Photocatalysis by titanium dioxide and polyoxometalate/TiO2 cocatalysts. Intermediates and mechanistic study

A representative polyoxometalate, alpha-12-tungstophosphatic acid (PW12(3-), POM), is loaded on the surface of TiO2 particles used as a cocatalyst to gain further insights into the underlying reaction mechanism and to estimate the feasibility of using the new POM/TiO2 cocatalyst in the photocatalytic degradation of 2,4-dichlorophenol (DCP) in aqueous media. Loading the PW12(3-) species on the surface of TiO2 enhances charge separation in the UV-illuminated TiO2, thereby accelerating the hydroxylation of the initial DCP substrate but not the mineralization of DCP, which is somewhat suppressed in the presence of the polyoxometalate. An increase in the load of POM increases the concentration of aromatic intermediates, and more toxic intermediates, such as 2,6-dichlorodibenzo-p-dioxin, 2,4,6-trichlorophenol, are detected in the PW12(3-)/TiO2 system. By contrast, cleavage of the whole conjugated structure of DCP predominates in TiO2 only dispersions. Strong ESR signals for the superoxide radical anionic species, O2*- (HO2* radicals in acidic media; pH < 5), are detected in TiO2 only dispersions; signals of O2*- are much weaker in the TiO2/ POM composite system under otherwise identical conditions. Experimental results infers that enhancement of charge separation in TiO2 photocatalysis does not always result in improvement of the efficiency of mineralization of organic substrates, and the reaction between organic radical cations and the formed superoxide radical anions may be responsible forthe mineralization of the chlorophenol.     

TiO2 photocatalysis of natural organic matter in surface water: impact on trihalomethane and haloacetic acid formation potential

In this study, changes in the physical and structural properties of natural organic matter (NOM) during titanium dioxide photocatalytic oxidation process were investigated using several complementary analytical techniques. Potential of the treated water to form trihalomethanes (THMs) and haloacetic acids (HAAs) was also studied. High-performance size exclusion chromatography analysis showed that NOM with apparent molecular weights of 1-4 kDa were preferentially degraded, leading to the formation of lower molecular weight organic compounds. Resin fractionation of the treated water demonstrated that the photocatalytic oxidation changed the affinity of the bulk organic character from predominantly hydrophobic to more hydrophilic. Short chain aldehydes and ketones were identified by mass spectroscopy as one of the key degradation products. The addition of hydrogen peroxide to photocatalysis was found to increase the degradation kinetics but did not affect the reaction pathway, thus producing similar degradation end products. The amount of THMs normalized per dissolved organic carbon (specific THM) formed upon chlorination of NOM treated with photocatalytic oxidation was reduced from 56 to 10 microg/mg. In contrast, the specific HAAs formation potential of the treated water remained relatively unchanged from the initial value of 38 microg/mg, which could be due to the presence of hydrophilic precursor compounds that were formed as a result of the photocatalytic oxidation process.     

Mechanistic studies of the photocatalytic degradation of methyl green: an investigation of products of the decomposition processes

The methyl green (MG) dye dissolves into an alkaline solution when the pH value is too high (pH 9). The cationic MG dye molecules are converted into the colorless carbinol base (CB) and produce crystal violet (CV) dye and ethanol by hydroxide anion. Thirty-three intermediates of the process were separated, identified, and characterized by HPLC-ESI-MS technique in this study and their evolution during the photocatalytic reaction is presented. Moreover, the other intermediates formed in the photocatalytic degradation MG processes were separated and identified by HPLC-PDA technique. The results indicated that the N-de-methylated degradation of CV dye took place in a stepwise manner to yield N-de-methylated CV species, and the N-de-alkylated degradation of CB also took place in a stepwise manner to yield N-de-alkylated CB species generated during the processes. Moreover, the oxidative degradation of the CV dye (or CB) occurs to yield 4-(N,N-dimethylamino)phenol (DAP), 4-(N,N-dimethylamino)-4'-(N',N'-dimethylamino)benzophenone (DDBP) and their N-de-methylated products [or to yield 4-(N-ethyl-N,N-dimethyl)aminophenol (EDAP), DDBP, 4-(N-ethyl-N,N-dimethylamino)-4'-(N',N'-dimethylamino)benzophenone (EDDBP), DAP, and their N-de-alkylated products], which were found for the first time. A proposed degradation pathway of CV and CB is presented, involving mainly the N-de-alkylation and oxidation reaction.     

