可见光活化过二硫酸盐对染料废水的降解研究

以染料废水中亚甲基蓝(MB)作为目标污染物,考察了可见光活化过二硫酸盐(PDS)体系中PDS浓度、溶液pH、MB初始质量浓度等因素对MB溶液降解性能的影响,并分析了该体系中主要的反应活性物种。结果表明:在酸性条件下,可见光活化PDS体系去除MB的效果较好,且提高PDS浓度有助于MB的降解;硫酸根自由基(·SO_(4)^(-))是MB降解反应的主要活性自由基,而羟基自由基(·OH)对去除MB的影响较小。可见光活化PDS作为一种新型高级氧化技术对染料废水中有机污染物的降解效果显著。

可见光活化过硫酸盐降解双(2-氯乙基)醚

研究了不同活化方式下过硫酸盐对双(2-氯乙基)醚(BCEE)的降解效果,重点考察了可见光活化过硫酸盐降解BCEE体系中过硫酸钠投加量、BCEE初始浓度、初始pH以及无机阴离子和腐殖酸对反应的影响。结果表明,酸性条件下BCEE的降解效果较好,且随着过硫酸钠投加量增大或BCEE初始浓度减小,BCEE的降解率提高。反应最佳条件为BCEE质量浓度4mg/L、过硫酸钠投加量20mmol/L、溶液初始pH调至3,降解过程符合一级动力学方程。溶液中存在CO23-、HCO3-或Cl-均对BCEE的降解有抑制作用,加入腐殖质则会促进BCEE的降解。通过液-液萃取进行前处理,使用气相色谱/质谱分析检测出3种降解中间产物,分别为1,2-二氯丙烷、氯甲酸异丙酯和氯甲酸氯乙酯。

Substrate-dependent photoreactivities of BiOBr nanoplates prepared at different pH values

In this study,we showed that BiO Br nanoplates prepared at different pH values have substratedependent photocatalytic activities under visible-light irradiation. The BiO Br nanoplates synthesized at pH 1（BOB-1） degraded salicylic acid more effectively than did those obtained at pH 3（BOB-3）,but the order of their photocatalytic activities in rhodamine B（RhB） degradation were reversed. Electrochemical Mott–Schottky and zeta-potential measurements showed that BOB-1 had a more positive valence band and lower surface charge,leading to superior photocatalytic activity in salicylic acid degradation under visible light. However,BOB-3 was more powerful in RhB degradation because larger numbers of superoxide radicals were generated via electron injection from the excited RhB to its more negative conduction band under visible-light irradiation; this was confirmed using active oxygen species measurements and electron spin resonance analysis. This study deepens our understanding of the origins of organic-pollutant-dependent photoreactivities of semiconductors,and will help in designing highly active photocatalysts for environmental remediation.

Visible-Light Activities of Erbium Doped BiVO4 Photocatalysts

Er-doped BiVO4 composite photocatalyst was hydrothermal synthesized and characterized by X-ray powder diffraction, scanning electron microscopy, energy-dispersive X-ray Spectroscopy, X-ray photoelectron spectroscopy, and UV-Vis diffuse reflectance spectra techniques. The activity of the catalyst was determined by oxidative decomposition of methyl orange in aqueous solution under visible-light irradiation. X-ray photoelectron spectroscopy and energy-dispersive X-ray Spectroscopy analysis revealed that the doped Er existed in the form of Er2O3. It also showed that the Er doping can enhance the visible-light absorption abilities of catalysts and their visible-light-driven photocatalytic activities in comparison with those of pure BiVO4.

