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Membrane filtration has been increasingly used for water treatment and wastewater reclamation in recent years. To further improve the effectiveness of membrane process and reduce membrane fouling, a highly reactive photocatalytic membrane, Ag-TiO(2)/hydroxiapiate (HAP, Ca(10)(PO(4))(6)(OH)(2))/Al(2)O(3), was employed to realize microfiltration (MF) coupling photocatalysis for surface water treatment. The effectiveness on the potential of membrane was investigated by removing humic acid (HA) test under different feed total organic carbon (TOC), light intensity and transmembrane pressure (TMP). The HA removal and anti-fouling property of as-prepared membrane was improved under UV irradiation, likely due to photocatalytic degradation of foulants along with filtration simultaneously. Under given feed water composition, increasing the light intensity resulted in increased removal of HA from aqueous solution. However, a limiting TMP seems to exist beyond which the increased HA removal cannot be sustained. Fouling behavior analysis indicated that the transition in fouling mode from initial pore blocking to cake filtration occurred much slower as UV irradiated. Furthermore, a superior efficiency on removal of trace organic contaminants, as well as milder flux reduction, was presented from surface water treatment, which demonstrated that the integrated system with enhanced performance is foreseen as an emerging technique for water treatment., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

To elucidate the relationship between photochemical functions with the structure of humic acids (HA), we developed a molecular imprinting method to separate the substances with given structure and investigated their photochemical behavior in aqueous solution. The substances with porphyrin-like core structure, such as chlorophyll or heme, were employed as template substances for preparing molecular imprinting polymers (MIP). The polymers were used to separate the substances with porphyrin-like structure from HA. Photochemical experiments were conducted to evaluate effects of the separated HA fractions on the photodegradation of coexisting organic pollutant. The results showed that all fractions bound by MIP accelerated photochemical degradation of coexisting 2,4-dichlorophenoxyacetic acid (2,4-D) under simulated sunlight (lambda>290 nm) irradiation, indicating that HA with porphyrin-like structure possesses better photoactivity than ones without the structure. The photochemical degradation of 2,4-D was enhanced when Fe(III), the ubiquitous element in natural aquatic systems, was added owing to the formation of Fe(III) complex with the HA. Electron paramagnetic resonance (EPR) spectra indicated that OH* and 1O2 radicals were generated in the solutions of HA fractions bound by MIP under simulated sunlight irradiation, implying that 2,4-D degradation could be related to oxidation reactions caused by reactive oxygen species (ROS).

The silicon-doped BiVO(4) film was fabricated by modified metalorganic decomposition (MOD) method. XRD analysis indicated that the crystal size of the BiVO(4) film was decreased from 32.4nm to 23.9nm by doping Si. The measurements of FT-IR spectra and the water contact angle showed that doping Si could elevate the surface hydrophilicity of the BiVO(4) film. The phenol elimination rate on the Si-doped BiVO(4) film electrode in the photoelectrocatalytic process was 1.84 times as great as that on the BiVO(4) film electrode. The enhanced photoelectrocatalytic performance was attributed to the decrease of the crystalline size and the enhancement of the hydrophilic performance., (Copyright (c) 2010 Elsevier B.V. All rights reserved.)

Inverse TiO(2) opal photonic crystal coupled TiO(2)/poly(3-hexylthiophene) (bilayer TiO(2)/P3HT) was structured on FTO substrate for efficient photocatalysis under visible light irradiation (lambda > 400 nm). We expected that the photocatalytic capability of this hybrid photocatalyst could be enhanced by the efficient visible light absorption owing to the photonic crystal structure and effective charge separation owing to the unique heterojunction built between TiO(2) and P3HT. The bilayer TiO(2)/P3HT photocatalyst was prepared first by depositing inverse TiO(2) opal on FTO substrate via replicating polystyrene opal, followed by spin coating a layer of TiO(2) nanoparticles on the inverse TiO(2) opal. The as prepared bilayer TiO(2) was modified by P3HT via dipping method. Environmental scanning electron microscopy (ESEM) images demonstrated that the as prepared photocatalyst was composed of inverse TiO(2) opal layer and TiO(2) nanoparticles layer. The UV-vis diffuse reflectance spectra showed that the optical absorption for bilayer TiO(2)/P3HT was more intensive than for pristine TiO(2) nanoparticle/P3HT (NP-TiO(2)/P3HT) in the range of 400-650 nm. The enhanced generation of photocurrent under visible light irradiation (lambda > 400 nm) was observed using the bilayer TiO(2)/P3HT. The results of photocatalytic experiments under visible light irradiation revealed that the pseudofirst-order kinetic constant of photocatalytic degradation of methylene blue using the bilayer TiO(2)/P3HT was 2.08 times as great as that using NP-TiO(2)/P3HT, showing the advantage of the unique structure in the bilayer TiO(2)/P3HT for efficient photocatalysis.

