Ternary Ag/AgCl/BiOIO_3 composites for enhanced visible-light-driven photocatalysis

Ternary Ag/AgC l/BiO IO3 composite photocatalysts are prepared by a facile method. Enhanced visible-light absorption and charge carrier separation are achieved after the introduction of Ag/AgC l particles into BiO IO3 systems,as revealed by ultraviolet-visible diffuse-reflectance spectrometry,photocurrent response and electrochemical impedance spectroscopy. The Ag/AgC l/BiO IO3 composites are applied to the visible-light photocatalytic oxidization of NO in air and exhibit an enhanced activity for NO removal in comparison with Ag/AgC l and pure BiO IO3. A possible photocatalytic mechanism for Ag/AgC l/BiO IO3 is proposed,which is related to the surface plasmon resonance effects of Ag metal and the effective carrier separation ability of BiO IO3. This work provides insight into the design and preparation of BiO IO3-based materials with enhanced visible-light photocatalysis ability.

Construction of 2D-2D TiO_2 nanosheet/layered WS_2 heterojunctions with enhanced visible-light-responsive photocatalytic activity

Constructing nanocomposites that combine the advantages of composite materials,nanomaterials,and interfaces has been regarded as an important strategy to improve the photocatalytic activity of TiO2.In this study,2D‐2D TiO2 nanosheet/layered WS2(TNS/WS2)heterojunctions were prepared via a hydrothermal method.The structure and morphology of the photocatalysts were systematically characterized.Layered WS2(~4 layers)was wrapped on the surface of TiO2 nanosheets with a plate‐to‐plate stacked structure and connected with each other by W=O bonds.The as‐prepared TNS/WS2 heterojunctions showed higher photocatalytic activity for the degradation of RhB under visible‐light irradiation,than pristine TiO2 nanosheets and layered WS2.The improvement of photocatalytic activity was primarily attributed to enhanced charge separation efficiency,which originated from the perfect 2D‐2D nanointerfaces and intimate interfacial contacts between TiO2 nanosheets and layered WS2.Based on experimental results,a double‐transfer photocatalytic mechanism for the TNS/WS2 heterojunctions was proposed and discussed.This work provides new insights for synthesizing highly efficient and environmentally stable photocatalysts by engineering the surface heterojunctions.

A Novel Visible-light-responsive Photocatalyst Bi1.5Cr0.5WO6 with Suitable Bandgap Structure and Its Application in Water Decontamination

Integrating the advantages of Bi and Cr elements in the bandgap engineering of metal oxides, a visible-light-responsive photocatalyst Bi1.5Cr0.5WO6 is successfully constructed and initially applied in water decontamination. The combination of UV-vis diffuses reflectance and the Mott-Schottky curve from electrochemical testing can be used to determine the conduction band and valence band of Bi1.5Cr0.5WO6 to be about –1.26 and 1.42 V, respectively. The location of energy band structure indicates that the superoxide free radical can be produced in Bi1.5Cr0.5WO6 photocatalytic system without hydroxyl group. This speculation is also confirmed by ESR experiment and active radical species scavenging experiments. In addition, the best photocatalytic performance of Bi1.5Cr0.5WO6 obtained under 180 ℃ is attributed to the smallest impedance and the strongest electronic migration capability.

Introducing Spin Polarization into Mixed-Dimensional Van der Waals Heterostructures for High-Efficiency Visible-Light Photocatalysis

The low separation efficiency of the photogenerated carrier and the poor activity of the surface redox reaction are the main barrier to further improvement of photocatalytic materials.To address these issues,introducing spin-polarized electrons in single-component photocatalytic materials emerged as a promising approach.However,the decreased redox ability of photocarriers in these materials becomes a new challenge.Herein,we mitigate this challenge with a carbon nitride sheet(CNs)/graphene nanoribbon(GNR)composite material that has a van der Waals heterostructures(vdWHs)and spin-polarized electron properties.Experimental results and theoretical calculations show that the heterostructure has a strong redox ability,high carrier-separation efficiency,and enhanced surface catalytic reaction.Consequently,the mixed-dimensional CNs/GNR vdWHs exhibit remarkable performance for H_(2)and O_(2)generation as well as CO_(2)production under visible-light irradiation without any cocatalyst.The spin-polarized vdWHs discovered in this study revealed a new type of photocatalytic materials and advanced the development of spintronics and photocatalysis.