Kinetics and mechanisms of photocatalytic degradation of (CH3)nNH(4-n)+ (0 < or = n < or = 4) in TiO2 suspension: the role of OH radicals

The photocatalytic degradation of a series of (CH3)nNH(4-n)+ (0 < or = n < or = 4) was systematically studied in the UV-illuminated TiO2 aqueous suspensions at pH ranges of 3-11. By investigating the pH-dependent kinetics and analyzing intermediates and products, we elucidated the mechanistic pathways and the role of OH radicals in the photocatalytic oxidation. The deprotonated neutral species more rapidly degraded than their protonated counterparts for these homologous compounds because the OH radicals favorably reacted with the lone-pair electron on the nitrogen atom. Therefore, the photocatalytic degradation was highly enhanced at alkaline solutions for all substances except (CH3)4N+. The H-atom abstraction (from (CH3)4N+) by OH radicals initiated successive demethylation processes to generate tri-, di-, and monomethylammonium/amine as an intermediate and NH3/NH4+ as a final product. On the other hand, the OH-addition to the N-atom with the lone-pair electron led to NO2-/NO3- whose production was highly favored at alkaline conditions. The photocatalytic degradation rates of (CH3)4N+ were comparable at both acidic and alkaline conditions, which could not be explained by a simple electrostatic surface charge model. By using OH-scavenging tert-butyl alcohol as a diagnostic probe into the mechanism, it is suggested that the photocatalytic oxidation of (CH3)4N+ at acidic conditions proceeds through free OH radicals in the solution bulk, not on the surface of TiO2.     

Transformation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by permanganate

The chemical oxidant permanganate (MnO(4)(-)) has been shown to effectively transform hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) at both the laboratory and field scales. We treated RDX with MnO(4)(-) with the objective of quantifying the effects of pH and temperature on destruction kinetics and determining reaction rates. A nitrogen mass balance and the distribution of reaction products were used to provide insight into reaction mechanisms. Kinetic experiments (at pH ～ 7, 25 °C) verified that RDX-MnO(4)(-) reaction was first-order with respect to MnO(4)(-) and initial RDX concentration (second-order rate: 4.2 × 10(-5) M(-1) s(-1)). Batch experiments showed that choice of quenching agents (MnSO(4), MnCO(3), and H(2)O(2)) influenced sample pH and product distribution. When MnCO(3) was used as a quenching agent, the pH of the RDX-MnO(4)(-) solution was relatively unchanged and N(2)O and NO(3)(-) constituted 94% of the N-containing products after 80% of the RDX was transformed. On the basis of the preponderance of N(2)O produced under neutral pH (molar ratio N(2)O/NO(3) ～ 5:1), no strong pH effect on RDX-MnO(4)(-) reaction rates, a lower activation energy than the hydrolysis pathway, and previous literature on MnO(4)(-) oxidation of amines, we propose that RDX-MnO(4)(-) reaction involves direct oxidation of the methylene group (hydride abstraction), followed by hydrolysis of the resulting imides, and decarboxylation of the resulting carboxylic acids to form N(2)O, CO(2), and H(2)O.     