Co-MOF as an electron donor for promoting visible-light photoactivities of g-C3N4 nanosheets for CO2 reduction

A possible mechanism for boosting the visible-light photoactivities of graphitic carbon nitride(g-C3N4)nanosheets for CO2 reduction via coupling with the electron donor Co-metal-organic framework(MOF)is proposed in this study.Specifically,Co-MOF as an electron donor is capable of transferring the photogenerated electrons in the lowest unoccupied molecular orbital(LUMO)to the conduction band of g-C3N4 to facilitate charge separation.As expected,the prepared Co-MOF/g-C3N4 nanocomposites display excellent visible-light-driven photocatalytic CO2 reduction activities.The CO production rate of 6.75μmol g–1 h–1 and CH4 evolution rate of 5.47μmol g–1 h–1 are obtained,which are approximately 2 times those obtained with the original g-C3N4 under the same conditions.Based on a series of analyses,it is shown that the introduction of Co-MOF not only broadens the range of visible-light absorption but also enhances the charge separation,which improves the photocatalytic activity of g-C3N4 to a higher level.In particular,the hydroxyl radical(·OH)experiment was operated under 590 nm(single-wavelength)irradiation,which further proved that the photogenerated electrons in the LUMO of Co-MOF can successfully migrate to g-C3N4.This work may provide an important strategy for the design of highly efficient g-C3N4-based photocatalysts for CO2 reduction.

Preparation of a fullerene[60]‐iron oxide complex for the photo‐fenton degradation of organic contaminants under visible‐light irradiation

Iron oxide（Fe2O3） was doped onto fullerene[60]（C（60）） to form a C（60）‐Fe2O3 composite using an easy and scalable impregnation method. The as‐prepared C（60）‐Fe2O3 samples were characterized by powder X‐ray diffraction, X‐ray photoelectron spectroscopy, scanning electron microscopy, high‐resolution transmission electron microscopy, UV‐vis absorption spectroscopy, Raman spec‐troscopy, and Fourier transform infrared spectroscopy. The photocatalytic activity of the C（60）‐Fe2O3 catalyst was evaluated by examining the degradation of methylene blue（MB）, rhodamine B（RhB）, methyl orange（MO）, and phenol under visible light（λ 420 nm） in the presence of hydrogen per‐oxide. The results showed that the catalyst exhibited excellent catalytic properties over a wide pH range 3.06–10.34. Under optimal conditions, 98.9% discoloration and 71% mineralization of MB were achieved in 80 min. Leaching test results indicated that the leaching of iron from the catalyst was negligible and that the catalyst had a high photocatalytic activity after five reaction cycles. The catalyst was also efficient in the degradation of RhB, MO, and phenol. These findings could be at‐tributed to the synergetic effects of C（60） and Fe2O3. We used active species trapping experiments to determine the main active oxidant in the photocatalytic reaction process and found that hydroxyl radicals played a major role in the entire process.

In situ fabrication of CdMoO4/g-C3N4 composites with improved charge separation and photocatalytic activity under visible light irradiation

To further improve the charge separation and photocatalytic activities of g-C3N4 and CdMoO4 under visible light irradiation,CdMoO4/g-C3N4 composites were rationally synthesized by a facile precipitation-calcination procedure.The crystal phases,morphologies,chemical compositions,textural structures,and optical properties of the as-prepared composites were characterized by the corresponding analytical techniques.The photocatalytic activities toward degradation of rhodamine B solution were evaluated under visible light irradiation.The results revealed that integrating CdMoO4 with g-C3N4 could remarkably improve the charge separation and photocatalytic activity,compared with those of pristine g-C3N4 and CdMoO4.This would be because the CdMoO4/g-C3N4 composites could facilitate the transfer and separation of the photoexcited electron-hole pairs,which was confirmed by electrochemical impedance spectroscopy,transient photocurrent responses,and photoluminescence measurements.Moreover,active species trapping experiments demonstrated that holes(h+)and superoxide radicals(?O2?)were the main active species during the photocatalytic reaction.A possible photocatalytic mechanism was proposed on the basis of the energy band structures determined by Mott-Schottky tests.This work would provide further insights into the rational fabrication of composites for organic contaminant removal.