Recent developments in visible-light photocatalytic degradation of antibiotics

With the significant discharge of antibiotic wastewater into the aquatic and terrestrial ecosystems, antibiotic pollution has become a serious problem and presents a hazardous risk to the environment. To address such issues, various investigations on the removal of antibiotics have been undertaken. Photocatalysis has received tremendous attention owing to its great potential in removing antibiotics from aqueous solutions via a green, economic, and effective process. However, such a technology employing traditional photocatalysts suffers from major drawbacks such as light absorption being restricted to the UV spectrum only and fast charge recombination. To overcome these issues, considerable effort has been directed towards the development of advanced visible light-driven photocatalysts. This mini review summarises recent research progress in the state-of-the-art design and fabrication of photocatalysts with visible-light response for photocatalytic degradation of antibiotic wastewater. Such design strategies involve the doping of metal and non-metal into ultraviolet light-driven photocatalysts, development of new semiconductor photocatalysts, construction of heterojunction photocatalysts, and fabrication of surface plasmon resonance-enhanced photocatalytic systems. Additionally, some perspectives on the challenges and future developments in the area of photocatalytic degradation of antibiotics are provided.

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.

MOF-templated tubular Ni_(1−x)Co_(x)S_(2)-CdS heterojunction with intensified direct Z-scheme charge transmission for highly promoted visible-light photocatalysis

Hollow semiconductor nanostructures with direct Z-scheme heterojunction have significant advantages for photocatalytic reactions,and optimizing the interfacial charge transmission of Z-scheme heterojunction is the hinge to achieve excellent solar conversion efficiency.In this work,tubular Ni_(1−x)Co_(x)S_(2)-CdS heterostructures with reinforced Z-scheme charge transmission were constructed through an In-metal-organic framework(MOF)templated strategy.The Z-scheme charge transfer mechanism was sufficiently confirmed by combining density functional theory(DFT)calculation,X-ray photoelectron spectroscopy(XPS),surface photovoltage spectroscopy(SPV),and radical testing results.Crucially,the use of sodium citrate complexant contributes to the formation of intimate heterointerface,and the Fermi level gap between CdS and NiS_(2)is enlarged through Co doping into NiS_(2),which enhances the built-in electric field and photo-carriers transmission driving force for Ni_(1−x)Co_(x)S_(2)-CdS heterojunction,resulting in an evidently promoted activity toward H2 evolution reaction(HER).Under visible-light(λ>400 nm)irradiation,the Ni_(1−x)Co_(x)S_(2)-CdS composite with 10 mol%Co doping and 80 wt.%CdS(NC_(0.10)S-80%CdS)achieved an outstanding HER rate up to 35.94 mmol·g^(−1)·h^(−1)(corresponding to the apparent quantum efficiency of 34.7%at 420 nm),approximately 76.4 times that of 3 wt.%Pt-loaded CdS and it is much superior to that of most CdS-based photocatalysts ever reported.Moreover,the good photocatalytic durability of Ni_(1−x)Co_(x)S_(2)-CdS heterostructures was validated by cycling and long-term HER tests.This work could inspire the development of high-performance Z-scheme heterojunction via optimizing the morphology and interfacial charge transmission.

BiOCl-Bi12O17Cl2 nanocomposite with high visible-light photocatalytic activity prepared by an ultrasonic hydrothermal method for removing dye and pharmaceutical

A BiOCl-Bi12O17Cl2 nanocomposite with a high visible-light response and a low photoinduced electron-hole pair recombination rate was successfully synthesized using an ultrasonic-hydrothermal method.The texture,structure,optical,and photocatalytic properties of the composite were characterized.The results showed that the composite had a sheet flower-like structure with a large specific surface area.Ultraviolet-visible diffuse reflection spectra and photoluminescence spectra showed that the composite had an excellent visible-light response and a low recombination rate of photoinduced electron hole pairs.The photocatalytic property of the composite was evaluated by the removal efficiency of rhodamine B and ciprofloxacin under visible-light illumination.The composite’s reaction rate constant of removing rhodamine B(/ciprofloxacin)was approximately 8.14(/4.94),42.63(/11.91)and 64.66(/36.07)times that of Bi12O17Cl2,P25,and BiOCl,respectively.Furthermore,the composite showed a wide applicable pH range and excellent reusability.Mechanism analysis showed that photogenerated holes played a dominant role and·O2–also contributed to photocatalytic degradation.In summary,this study presents a high-efficiency photocatalyst for wastewater treatment.

Photocatalytic Dye Methyl Orange Decomposition on Ternary Sulfide (CdIn2S4) under Visible-light

A novel and efficient photocatalyst, CdIn2S4, was simply prepared by a programmed temperature hydrothermal method. The product had a nanometer size （10-15 nm） and strong absorption in the range of 200 to 580 nm, and it exhibited visible-light photocatalytic activity to decompose dye methyl orange in aqueous system.