Facile and effective approaches were developed to fabricate the inverse TiO2/Pt opals Schottky structures on the Ti substrate. The as-prepared samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and diffuse reflectance UV-vis spectra (DRS), respectively. The results indicate that these samples were of ordered network, which was built by the Pt skeleton frame and the outer TiO2 layer. The TiO2 layer was identified as anatase with the preferential orientation of (101) plane. The experiments of short-circuit photocurrent (SCPC) and photocatalytic degradation of phenol were also conducted under the UV irradiation in order to evaluate the photoactivity of the samples. By tuning the red edge of photonic stop-band overlapping the absorption maximum of anatase (at 360 nm), both the UV absorption and the carrier separation of the samples were improved. The kinetic constant using the optimal inverse TiO2/Pt opals (0.992 h(-1)) was about 1.5 times as great as that of the disordered inverse TiO2/Pt opals (TiO2/Pt-mix) and was 3.3 times as great as that of pristine TiO2 nanocrystalline film (TiO2-nc) on Ti substrate.

For the sake of utilizing the light-harvesting ability of Si in pollution control, the p-silicon nanowire (SiNW)/TiO2 core/shell heterojunction arrays have been synthesized. Based on the surface photovoltage (SPV) measurement, these p-SiNW/TiO2 heterojunction arrays display considerable SPV response to the light with wavelength ranging from 300 to 700 nm. Under the protection of TiO2 shell, the SiNW core could harvest visible light stably in aqueous solution. The resistivity of the starting Si wafer has a distinct influence on the cathodic behaviors of p-SiNW/TiO2 arrays. The higher photocurrent is observed for the sample using the starting Si wafer with moderate resistivity, in contrast with those using high- or low-resistivity starting Si wafer. In the photoelectrocatalytic experiments of phenol degradation under visible light irradiation conditions, the kinetic constant using p-SiNW/TiO2 cathode (0.983 h(-1)) is 17.7 times larger than that (0.0523 h(-1)) of TiO2 film on p type Si wafer (p-Si/TiO2). This result demonstrates that p-SiNW/TiO2 cathode could utilize visible lightto decompose phenol with a considerable efficiency. The mechanism of phenol degradation is considered that the photogenerated electrons from p-SiNW/TiO2 cathode could be scavenged by dissolved oxygen first followed by generation of hydroxyl radicals species via a chain reaction, and finally phenol could be oxidized. By constructing this kind of heterojunctions, many other narrow-band gap semiconductors might be utilized as photocatalysts in pollution control, consequently, the optimal sunlight harvesting would be achieved.

Chlorinated organic compounds are generally of great concern, but many uncertainties exist regarding how they are generated. To illustrate the possibility of photochemical formation of organochlorine compounds in natural water, the phototransformation of bisphenol A (BPA) in aqueous saline solution containing Fe(lll) and fulvic acid (FA), and in coastal seawater under simulated solar light irradiation was investigated. 2-(3-Chloro-4-hydroxyphenyl)-2-(4-hydroxyphenyl) propane (3-CIBPA) and 2,2-bis(3-chloro-4-hydroxyphenyl) propane (3,3-diCIBPA) were the main chlorinated derivatives during the processes. Laser flash photolysis (LFP) and electron spin resonance (ESR) results indicated that the chlorination of BPA was most likely due to the formation of Cl2(*-) radical as a consequence of Fe(III) irradiation, yielding Cl* and OH* radical species and finally forming Cl2(*-) radical upon further reaction with chloride. The formation of Fe(III)-FA complex, which is a normal coexistence configuration of Fe(III) and FA in natural water, promoted the BPA chlorination through producing more Cl2(*-) radical. Moreover, FA had two opposite effects: forming Fe(III)-FA complex to enhance Cl2(*-) formation and competing radicals with BPA, which resulted in different overall effects at different concentrations: BPA chlorination was enhanced with the increasing of FA concentration ([FA]) when [FA] < 3.2 mg L(-1); when the concentration of FA was as high as 10 mg L(-1), it slowed down obviously. The described BPA photochlorination process took place from pH 6.3 to 8.5 and increased with the increasing of chloride concentration, indicating it could occur universally in natural saline surface water. These results propose a natural photochemical source for organochlorine compounds.