Cobalt-mediated activation of peroxymonosulfate and sulfate radical attack on phenolic compounds. implications of chloride ions

The sulfate radical pathway of the room-temperature degradation of two phenolic compounds in water is reported in this study. The sulfate radicals were produced by the cobalt-mediated decomposition of peroxymonosulfate (Oxone) in an aqueous homogeneous system. The major intermediates formed from the transformation of 2,4-dichlorophenol were 2,4,6-trichlorophenol, 2,3,5,6-tetrachloro-1,4-benzenediol, 1,1,3,3-tetrachloroacetone, pentachloroacetone, and carbon tetrachloride. Those resulting from the transformation of phenol in the presence of chloride ion were 2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 1,1,3,3-tetrachloroacetone, and pentachloroacetone. In the absence of chloride ion, phenol transformed into 2,5-cyclohexadiene-1,4-dione (quinone), 1,2-benzenediol (catechol), and 1,4-benzenediol (hydroquinone). Several parameters were varied, and their impact on the transformation of the organic compounds is also discussed. The parameters varied were the initial concentration of the organic substrate, the dose of Oxone used, the cobalt counteranion, and in particular the impact of chloride ions and the quenching agent utilized for terminating the reaction. This is one of the very few studies dealing with intermediates formed via sulfate radical attack on phenolic compounds. It is also the first studythat explores the sulfate radical mechanism of oxidation, when sulfate radicals are generated via the Co/Oxone reagent. Furthermore, it provides strong evidence on the interaction of chloride ions with sulfate radicals leading to halogenation of organics in water.     

TiO₂-photocatalytic reduction of pentavalent and trivalent arsenic: production of elemental arsenic and arsine

Heterogeneous photocatalytic reduction of As(V) and As(III) at different concentrations over TiO(2) under UV light in deoxygenated aqueous suspensions is described. For the first time, As(0) was unambiguously identified together with arsine (AsH(3)) as reaction products. As(V) reduction requires the presence of an electron donor (methanol in the present case) and takes place through the hydroxymethyl radical formed from methanol oxidation by holes or hydroxyl radicals. On the contrary, As(III) reduction takes place through direct reduction by the TiO(2)-conduction band electrons. Detailed mechanisms for the photocatalytic processes are proposed. Although reduction to solid As(0) is convenient for purposes of As removal from water as a deposit on TiO(2), attention must be paid to formation of AsH(3), one of the most toxic forms of As, and strategies for AsH(3) treatment should be considered.     

Evaluation of the intrinsic photocatalytic oxidation kinetics of indoor air pollutants

This paper presents a methodology for the evaluation of the intrinsic photocatalytic oxidation (PCO) kinetics of indoor air pollutants. It combines computational fluid dynamics (CFD) modeling of the fluid flow in the reactor with radiation field modeling and photocatalytic reaction kinetics to yield a rigorous model of a flat-plate, single-pass, flow-through photocatalytic reactor for indoor air purification. This method was applied to model the PCO of trichloroethylene (TCE) in humidified air and to derive kinetic parameters directly from kinetic data in an integral flow reactor. Steady-state PCO experiments of TCE over irradiated TiO2 (Degussa P25) thin films immobilized on glass supports were carried out at different radiation intensities, flow rates, and inlet substrate concentrations. The oxidation rate of TCE was found to be first-order on the incident photon flux and to follow a Langmuir-Hinshelwood type reaction kinetics rate law. Mass transfer resistances were observed at Reynolds numbers less than 46. Apparent quantum yields were found to be up to 0.97 mol Einstein(-1). A comparison of the model prediction with the experimental results in an integral reactor yielded pollutant-specific kinetic rate parameters which were independent of reactor geometry, radiation field, and fluid-dynamics. The kinetic parameters would,therefore, be more universally applicable to the design and scale-up of photocatalytic reactors for indoor air purification.     