Pivotal roles of artificial oxygen vacancies in enhancing photocatalytic activity and selectivity on Bi_2O_2CO_3 nanosheets

There is an increasing interest in bismuth carbonate(Bi2O2CO3,BOC)as a semiconductor photocatalyst.However,pure BOC strongly absorbs ultraviolet light,which drives a high recombination rate of charge carriers and thereby limits the overall photocatalysis efficiency.In this work,artificial oxygen vacancies(OV)were introduced into BOC(OV-BOC)to broaden the optical absorption range,increase the charge separation efficiency,and activate the reactants.The photocatalytic removal ratio of NO was increased significantly from 10.0%for pure BOC to 50.2%for OV-BOC because of the multiple roles played by the oxygen vacancies.These results imply that oxygen vacancies can facilitate the electron exchange between intermediates and the surface oxygen vacancies in OV-BOC,making them more easily destroyed by active radicals.In situ DRIFTS spectra in combination with electron spin resonance spectra and density functional theory calculations enabled unraveling of the conversion pathway for the photocatalytic NO oxidation on OV-BOC.It was found that oxygen vacancies could increase the production of active radicals and promote the transformation of NO into target products instead of toxic byproducts(NO2),thus the selectivity is significantly enhanced.This work provides a new strategy for enhancing photocatalytic activity and selectivity.

One-pot topotactic synthesis of Ti^(3+) self-doped 3D TiO_2 hollow nanoboxes with enhanced visible light response

Ti^（3＋） self-doped anatase three-dimensional（3D） TiO_2 hollow nanoboxes were synthesized via a topological transformation process involving template participation by a facile one-pot hydrothermal treatment with an ethanol solution of zinc powder and TiOF_2. It is worth noting that the 3D TiO_2 hollow nanoboxes are assembled from six single-crystal nanosheets and have dominant exposure of the {001} facets. It is found from EPR spectra that adding zinc powder is an environment-friendly and effective strategy to introduce Ti^（3＋） and oxygen vacancy（Ov） into the bulk of 3D hollow nanoboxes rather than the surface, which is responsible for their enhanced visible photocatalytic properties.The photocatalytic activity was evaluated by measuring the formation rate of hydroxide free radicals using 7-hydroxycoumarin as a probe. The sample prepared with zinc/TiOF_2 mass ratio of0.25 exhibited the highest RhB photodegradation activity under visible-light irradiation with a degradation rate of 96%, which is 4.0-times higher than that of pure TiO_2. The results suggest a novel approach to construct in-situ 3D hierarchical TiO_2 hollow nanoboxes doped with Ti^（3＋） and Ov without introducing any impurity elements for superior visible-light photocatalytic activity.

Synergy of adsorption and visible light photocatalysis to decolor methyl orange by activated carbon/nanosized CdS/chitosan composite

Activated carbon/nanosized CdS/chitosan(AC/n-CdS/CS) composites as adsorbent and photoactive catalyst were prepared under low temperature(≤60 ℃) and ambient pressure.Methyl orange(MO) was chosen as a model pollutant to evaluate synergistic effect of adsorption and photocatalytic decolorization by this innovative photocatalyst under visible light irradiation.Effects of various parameters such as catalyst amount,initial MO concentration,solution pH and reuse of catalyst on the decolorization of MO were investigated to optimize operational conditions.The decolorization of MO catalyzed by AC/n-CdS/CS fits the Langmuir-Hinshelwood kinetics model,and a surface reaction,where the dyes are absorbed,is the controlling step of the process.Decolorization efficiency of MO is improved with the increase in catalyst amount within a certain range.The photodecolorization of MO is more efficient in acidic media than alkaline media.The decolorization efficiency of MO is still higher than 84% after five cycles and 60 min under visible light irradiation,which confirms the reusability of AC/n-CdS/CS composite catalyst.

Preparation of TiO_2 photocatalyst loaded with V_2O_5 for O_2 evolution

TiO2 photocatalysts loaded with V2O5 were prepared via a modified hydrolysis process,and characterized by X-ray diffraction,transmission electron microscopy,Raman spectra and diffuse reflectance UV-Vis spectra measurements. The photocatalytic activity of V2O5/TiO2 was investigated by employing splitting of water for O2 evolution. The results indicate that V2O5 loading can pronouncedly improve the photocatalytic activity of TiO2 with Fe3+ as an electron acceptor under UV or visible light irradiation. The optimum mass fraction of the loaded V2O5 is 8%,and the largest speed of O2 evolution for 8%V2O5 (mass fraction) loaded TiO2 catalyst is 118.2 μmol/(L.h) under UV irradiation,and 83.7 μmol/(L.h) under visible light irradiation.

