is a strong oxidant which can either oxidize a compound directly. It has an elemental composition of C19 H10 Cl2 N6 Na2 O7 S2 and its chemical structure is shown in Fig. A glass column of 430 mm height. it is important for the excited electron in the conduction band to be scavenged by an external agent to prevent its recombination with the positive hole. TiO2 is environmentally acceptable by being fairly inert biologically and chemically. degradation of major classes of organic pollutants can be achieved at ambient conditions.. we investigated the PCO of a common monoazo dye Procion Red MX-5B. First. silk and wool. 1999). 1995).

Sampled suspensions were centrifuged at 13. length of 538 nm after adjusting the pH of the sample to 10.3. 3. Chemical analysis Decolorization of Procion Red MX-5B was monitored by measuring absorbance with a Milton Roy Spectronic 3000 Array spectrophotometer at a wave- Fig. 500 mg/l. All TOC data reported had been subtracted for background concentration of TOC. 10 mM. initial pH.0 (the natural pH of the reaction solution).) . Model T-15L/8D). To study the effects of the different physico-chemical parameters. The suspension was then irradiated by UV and 1-ml samples were collected at specific time intervals to monitor the change in dye concentration.5–5. Since the PCO reaction with Procion Red MX-5B. Degradation and mineralization was monitored by determining sulfate ion and total organic carbon (TOC) concentrations in the reaction solution. So et al. 3. 3. Effect of initial dye concentration The effect of initial dye concentrations ranging from 5 to 40 mg/l on decolorization of Procion Red MX-5B by PCO was investigated. UV intensity. UV intensity. 23°C (room temperature). 1994) and other organic compounds (Mills et al. initial pH. 1992. samples of 1. UVP). initial temperature. UV intensity (at 365 nm) of each light was determined by a digital radiometer (model UVX.C..4.000 rpm for 15 min in eppendorf tubes to remove the TiO2 powder. The supernatants were analyzed for dye concentration by spectrophotometry. 40-mg/l dye solution under the following conditions: TiO2 . Results are means of duplicates and error bars represent 1 S. 4:26 mW=cm2 . initial pH. 15 min) to remove the TiO2 particles before analysis. Each has a power consumption rate of 15 W and an average UV output intensity of 2:13 mW=cm2 (ranging from 2. 2..06 to 2:21 mW=cm2 ) at 365 nm as determined at the center of the photoreactor.5. temperature.D. / Chemosphere 46 (2002) 905–912 907 sion at 365 nm (Vilber-Lourmat. (Experimental conditions: TiO2 .0. absorbance value at 538 nm of the reaction solution measured by spectrophotometry (see Section 2. only the one of interest was varied while the others were maintained at levels as described earlier.5– 5. Results and discussion Experiments for characterization and optimization of the PCO process were generally conducted with a 150ml. 4. Mineralization of the dye Mineralization of Procion Red MX-5B by PCO was studied with a 40-mg/l dye solution under optimal conditions that resulted in maximum decolorization rates. Total organic carbon (TOC) was analyzed by a Shimadzu TOC analyzer (model 5000A). Similar observations 2. 5. The k’s thus calculated were used as the basis for comparison of reaction rates under different conditions. 100 mg/l.000 rpm. like other azo dyes (Hustert and Zepp. 4:26 mW=cm2 . For the calculation of k 0 in this study. H2 O2 . The UV lights and the glass column were enclosed in a stainless steel shield with an open top where an electrical fan was mounted to vent the heat inside the reactor. 2.M. 1993). a decrease in the rate constant was observed upon the increase of initial dye concentration. 4.0. 100 mg/l. Characterization of the photocatalytic oxidation reaction 3. As depicted in Fig. For monitoring of sulfate ion concentration. For TOC determination. apparently followed first-order kinetics with the pseudofirst-order rate constant ðk 0 Þ. These conditions were (at a UV intensity of 17 mW=cm2 and a temperature of 23°C): TiO2 . A suspension of TiO2 and the dye was first mixed well and equilibrated in the dark for at least 10 min. The total UV intensity was controlled by turning on different number of UV lights and the maximum intensity was 17 mW=cm2 (with all eight UV lights on). Sulfate ions were analyzed by a Dionex ion chromatograph (model LC20) equipped with an anion-exchange column (IonPac AS-4A-SC) and a conductivity detector. Effect of initial dye concentration on the pseudo-firstorder rate constant for the photocatalytic oxidation of Procion Red MX-5B. 23°C.1.3 ml were collected and centrifuged (13. The initial pH was varied from 2 to 10 by the addition of HCl or NaOH. Davis et al. 5-ml aliquots were collected and filtered ð0:2 lm pore size) before analysis.5) was used in place of dye concentration as the two bear a linear relationship as determined previously.