In-situ hydrothermal synthesized γ-Al_2O_3/O-g-C_3N_4 heterojunctions with enhanced visible-light photocatalytic activity in water splitting for hydrogen

In this work, γ-Al2O3and hydrogen peroxide treated g-C3N4(O-g-C3N4) were combined through a novel in-situ hydrothermal method to form heterojunction structured photocatalysts. These photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy and photoluminescence spectroscopy (PL). FT-IR results indicate that oxygen functional groups can be grafted on the surface of O-g-C3N4by hydrogen peroxide treatment. The visible light photocatalytic hydrogen evolution rate was investigated in 10 vol% TEOA aqueous solution. The optimal Al2O3mass content is set to be 20 wt% and the corresponding hydrogen evolution rate is 1288 µmol/h/g which is approximately 6, 3 folds that of pristine g-C3N4and O-g-C3N4respectively and 1.6 folds that of mechanical mixed composite with the same Al2O3mass content. The photocurrent density–time curves were carried out under visible light illumination for four on–off cycles. The electrochemical impedance spectroscopy (EIS) measurements verified the enhanced separation efficiency of electron–hole pairs. This work raised a new method to form the heterojunction structured photocatalysts and achieved a remarkable improvement of the photocatalytic activity in water splitting for hydrogen under visible light irradiation. © 2016

Facile fabrication of ZnIn2S4/SnS2 3D heterostructure for efficient visible-light photocatalytic reduction of Cr（Ⅵ）

Photocatalytic method has been intensively explored for Cr(VI)reduction owing to its efficient and environmentally friendly natures.In order to obtain a high efficiency in practical application,efficient photocatalysts need to be developed.Here,ZnIn2S4/SnS2 with a three-dimensional(3D)heterostructure was prepared by a hydrothermal method and its photocatalytic performance in Cr(VI)reduction was investigated.When the mass ratio of SnS2 to ZnIn2S4 is 1:10,the ZnIn2S4/SnS2 composite exhibits the highest photocatalytic activity with 100%efficiency for Cr(VI)(50 mg/L)reduction within 70 min under visible-light irradiation,which is much higher than those of pure ZnIn2S4 and SnS2.The enhanced charge separation and the light absorption have been confirmed from the photoluminescence and UV-vis absorption spectra to be the two reasons for the increased activity towards photocatalytic Cr(VI)reduction.In addition,after three cycles of testing,no obvious degradation is observed with the 3D heterostructured ZnIn2S4/SnS2,which maintains a good photocatalytic stability.

Sequential Growth of Cs_(3)Bi_(2)I_(9)/BiVO_(4)Direct Z-Scheme Heterojunction for Visible-Light-Driven Photocatalytic CO_(2)Reduction

The high exciton binding energy and lack of a positive oxidation band potential restrict the photocatalytic CO_(2)reduction efficiency of lead-free Bi-based halide perovskites Cs_(3)Bi_(2)X_(9)(X=Br,I).In this study,a sequential growth method is presented to prepare a visible-light-driven(λ>420 nm)Z-scheme heterojunction photocatalyst composed of BiVO_(4)nanocrystals decorated on a Cs_(3)Bi_(2)I_(9)nanosheet for photocatalytic CO_(2)reduction coupled with water oxidation.The Cs_(3)Bi_(2)I_(9)/BiVO_(4)Z-scheme heterojunction photocatalyst is stable in the gas-solid photocatalytic CO_(2)reduction system,demonstrating a high visible-light-driven photocatalytic CO_(2)-to-CO production rate of 17.5μmol/(g·h),which is approximately three times that of pristine Cs_(3)Bi_(2)I_(9).The high efficiency of the Cs_(3)Bi_(2)I_(9)/BiVO_(4)heterojunction was attributed to the improved charge separation in Cs_(3)Bi_(2)I_(9).Moreover,the Z-scheme charge-transfer pathway preserves the negative reduction potential of Cs_(3)Bi_(2)I_(9)and the positive oxidation potential of BiVO_()4.This study off ers solid evidence of constructing Z-scheme heterojunctions to improve the photocatalytic performance of lead-free halide perovskites and would inspire more ideas for developing leadfree halide perovskite photocatalysts.

Preparation and Visible-Light Photocatalytic Activity of FeTPP-Cr-TiO2 Microspheres