Facile fabrication of CdS-metal-organic framework nanocomposites with enhanced visible-light photocatalytic activity for organic transformation

Visible-light-initiated organic transformations have received much attention because of low cost, relative safety, and environmental friendliness. In this work, we report on a novel type of visible-light-driven photocatalysts, namely, porous nanocomposites of CdS-nanoparticle-decorated metal-organic frameworks （MOF）, prepared by a simple solvothermal method in which porous MIL-100（Fe） served as the support and cadmium acetate （Cd（Ac）2） as the CdS precursor. When the selective oxidation of benzyl alcohol to benzaldehyde is used as the probe reaction, the results show that the combination of MIL-100（Fe） and CdS semiconductor can remarkably enhance the photocatalytic efficiency at room temperature, as compared to that of pure CdS. The enhanced photocatalytic performance can be attributed to the combined effects of enhanced light absorption, more efficient separation of photogenerated electron-hole pairs, and increased surface area of CdS due to the presence of MIL-100（Fe）. This work demonstrates that MOF-based composite materials hold great promise for applications in the field of solar-energy conversion into chemical energy.

Photocatalysis with visible-light-active uranyl complexes

Atomic energy is an important part of current energy resources.Production of nuclear weapons and applications of nuclear fuels in nuclear power plants have accumulated numerous spent fuels containing238U compounds,which are critical nuclear materials.How to reduce the nuclear wastes and to make use of the spent uranium are key scientific issues of environmental and nuclear science.We have reviewed here the physiochemical properties and photocatalytic mechanisms of homogeneous and heterogeneous uranium-containing materials.The current research efforts demonstrate that spent fuels can become promising new photocatalytic materials.

Microwave-assisted hydrothermal synthesis of cube-like Ag-Ag_2MoO_4 with visible-light photocatalytic activity

Cube-like Ag-Ag2MoO4 composite has been successfully prepared in the presence of PVP （potyvinylpyrrolidone） via a facile microwave-assisted hydrothermal process. Studies of its photocatalytic performance in the decomposition of RhB indicate that the cube-like Ag-Ag2MoO4 composite exhibits good catalytic activities under visible-light irradiation. The face that Ag pro- motes the absorption of visible light may be attributed to the surface plasmon resonance. Further XRD characterization after recycle photocatalytic tests confirms that partial Ag~ ions in Ag2MoO4 have been reduced to metallic Ag. Reaction temperature, reaction time and the amount of PVP have also been studied and found to play crucial roles in the formation of the cube-like microstructures.

Maximizing the visible light photoelectrochemical activity of B/N-doped anatase TiO_2 microspheres with exposed dominant {001} facets

Anatase TiO2 microspheres with exposed dominant {001} facets were doped with interstitial boron to have a concentration gradient with the maximum concentration at the surface. They were then further doped with substitutional nitrogen by heating in an ammonia atmosphere at different temperatures from 440 to 560℃ to give surface N concentrations ranging from 7.03 to 15.47 at%. The optical absorption, atomic and electronic structures and visible-light photoelectrochemical water oxidation activity of these materials were investigated. The maximum activity of the doped TiO2 was achieved at a nitrogen doping temperature of 520℃ that gave a high absorbance over the whole visible light region but with no defect-related background absorption.