酸性红37光催化降解动力学的响应曲面法优化及其转化机制

为探索单偶氮染料酸性红37 在水溶液中降解的可行性及在活性氧物种作用下可能的迁移转化机制,利用光催化技术并根据中心复合实验设计原理建立了不同因素对酸性红37 光催化降解效率影响的二次回归方程,得出酸性红37光催化降解的最优条件：催化剂（P25TiO2）质量浓度为2.3 g/L,底物浓度为90μmol/L,温度为12.5 ℃,溶液初始pH值为8.7。研究结果表明：水溶液中不同阴阳离子对酸性红37 降解动力学的影响较大,其中Na+、Fe2+、Fe3+和Zn2+ 等对酸性红37 的降解具有明显的抑制作用,而Cu2+则体现了一定程度的促进作用;然而CrO42-、SO42-、ClO3-、MnO4- 和Cl- 则对其降解均体现了不同程度的抑制作用。最后利用气相色谱质谱联用仪对酸性红37的光催化降解产物进行了初步的分离并进行分析,认为光催化过程中酸性红37分子中N=N和C-N键断裂后的进一步羟基化反应是其主要的降解途径。     

Formation of Pb(III) intermediates in the electrochemically controlled Pb(II)/PbO₂ system

The formation of lead dioxide PbO(2), an important corrosion product in drinking water distribution systems with lead-bearing plumbing materials, has been hypothesized to involve Pb(III) intermediates, but their nature and formation mechanisms remain unexplored. This study employed the electrochemical (EC) method of rotating ring disk electrode (RRDE) and quantum chemical (QC) simulations to examine the generation of intermediates produced during the oxidation of Pb(II) to PbO(2). RRDE data demonstrate that PbO(2) deposition and reduction involves at least two intermediates. One of them is a soluble Pb(III) species that undergoes further transformations to yield immobilized PbO(2) nanoparticles. The formation of this intermediate in EC system is mediated by hydroxyl radicals (OH(?)), as was evidenced by the suppression of intermediates formation in the presence of the OH(?) scavenger para-chlorobenzoic acid. QC simulations confirmed that the oxidation of Pb(II) by OH(?) proceeds via Pb(III) species. These results show that Pb(III) intermediates play an important role in the reactions determining transitions between Pb(II) and Pb(IV) species and could impact lead release in drinking water.     

The aqueous degradation of butylated hydroxyanisole by UV/S2O8(2-): study of reaction mechanisms via dimerization and mineralization

Three distinctive phases of BHA reactivity toward UV/ S2O8(2-) at acidic, neutral, and basic pH range were examined, where 80-100% mineralization has been observed within an hour of irradiation under 254 nm. A reduction in solution pH during the reaction was observed mainly due to the complete conversion of S2O8(2-) to sulfate ion together with proton generation. Seven measurable intermediates were found via an oxidation and dimerization process at all tested pH levels. The BHA decay mechanisms are quite different in acidic condition and at other pH levels. There are three unique intermediates that are only detectable at pH 3 via two additional pathways. This is due to the generation of weaker oxidants or radicals which results in a slower degradation of the BHA, and therefore, the accumulation of these intermediates to detectable levels. The rate of BHA decay generally increases from low to high pH levels; however, the corresponding mineralization at higher pH is retarded due to the futile process of recombining radicals and involvement of intermediates. Therefore, neutral pH was suggested to be the optimum condition in terms of mineralization and moderate efficiency in removing BHA.     

Design of BDD-TiO2 hybrid electrode with P-N function for photoelectroatalytic degradation of organic contaminants

P-N hybrid electrode of boron-doped diamond (BDD) and TiO2 were designed and fabricated via selective deposition of TiO2 onto BDD electrode. This hybrid electrode exhibit high photoelectrocatalytic activities toward degradation of acid orange II (AOII) and 2, 4-dichloropheonl (2,4-DCP) due to the P-N effect and high electrocatalytic and photocatalytic activities of BDD electrode and TiO2 particles. The structures of TiO2 and BDD were confirmed by Raman spectra analysis. Atom force microscopy and scanning electron microscopy showed that the TiO2 deposits consist of adherent nanomicro-sized particles, scattered on the BDD substrate. AOII and 2,4-DCP in a solution can be efficiently degraded at the hybrid electrode in the photoelectrocatalysis (PEC) process. Effect of applied bias potentials and solution pH values on AOII and 2,4-DCP degradation were investigated. In the electro-oxidation process, some intermediates such as phenols were detected and they accumulated with the reaction evolution based on the analysis of UV-vis and GC-MS variation. By contrast, phenols intermediates will be degraded with the reaction evolution in the photoelectrocatalysis process. And, organic aromatic and aliphatic carboxylic acids were detected. Furthermore, different degradation mechanism of AOII and 2,4-DCP in the electro-oxidation, photocatalysis, and photoelectrocatalysis is proposed.     