Ag particles were doped on BiVO(4) film by photoreduction technique. XRD analysis indicated that the chemical state of the Ag particles was metallic Ag. TEM observation confirmed that the sizes of the Ag particles were 10-20nm. The investigation of the phenol degradation demonstrated that the photocatalytic (PC) degradation rate of the phenol on the Ag doped BiVO(4) film was enhanced by 1.61 times in PC process and by 42.7 times in photoelectrocatalytic (PEC) process compared with that of the BiVO(4) film. The transportation of the electrons from the BiVO(4) to Ag driven by the schottky barrier formed between Ag and BiVO(4) can increase the charge carrier separation, and consequently enhance the PC performance. The enhancement of the PC ability in PEC process could be attributed to the simultaneous movements of the photogenerated electrons to external circuit and the photogenerated holes to the Ag particles deposited on the BiVO(4) film. In 4h, the elimination efficiency and the TOC removal efficiency of phenol on the Ag doped BiVO(4) film in PEC process were 94.1% and 61.0%, respectively.

To elucidate the existence of phthalocyanine-like (Pc-like) substances in humic acids (HA) and their roles in photochemical transformation of organic pollutants, Pc-imprinted polymers (MIP) were synthesized successfully and employed to separate Pc-like substances from HA. The fraction bound by MIP (F(mip-b)) presented better photochemical activity for degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution irradiated by simulated sunlight. The pseudo-first-order rate constant of 2,4-D photodegradation with the presence of F(mip-b) was 2.5 times as high as that in solution containing effluent fraction (F(eff)). These results show the key role of some HA with special structures in photochemistry and are helpful for better understanding phototransformation of environmental contaminants in natural aquatic systems.

Thermal remediation of the soil contaminated with crude oil using microwave heating enhanced by carbon fiber (CF) was explored. The contaminated soil was treated with 2.45 GHz microwave, and CF was added to improve the conversion of microwave energy into thermal energy to heat the soil. During microwave heating, the oil contaminant was removed from the soil matrix and recovered by a condensation system of ice-salt bath. The experimental results indicated that CF could efficiently enhance the microwave heating of soil even with relatively low-dose. With 0.1 wt.% CF, the soil could be heated to approximately 700 degrees C within 4 min using 800 W of microwave irradiation. Correspondingly, the contaminated soil could be highly cleaned up in a short time. Investigation of oil recovery showed that, during the remediation process, oil contaminant in the soil could be efficiently recovered without causing significant secondary pollution.

Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil-water distribution coefficients (K(oil)). The resulting oil-contaminated soil-water distribution coefficients (K(d)) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C(oil)) but sorption-reducing (competitive) effects at intermediate C(oil) (approximately 1 g kg(-1)). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K(d) at C(oil) above approximately 1 g kg(-1) were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.

ZnIn2S4 film was fabricated on Ti substrate by a two-step approach including electrodeposition and annealing. The film obtained after electrodeposition was composed of Zn, In, and S. Then this precursor film was gradually converted to hexagonal phase ZnIn2S4 during the process of annealing in a nitrogen flow. The crystallographic structures and photoresponse ability of the film could be affected significantly by the annealing temperature. From diffuse reflection spectra, ZnIn2S4 film annealed at 500 degrees C exhibited the highest absorption intensity in visible light region among all the samples, resulting in a high photoresponse in the electrochemical measurement. The microstructures of ZnIn2S4 were characterized by transmission electron microscopy, and the results indicated that the interlayer distance was 0.295 nm, corresponding to d(104) space of hexagonal ZnIn2S4. Energy-dispersive X-ray spectra showed that the atomic ratio of Zn:In:S was 9.3:20.3:39.5, which was close to the stoichiometry ZnIn2S4. The photocatalytic ability of ZnIn2S4 was investigated by photoelectrocatalytic inactivation of Escherichia coli ( E. coli) with the initial concentration of approximately 3 x 10(8) colony forming units per milliliter. More than 3 logs of E. coli were killed within 60 min with the ZnIn2S4 film under visible light, and when the photocatalytic process was assisted by a 0.6 V positive potential, no surviving bacteria were detected after 60 min of inactivation.