Thermostable Nitrogen-Doped HTiNbO5 Nanosheets with a High Visible-Light Photocatalytic Activity

Nitrogen-doped HTiNbO5 nanosheets have been successfully synthesized by first exfoliating layered HTiNbO5 in tetrabutylammonium hydroxide （TBAOH） to obtain HTiNbO5 nanosheets and then heating the nanosheets with urea. The resulting samples were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, scanning electron microscopy （SEM）, energy-dispersive X-ray （EDX）, X-ray photoelectron spectroscopy （XPS）, UV-vis spectroscopy and N2 adsorption-desorption measurements. It was found that N-doping resulted in a much higher thermostability of the layered structure, intrinsic bandgap narrowing and a visible light response. The doped nitrogen atoms were mainly located in the interstitial sites of TiNbOs- lamellae and chemically bound to hydrogen ions. Compared with N-doped HTiNbOs, N-doped HTiNbO5 nanosheets had a much larger specific surface area and richer mesoporosity due to fee rather loose and irregular arrangement of fitanoniobate nanosheets. Both N-doped layered HTiNbOs and HTiNbO5 nanosheets showed a very high visible-light photocatalytic activity for the degradation of rhodamine B （RhB） aqueous solution. Moreover, due to the considerably larger surface area, richer mesoporosity and stronger acidity, N-doped HTiNbO5 nanosheets had an even higher activity than N-doped HTiNbOs, although the latter had a stronger absorption in the visible region. The dye molecules were mainly degraded to aliphatic organic compounds and partially mineralized to CO2 and/or CO, rather than being simply decolorized. The effect of photosensitization was insignificant and RhB was degraded mainly via the typical photocatalytic reaction routes. Two different reaction routes for the photodegradation of RhB under visible light irradiation over N-doped HTiNbO5 nanosheets have been proposed. The present method can be extended to a large number of layered metal oxides that have the characteristics of intercalation and exfoliation, thus providing new opportunities for the fabrication of highly effective and potentially practical visible-light photocatalysts.

PbCrO_4 yellow-pigment nanorods: An efficient and stable visible-light-active photocatalyst for O_2 evolution and photodegradation

Here, PbCrO4 nanorods, a commonly used and low-cost yellow pigment, was synthesized via a simple pre-cipitation reaction and can serve as a highly efficient oxygen production and photodegradation photocatalyst. The obtained PbCrO4 nanorods exhibit excellent stability and pho-tocatalytic performance for O2 evolution from water. The production rate is approximately 314.0μmol h^-1 g^-1 under visible light, and the quantum efficiency is approximately 2.16% at 420±10 nm and 0.05% at 600±10 nm. In addition, the PhCrO4 shows good degradation performance for methylene blue, methyl blue, methyl orange and phenol under visible-light irradiation. These results indicate that it is potential to fabricate an effective, robust PbCrO4 photocatalyst by trans-forming heavy-metal pollutants Pb（II） and Cr（VI） into a highly efficient O2 evolution and photodegradation material. This strategy which uses pollutant to produce clean energy and degrade contaminants is completely green and environmentally benign, and thus could be a promising way for practical environmental applications. Keywords： 02 evolution, pollutant, PbCrO4 nanorods, visible-light-active, photocatalyst

Synthesis of novel CaCO_3/Ag_2CO_3/Ag I/Ag plasmonic photocatalyst with enhanced visible light photocatalytic activity.

In this work, novel CaCO3/Ag2CO3/AgI/Ag plasmonic photocatalysts were successfully synthesized by a two-step in situ ion exchange process and their photocatalytic properties were studied. The morphology, crystal structure and optical properties of the as-prepared CaCO3/Ag2CO3/AgI/Ag nanocomposites were characterized by transmission electron microscopy （TEM）, X- Ray diffraction （XRD）, and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the obtained nanocomposites was evaluated by the photodegradation of methyl orange （MO） under visible light irradiation. It was found that the as-prepared CaCO3/Ag2CO3/AgI/Ag plasmonic photocatalyst exhibits high visible light photocatalytic activity. With an optimized composition, MO dye can be decomposed by more than 94% within 15 min under visible light irradiation. Moreover, the photocatalytic stability could be greatly improved upon the addition of Na2CO3 into the photocatalytic system. From the proposed photocatalytic mechanism, the strong surface plasmon resonance effect of Ag nanoparticles and the efficient separation of photogenerated electrons and holes can effectively enhance the photocatalytic performance of the CaCO3/Ag2COj AgI/Ag composites.