4:26 mW=cm2 . 23°C. 1999). So et al. Such an effect was expected as UV intensity determines the amount of photon absorbed by the catalyst. / Chemosphere 46 (2002) 905–912 have also been reported for the PCO of other dyes and organic compounds (Davis et al. TiO2 . the observed enhancement in decolorization is probably due to an increased number of available adsorption and catalytic sites on TiO2 . 3. 2000). initial pH. One possible cause for such results is the UV-screening effect of the dye itself. In the absence of the catalyst.0. their occurrence was clearly indicated by the presence of about 8% of organic carbon (TOC) remaining when more than 90% of the dye was decolorized. part of Fig. (Experimental conditions: dye. however. 4. At the concentration range from 100 to 500 mg/l. Effect of UV intensity on the pseudo-first-order rate constant for the photocatalytic oxidation of Procion Red MX5B. 1998). Effect of catalyst loading The effect of UV intensity on the decolorization of Procion Red MX-5B is shown in Fig. These intermediates may include aromatics. (Mills et al.D.0. 1993. 1999).3. 1998.. In addition.. In addition. Decolorization started when 100 mg/l of TiO2 was added and the rate increased sharply with catalyst loading up to 500 mg/l.2. Lea and Adesina.) 3. They may compete with the dye molecules for the limited adsorption and catalytic sites on the TiO2 particles (Ollis et al. Results are means of duplicates and error bars represent 1 S.. 1998. ketones and organic acids as shown by previous studies with various aromatic compounds (Serpone et al. UV intensity. A further increase in catalyst loading. 23°C.. no decolorization was observed. 40 mg/l.908 C. (Experimental conditions: dye. may cause light scattering and screening effect and thus reducing the specific activity of the catalyst (Lea and Adesina. 1998). aldehydes. Goncalves et al. 5. In such a condition. a significant amount of UV may be absorbed by the dye molecules rather than the TiO2 particles and thus reduces the efficiency of the catalytic reaction (Mills et al. 1994. The pseudofirst-order rate constant steadily increased with UV intensity and showed a largely linear relationship.. It appears that the UV intensities tested in our study lie within the linear range where utilization of the light energy is the most efficient.M. 5. 40 mg/l. 1993. Results are means of duplicates and error bars represent 1 S. However. Similar observations were also reported in other studies on dyes and various organics (Davis et al. Another possible cause is the interference from intermediates formed upon PCO of the parental dye. agglomeration and sedimentation of the TiO2 particles were observed in our study when 2000 mg/l of TiO2 was added to the dye solution. temperature. The result is consistent with previous studies which generally observed an increase in PCO rate with UV intensity The effect of TiO2 loading on decolorization rate is presented in Fig. Such a suppression would be even more pronounced in the presence of an elevated level of degradation intermediates formed upon an increased initial dye concentration. Lea and Adesina. 5. Tanaka et al. 1999).. 1993). temperature. Effect of titanium dioxide concentration on the pseudofirst-order rate constant for the photocatalytic oxidation of Procion Red MX-5B. Lea and Adesina. Poulios and Aetopoulou. Although we have not yet identified the intermediates formed during the PCO of Procion Red MX-5B. previous studies also show that the relationship between reaction rate and UV intensity starts to change from first-order (rate / UV intensity) to half-order [rate / (UV intensity)1=2 ] when UV intensity is increased beyond a certain value (approximately 25 mW=cm2 ) (Herrmann. only a slight enhancement was observed when TiO2 concentration further increased to 2000 mg/l.D. At a high dye concentration.. 5. initial pH. 4.. Effect of UV intensity . 1998. 100 mg/l.) Fig. 1994.. d’Hennezel et al. 1989) and thus inhibit decolorization.