Organic aerosol formation during the atmospheric degradation of toluene

Organic aerosol formation during the atmospheric oxidation of toluene was investigated using smog chamber systems. Toluene oxidation was initiated by the UV irradiation of either toluene/air/NOx or toluene/air/CH3ONO/NO mixtures. Aerosol formation was monitored using scanning mobility particle sizers and toluene loss was monitored by in-situ FTIR spectroscopy or GC-FID techniques. The experimental results show that the reaction of OH radicals, NO3 radicals and/or ozone with the first generation products of toluene oxidation are sources of organic aerosol during the atmospheric oxidation of toluene. The aerosol results fall into two groups, aerosol formed in the absence and presence of ozone. An analytical expression for aerosol formation is developed and values are obtained for the yield of the aerosol species. In the absence of ozone the aerosol yield, defined as aerosol formed per unit toluene consumed once a threshold for aerosol formation has been exceeded, is 0.075 +/- 0.004. In the presence of ozone the aerosol yield is 0.108 +/- 0.004. This work provides experimental evidence and a simple theory confirming the formation of aerosol from secondary reactions.     

Kinetics of simultaneous photocatalytic degradation of phenolic compounds and reduction of metal ions with nano-TiO2

The simultaneous photocatalytic degradation of phenol and 4-nitrophenol and reduction of metal ions like copper (Cu2+) and chromium (Cr6+) was studied with solution combustion synthesized nanoanatase TiO2 (CS TiO2) and commercial titania, Degussa P-25. The presence of metal ion reduces the rate of degradation of phenol and 4-nitrophenol. It was found that Cu2+ reduction to Cu+ is accelerated in the presence of phenol. In the case of Cr6+, CS TiO2 enhances the initial adsorption of Cr6+ and complete reduction is achieved within the first 10 min of UV irradiation. The presence of phenol or 4-nitrophenol also enhances the initial adsorption of Cr6+ and its reduction. The metal ion reduction in the presence of CS TiO2 is compared with that of Degussa P-25. The rate of reduction of metal ions in presence of Degussa P-25 is twice as slow as that of CS TiO2 in presence of both phenol and 4-nitrophenol. The presence of Cu2+ and Cr6+ also induces the formation of the intermediates which were not observed for the phenol-CS TiO2 system. The formation and consumption of the intermediates are modeled with a simple series reaction mechanism. A detailed dual-cycle, multistep reaction mechanism of TiO2 photocatalysis for the simultaneous degradation and reduction is proposed and the model is developed following the network reduction technique. The kinetic rate constants in the model are evaluated for the systems studied.     