A TiO2-boron doped diamond (TiO2-BDD) heterojunction was employed as a photocatalyst to simultaneously oxidize an azo dye C.I. reactive yellow 15 (RY15) and reduce hexavalent chromium (Cr(VI)). This heterojunction was fabricated first by depositing a BDD film on a Ti sheet in a hot filament chemical vapor deposition reactor, followed by covering a layer of TiO2 in a metal-organic chemical vapor deposition system. The morphology of this heterojunction was characterized by using a scanning electron microscope (SEM). X-ray diffraction (XRD), Raman spectroscopy, and current-voltage (I-V) measurement were used to characterize its structures. Additionally, the characterization of surface photovoltage showed that the TiO2-BDD heterojunction exhibited a higher photovoltage response and a better ability for charge separation than the photocatalyst of TiO2 directly deposited on a Ti sheet (TiO2-Ti). The photocatalytic experiments revealed that the kinetic constants for the oxidation of RY15 and the reduction of Cr(VI) were, respectively, increased by 85 and 71% when the photocatalyst of TiO2-Ti was replaced by the TiO2-BDD heterojunction. Meanwhile, a significant synergy was confirmed in the simultaneous oxidation of RY15 and reduction of Cr(VI). The enhanced photocatalytic ability of the TiO2-BDD composite could be attributed to the heterojunction. The possible photocatalytic mechanism was also discussed.

A single-step route was developed for the direct growth of tungsten oxide nanobelt arrays by heating a tungsten sheet without additional catalysts or reactants. X-ray diffraction and Raman analysis indicated that the tungsten oxide nanobelts were monoclinic. The surface photovoltage signal and photocurrent density of the tungsten oxide nanobelt arrays clearly suggested a high photoconversion ability. Further investigation demonstrated that the photoelectrocatalytic activity of the nanobelt arrays was higher than that of a tungsten oxide film when using phenol as the probe molecule.

The photochemical formation of Fe(II) and hydrogen peroxide (H 2O 2) coupled with humic acids (HA) was studied to understand the significance of iron cycling in the photodegradation of atrazine under simulated sunlight. The presence of HA significantly enhanced the formation of Fe(II) and H 2O 2, and their subsequent product, hydroxyl radical ( (*)OH), was the main oxidant responsible for the atrazine photodegradation. During 60 h of irradiation, the fraction of iron presented as Fe(II) (Fe(II)/Fe(t)) decreased from 20-32% in the presence of the Fe(III)-HA complex to 10-22% after adding atrazine. The rate of atrazine photodegradation in solutions containing Fe(III) increased with increasing HA concentration, suggesting that the complexation of Fe(III) with HA accelerated the Fe(III)/Fe(II) cycling. Using fluorescence spectrometry, the quenching constant and the percentage of fluorophores participating in the complexation of HA with Fe(III) were estimated by the modified Stern-Volmer equation. Fourier transform infrared spectroscopy (FTIR) offered the direct evidence that Fe(III)-carboxylate complex could be formed by ligand exchange of HA with Fe(III). Based on all the information, a possible reaction mechanism was proposed.

Catalytic wet air oxidation (CWAO) is a promising method for the treatment of heavily contaminated wastewater. However, its application is restricted due to severe operation conditions (high pressure and high temperature). A microwave (MW) assisted oxidation method was investigated aiming to treat heavily contaminated wastewater under milder conditions. H-acid (1-amino-8-naphthol-3, 6-disulfonic acid) was selected as target compound to evaluate the performance of this novel process. The removal of H-acid and TOC (total organic carbon) for H-acid solution of 3000 mg/L reached as high as 92.6% in 20 min and 84.2% in 60 min, respectively under optimal conditions. The existence of activated carbon and oxygen proved to be critical for effective treatment. The activated carbon acted not only as a catalyst for H-acid decomposition, but also as a special material for the absorption of MW energy. Air was supplied to the reactor as an oxygen source at constant flows. The amino group in H-acid was converted ultimately into nitrate, and sulfonic group into sulfate. This observation gave an evidence of H-acid mineralization although other organic intermediates were unable to be determined. The value of BOD(5)/COD (ratio of 5d biochemical oxygen demand to chemical oxygen demand) increased from 0.008 to 0.467 indicating a significant improvement of biodegradability for the solution, which is beneficial for the further biological treatment of the wastewater.