however. was observed when the concentration further increased to 20 and 40 mM. (5) and (6)) and as a conductionband electron acceptor (Eq. the PCO reaction will be inhibited when Fig. Effect of initial pH on the pseudo-first-order rate constant for the photocatalytic oxidation of Procion Red MX-5B. (8)) and  OH (Eqs.. Malato et al. 1993). pH changes can thus influence the adsorption of dye molecules onto the catalyst surfaces. However. H2 O2 can also become a scavenger of valenceband holes (Eq.C. the charge of the dye molecules with ionizable functional groups and the surface of the TiO2 catalyst are both pH dependent.  OH can be formed by the reaction between hydroxide ion and positive hole. 1997. 100 mg/l. It can both act as a source of  OH (Eqs. Furthermore. Little enhancement. 3. / Chemosphere 46 (2002) 905–912 the catalyst surface probably became unavailable for photon absorption and dye adsorption. First. As described in Section 1.M.) Fig. 1999). As seen in Fig. 1998. 1998):  As both hþ VB and OH are strong oxidants for organic compounds. whose degradation was the fastest at more alkaline pHs. 23°C. So et al. A concentration of 10 mM appears to be optimal. 6.. Similar results were also reported by Hustert and Zepp (1992) and Tang and An (1995) for acidic azo dyes bearing sulfonate groups. Poulios and Aetopoulou. UV intensity. 1999). Previous studies indicate that pH may affect PCO in a number of ways. Effect of pH Decolorization of Procion Red MX-5B was markedly enhanced by the addition of H2 O2 . TiO2 . 40 mg/l. temperature. 6. 7 shows the effect of pH on the decolorization of Procion Red MX-5B in the presence of 100 mg/l of TiO2 and the absence of hydrogen peroxide. Decolorization was the fastest at pH 10 and the pseudo-first-rate constant gradually decreased with the lowering of pH. 3. (7)) to prevent electron–hole recombination. as indicated in Equation 3. Results are means of duplicates and error bars represent 1 S. (9) and (10)) (Legrini et al.. Third. 4:26 mW=cm2 . Poulios and Aetopoulou. 4:26 mW=cm2 . Similar observations were also reported in previous studies where an increase in H2 O2 level enhanced PCO rate up to an optimal point beyond which inhibition occurred (Malato et al. an important step for PCO to take place (Fox and Dulay. the TiO2 particles tend to agglomerate under acidic condition and the surface area available for dye adsorption and photon absorption would be reduced (Fox and Dulay.0. An alkaline condition would thus favor  OH formation and enhance degradation. (Experimental conditions: dye.. H2 O2 can be adsorbed onto TiO2 particles to modify their surfaces and subsequently decrease its catalytic activity (Malato et al. 23°C. 1993. the pseudo-first-order rate constant increased by about 10fold when H2 O2 concentration changed from 0 to 10 mM. (Experimental conditions: dye. 40 mg/l.) þ H2 O2 þ 2hþ VB ! O2 þ 2H H2 O2 þ  OH ! H2 O þ HO2 HO2 þ  OH ! H2 O þ O2 ð8Þ ð9Þ ð10Þ . Results are means of duplicates and error bars represent 1 S. temperature. initial pH. when present at high concentration. H2 O2 serves two roles in PCO to cause an enhancement effect. no H2 O2 . Effect of hydrogen peroxide concentration on the pseudo-first-order rate constant for the photocatalytic oxidation of Procion Red MX-5B. 100 mg/l. 1998). However. 1993). different optimal pHs (6–7) have also been observed for the PCO of other sulfonated azo dyes (Tang et al. thus bringing little stimulation to the catalytic reaction. Fig. Effect of hydrogen peroxide 909 H2 O2 level gets too high..4. TiO2 .5. 5. 7. UV intensity.D.D. Second.