Pu(V)O2+ adsorption and reduction by synthetic hematite and goethite

Changes in aqueous- and solid-phase plutonium oxidation state were monitored over time in hematite (alpha-Fe2O3) and goethite (alpha-FeOOH) suspensions containing 239Pu(V)-amended 0.01 M NaCl. Solid-phase oxidation state distribution was quantified by leaching plutonium into the aqueous phase and applying an ultrafiltration/solvent extraction technique. The technique was verified using oxidation state analogues of plutonium and sediment-free controls of known Pu oxidation state. Batch kinetic experiments were conducted at hematite and goethite concentrations between 10 and 500 m2 L(-1) in the pH range of 3-8. Surface-mediated reduction of Pu(V) was observed for both minerals at pH values of 4.5 and greater. At pH 3 no adsorption of Pu(V) was observed on either goethite or hematite; consequently, no reduction was observed. For hematite, adsorption of Pu(V) was the rate-limiting step in the adsorption/reduction process. In the pH range of 5-8, the overall removal of Pu(V) from the system (solid and aqueous phases) was found to be approximately second order with respect to hematite concentration and of order -0.39 with respect to the hydrogen ion concentration. The overall reaction rate constant (k(rxn)), including both adsorption and reduction of Pu(V), was 1.75+/-2.05 x 10(-10) (m(-2) L)(-2.08) (mol(-1) L)(-0.39) (s(-1)). In contrast to hematite, Pu(V) adsorption to goethite occurred rapidly relative to reduction. At a given pH,the reduction rate was approximately independent of the goethite concentration, although the hydrogen ion concentration (pH) had only a slight effect on the overall reaction rate. For goethite, the overall reaction rates at pH 5 and pH 8 were 6.0 x 10(-5) and 1.5 x 10(-4) s(-1), respectively. For hematite, the reaction rate increased by 3 orders of magnitude across the same pH range.     

基于ESR光谱技术检测食品中自由基的研究进展

自由基是食品在发生氧化过程中形成的高度反应性中间体,针对食品体系中自由基的检测可以用来评价食品的氧化程度。电子自旋共振技术(Electron Spin Resonance,ESR)可以提供有用的结构信息使自由基被识别,ESR已成功检测不同食品中存在的自由基。本文介绍了ESR技术在不同食品体系中检测自由基的应用,分析了自旋捕获在ESR检测食品中自由基的效果,阐述了ESR检测技术在预测食品氧化稳定性方面发挥的作用。ESR技术可以为食品体系中自由基的跟踪、评定及食品氧化稳定性的预测提供理论依据。     

Mechanism of perchlorate formation on boron-doped diamond film anodes

This research investigated the mechanism of perchlorate (ClO(4)(-)) formation from chlorate (ClO(3)(-)) on boron-doped diamond (BDD) film anodes by use of a rotating disk electrode reactor. Rates of ClO(4)(-) formation were determined as functions of the electrode potential (2.29-2.70 V/standard hydrogen electrode, SHE) and temperature (10-40 °C). At all applied potentials and a ClO(3)(-) concentration of 1 mM, ClO(4)(-) production rates were zeroth-order with respect to ClO(4)(-) concentration. Experimental and density functional theory (DFT) results indicate that ClO(3)(-) oxidation proceeds via a combination of direct electron transfer and hydroxyl radical oxidation with a measured apparent activation energy of 6.9 ± 1.8 kJ·mol(-1) at a potential of 2.60 V/SHE. DFT simulations indicate that the ClO(4)(-) formation mechanism involves direct oxidation of ClO(3)(-) at the BDD surface to form ClO(3)(?), which becomes activationless at potentials > 0.76 V/SHE. Perchloric acid is then formed via the activationless homogeneous reaction between ClO(3)(?) and OH(?) in the diffuse layer next to the BDD surface. DFT simulations also indicate that the reduction of ClO(3)(?) can occur at radical sites on the BDD surface to form ClO(3)(-) and ClO(2), which limits the overall rate of ClO(4)(-) formation.     