pH 10 was found to be the optimal point under the given experimental conditions (TiO2 .0. A more thorough study will be undertaken to seek an explanation for such observations. 10 mM. 17 mW=cm2 .D. UV intensity. temperature. We also investigated the effect of pH in the presence of 500 mg/l of TiO2 and 10 mM of H2 O2 . were very different from those obtained with 100 mg/l of TiO2 and no H2 O2 .D.0. total organic carbon loss and sulfate ion formation during the photocatalytic oxidation of Procion Red MX-5B under optimal conditions. 10 mM. Results are means of duplicates and error bars represent 1 S. initial pH. and how the elevated TiO2 and H2 O2 concentrations would have such a different impact on the optimal pH of the PCO reaction. TiO2 . (Experimental conditions: dye. pH. we cannot explain why only the significant interaction between pH and concentration of TiO2 or H2 O2 in the PCO degradation of the dye. 40 mg/l. 100 mg/l. The results. 8.M. (Experimental conditions: dye. H2 O2 . at a UV intensity of 17 mW=cm2 and a temperature of 23°C. a high pH would have hindered the adsorption of Procion Red MX-5B onto the TiO2 surfaces as both would be predominantly negatively charged. / Chemosphere 46 (2002) 905–912 Fig. However. Decolorization. 23°C. H2 O2 concentration. 8. thus lowering the PCO rate at acidic pH. temperature. H2 O2 . 500 mg/l. This might have reduced the availability of catalyst surface for dye adsorption and photon absorption. no H2 O2 ).) In this study.6. agglomeration of TiO2 particles was indeed observed in our study. So et al. TiO2 . 40 mg/l. 500 mg/l. 23°C. This may indicate that the dye is highly susceptible to be attacked by  OH despite a weak adsorption of the dye onto the catalyst. were found to be: TiO2 concentration. As seen in Fig. 3. 4:26 mW=cm2 . the optimal conditions for the PCO of Procion Red MX-5B.) . UV intensity. the highest decolorization rate was observed at pH 3–5 and the pseudofirst-order rate constant decreased with pH. 10 mM. Effect of initial pH on the pseudo-first-order rate constant for the photocatalytic oxidation of Procion Red MX-5B at elevated TiO2 and H2 O2 concentrations. On the other hand. Mineralization of Procion red MX-5B under optimal conditions Based on the results obtained in the characterization experiments. 9. At this point. Results are means of duplicates and error bars represent 1 S. at pH 2–4. the two conditions which were shown to bring the greatest enhancement to decolorization. Degradation and mineralization of Procion Red MX-5B by PCO under such conditions was studied by Fig.910 C. 500 mg/l. however. 5. 5.

at 17 mW=cm2 of UV irradiation and room temperature (23°C). the residual TOC observed in our study may be attributed to some triazine-related compound(s) like cyanuric acid. 1994. The TOC level then declined with time but almost remained at a constant level (about 1.. pp.0. O. H. Fulk. The Chinese University of Hong Kong..A.S. Li. Release of sulfate ions upon dye degradation was a little slower than decolorization but was much faster than TOC loss. Fig.. Biotechnical treatment of wastewater containing azo dyes.T. Dai. P. S. initial pH. G. Water Environment Research 66. Photochemical treatment of solutions of azo dyes containing TiO2 . indicating the formation of organic intermediates derived from the dye. most of the total sulfate ions released were observed within the first 20 min.M.C. 1999.3. previous works show that TiO2 -mediated PCO of some triazine-derived compounds can be very slow (with half-life in hours) and cyanuric acid (2. G. As indicated by the absorbance at 538 nm. Oliveira-Campos. In addition. 5. 407–411. / Chemosphere 46 (2002) 905–912 monitoring TOC loss and sulfate ion formation in the dye solution. Catalyst Today 53. 1996a. E. 1981.L... R. Mutagenicity testing of some commonly used dyes. Dulay. 1996. were determined to be: TiO2 concentration. M. K.. Heterogeneous photocatalysis. Plas^encia. Journal of Photochemistry and Photobiology A: Chemistry 118. Ollis. however. the persistence of a low but constant level of TOC in solution suggests the accumulation of dead-end product(s) which is(are) resistant to degradation by the PCO reaction. probably triazine derivative(s). Y. d’Hennezel. In: Proceedings of the 4th Mainland–Taiwan Environmental Technology Seminar. Mineralization.P. Study on the relationship between structure of synthetic organic chemicals and their biodegradability. L.. 10 mM. 781–786. 500 mg/l. Applied and Environmental Microbiology 42.. Further study under these optimized conditions to decolorize/degrade azo dyes with mono-. 1999. Advances in Environmental Sciences 4.. W. vol. 354–367. Song. Y.. 1. Zhuang. however. J. Dai.4. 1–9. So was partially supported by a Postdoctoral Fellowship of the Research Committee... remained almost unchanged within the same period of time. 197–204.. S. C.. M. the dye can be decolorized in 20 min and mineralized by 90% in 80 min. Under these conditions. I.E. A. 1997)... 1995. may have accumulated probably due to resistance to degradation by the TiO2 -mediated PCO reaction..R.. 1999.K. Therefore. 341–357.a. Gainer. . di-. Environmental Chemistry 14. 641–648. Fox. Song. 4. initial H2 O2 concentration. Zhuang. In a later experiment with a 200-mg/l dye solution. O’Neal. Wu.W.. Optimal physico-chemical conditions for the degradation a 40-mg/l dye solution.M. P..M..T.S. Wong. the parental dye was decolorized by >90% within the first 10 min... was not complete. These results indicate that the fast decolorized dye was followed by much slower mineralization of intermediates formed subsequently.5-triazine) is usually found as a dead-end product due to its high resistance to degradation by the PCO process (Minero et al. Y. cyanuric acid has a relatively low toxicity and is biodegradable (Minero et al. Conclusions We characterized the PCO of a monoazo dye Procion Red MX-5B. indicating that the removal of sulfonate groups is an early step in the degradation process. Yan. 1993. Chemical Reviews 93. Photocatalytic decolorization of wastewater dyes.M. Acknowledgements The study was supported by a research grant of Research Grant Council. On the other hand... Study on azo dyes structure–biodegradability relationships. A.M..6-trihydroxy1. 4 mg/l) was also observed after 7 h of irradiation (data not shown). Benzene and toluene gas-phase photocatalytic degradation over H2 O and HCl pretreated TiO2 : by-products and mechanisms. 9 shows the changes of dye. M. Davis.. Hong Kong SAR Government to P. J. Despite its resistance to PCO.F.. 1998. it should be readily removed by biological treatment systems and is unlikely to pose a problem to the environment. Pichat. 2000). References Chung. Thus.. So et al. The short reaction times (20 min and 80 min for decolorization and min- 911 eralization. efficient and economic treatment of wastewater containing azo dye.M. Y. M. Dai. W.. S. Similar results have also been reported for other azo dyes constituted of triazine derivatives (Hu and Wang. triand tetra-azo bonds by PCO will determine the relations between the structure and PCO degradation. D. Andres. Furthermore. Chen.T. Chemosphere 39.2 mg/l) up to 120 min of irradiation. Herrmann. Heterogeneous photocatalysis: fundamentals and applications to the removal of various types of aqueous pollutants. Wang. Chen. Pinto.S. 115–129. TOC and sulfate ion concentrations in the reaction solution during the PCO process. T.J. 50–53.. 1997). Goncalves..J. respectively) indicate that PCO can be used as a simple. Queiroz. In addition. TOC in the solution. using other azo dyes with structure similar to Procion Red MX-5B may provide further information to identify intermediate products of PCO degradation of azo dyes.F. Zhuang. the persistence of a higher level of residual TOC (c. Dead-end product(s).

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