Heterogeneous photocatalytic reduction of chromium(VI) over TiO2 particles in the presence of oxalate: involvement of Cr(V) species

Cr(VI) photocatalytic reduction experiments over TiO2 particles under near UV irradiation in the presence of excess oxalate were performed at acid pH (2 and 3) and under air and N2 bubbling. Initial photonic efficiencies for Cr(VI) reduction are nearly the same under aerobic and anaerobic conditions, but show a significant increase at the lowest pH. At pH 2, the addition of oxalate facilitates Cr(VI) reduction, hindering the electron-shuttle mechanism taking place in pure water. The oxalate synergistic effect at pH 2 is lower than that previously found for EDTA and negligible at pH 3. Chromium(V) oxalate concentration profiles were obtained by EPR spectroscopy in the presence of excess oxalate at pH 1.5. Coordinated Cr(V) complexes [Cr(V)(O)(Ox)2]-, [Cr(V)(OH2)(Ox)2]-, and [Cr(V)(O)(OH)2(Ox)]- were identified, on the basis of the comparison of their corresponding g values with recent literature data. The kinetic analysis of the temporal evolution of the paramagnetic Cr(V) species indicates also an effective photocatalytic degradation of chromium(V) oxalate complexes. This new evidence reinforces previous findings regarding sequential one-electron-transfer processes in Cr(VI) photocatalytic reduction, suggesting that this route may represent a general behavior for the Cr(VI) reduction over UV-irradiated TiO2 particles.     

The hydrogen peroxide-assisted photocatalytic degradation of alachlor in TiO2 suspensions

Photocatalytic degradations of alachlor in TiO2 suspensions with and without the use of hydrogen peroxide were studied using two different monochromatic UV irradiations (300 and 350 nm). Direct photolysis of alachlor was a rather slow process, but the addition of TiO2 enhanced the reaction rates by 12 and 26 times using 300 and 350 nm UV irradiation, respectively. The results showed that a low H2O2 dosage in photocatalysis using 300 nm UV would enhance the rates by 3.3 times, but an overdose of H2O2 will retard the rate due to the hydroxyl radicals are consumed. However, this process is impracticable at 350 nm due to the absorption characteristic of H2O2. A neutral initial pH level was found to favor the H2O2 assisted photocatalysis at 300 nm UV illumination. Eleven major intermediates were identified by liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) and MS/MS. The major degradation mechanisms of H2O2-assisted alachlor photocatalysis include dechlorination, dealkylation, hydroxylation, cyclization, scission of C-O bond, and N-dealkylation. Bell-shaped evolution profiles of different intermediates were observed. Degradation pathways were proposed accordingly to illustrate series of degradation steps. The TOC analysis revealed the different stages of the reaction.     

TiO2-based photocatalytic degradation of 2-chlorophenol adsorbed on hydrophobic clay

The combination of adsorption and heterogeneous photocatalysis has been investigated as a promising technology for the removal of organic water pollutants. A laboratory study of the removal and decomposition of 2-chlorophenol (2-CP) as a toxic organic pollutant was carried out under various conditions with an organophilized clay mineral (hexadecylpyridinium chloride-modified montmorillonite; HDPM) as adsorbent and Degussa P25 TiO2 as photocatalyst. Three different oxidation processes leading to the degradation of 2-CP were compared: direct photolysis, heterogeneous photocatalysis in a TiO2 suspension, and the decomposition of substrate adsorbed on HDPM in the presence of TiO2. Both the degradation of 2-CP and the formation of intermediates were analyzed by HPLC, the total organic carbon content and the total organic and inorganic chloride contents were measured to monitor the mineralization process, and X-ray diffraction and thermoanalytical measurements were made to characterize the hydrophobic clay adsorbent. The heterogeneous photocatalytic degradation of dissolved (2-CP/UV/TiO2) and desorbed 2-CP (2-CP/HDPM/UV/TiO2) appeared to be equally efficient, whereas direct photolysis of 2-CP was far less efficient in the oxidative destruction. HDPM proved to be a suitable adsorbent, capable of adsorbing toxic organics from water. It was demonstrated that the adsorbent (at relatively high concentration) did not decrease the rate of mineralization of 2-CP. The results confirmed that the adsorbent retains its structure and composition during the mineralization process, and thus it can be reused without regeneration. The combination of adsorption and heterogeneous photocatalysis studied may be an efficient and economical means of accumulating, removing, and oxidizing organic water contaminants, and its application is in accordance with the growing environmental demands.