Tetraphenyl-porphyrin iron （FeTPP） was chosen to sensitize Cr doped TiO2 （Cr-TiO2） nanoparticles, a novel multimodified photocatalyst FeTPP-Cr-TiO2 with excellent visible- light photocatalytic activity was successfully synthesized. The FeTPP-Cr-TiO2 microspheres were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electronic microscopy, X-ray photoelectron spectroscopy, UV-Vis diffuse reflectance spectra and N2 adsorption-desorption isotherms. The photocatalytic activity of FeTPP-Cr-TiO2 was evaluated by degradations of methylene blue in aqueous solution under irradiation with Xe lamp （150 W）. The results showed that the FeTPP-Cr-TiO2 multimodified photocatalyst was anatase phase with high specific surface area （74.7 m^2/g）, and exhibited higher photocatalytic degradation efficiency than Cr-TiO2 and FeTPP-TiO2. The photocatalytic degradations of three quinolone antibiotics （lomefioxacin, norfioxacin, and ofioxacin） were further estimated for the feasibility of practical application of catalyst in wastewater treatment. It is desirable that photodegradation of antibiotics with FeTPP-Cr-TiO2 achieved pretty high degradation rates and all followed the pseudo first-order reaction model, and the rate constants k of 3.02×10^-2, 2.81×10^-2, and 3.86×10^-2 min-1 and the half-lifes t1/2 of 22.9, 24.6, and 17.9 min were achieved respectively.

Hydrothermal Synthesis of CdIn_2S_4 and Photocatalytic Degradation of Methyl Orange under Visible-light Irradiation

CdIn2S4 microspheres were synthesized by a facile hydrothermal method with the temperature ranging from 120 to 200 ℃. X-ray diffraction, UV-vis diffuse reflectance spectroscopy, nitrogen sorption analysis, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy were used to characterize the products. It was found that the crystallographic structure and optical property of the products synthesized at different temperature were almost the same. The SBEX of CdIn2S4 products decreased when the synthesized temperature increased, and the largest SBET was 33.16 m2 g-1 （120 ℃ sample）. The degradation of methyl orange （MO） under the visible-light irradiation had been used as a probe reaction to investigate the photocatalytic activity of the as-prepared CdIn2S4, which showed that the CdIn2S4 sample synthesized at 120 ℃ presented the best photocatalytic activity for MO degradation.

Optimization of Preparation Conditions of Modified Oyster Shell Powder/Ce-N-TiO2 by Response Surface Methodology (RSM)

A new composite photocatalyst of modified oyster shell powder/Ce-N-TiO2 was prepared by sol-gel method. Based on single factor experiment, Ce doping rate, N doping rate and calcination temperature were taken as input variables. Based on the central composite design (BBD) response surface model, two functional relationship models between three independent variables and glyphosate removal rate were established to evaluate the influence degree of independent variables and interaction on catalyst. The significance of the model and regression coefficient was tested by variance analysis. The analysis of the obtained data showed that the degradation performance of the composite photocatalyst was significantly affected by the calcination temperature and the rate of N doping, while the rate of Ce doping had little effect;at the calcination temperature of 505.440°C, the degradation rate of glyphosate reached the maximum of 82.15% under the preparation conditions of 17.057 mol% N doping and 0.165 mol% Ce doping, respectively.

Box-Behnken响应面法优化La掺杂钨酸铋光催化剂的制备及降解染料废水

本文以五水合硝酸铋[Bi(NO_(3))_(3)·5H_(2)O]、二水合钨酸钠(Na_(2)WO_(4)·2H_(2)O)及水合硝酸镧[La(NO_(3))_(3)·nH_(2)O],为主要原料,采用水热法制备La-Bi_(2)WO_(6)催化剂,光催化降解以甲基橙为模型反应的染料废水,通过可见分光光度计,对模型污染物的吸光度进行测定进而得出降解率。主要研究了镧掺杂量、水热温度、水热时间等条件对La-Bi_(2)WO_(6)光催化剂性能的影响。并用Box-Behnken响应面法设计并优化实验条件,分析各影响因素间的交互作用。结果表明:当镧掺杂量为5.5%,178.69℃下,时间为3.89 h时,制备的La掺杂钨酸铋光催化剂的催化效果最好。

基于氯自由基链式反应的臭氧可见光消除研究

随着地球大气中臭氧(O_(3))浓度的逐年升高,臭氧已成为大气污染治理的一个重要污染物.羟基自由基光催化反应对臭氧消除性能偏低,仅提高羟基自由基产量的改性方法已不适用于臭氧光催化消除.本文以Bi_(2)WO_(6)为基础,先后进行了Fe掺杂以及TiO_(2)负载,制备了一系列Fe-Bi_(2)WO_(6)@TiO_(2)复合材料,并对复合材料进行了物性表征及臭氧催化活性测试.结果表明,Fe-Bi_(2)WO_(6)@TiO_(2)材料具有典型的包覆结构,表现出可见光响应并激发了氯自由基的生成.氯自由基作为消除O_(3)的活性物种,驱动了一种类似“臭氧层空洞效应”的光化学反应机制,即表面氯化的TiO_(2)受光激发产生氯自由基,引发链式反应,大幅提升了臭氧分解的性能.Fe-Bi_(2)WO_(6)@TiO_(2)对O_(3)的消除率最大为93%.氯自由基的引入以及复合材料可见光响应的拓展,可大幅提升光催化臭氧消除能力.

Trifluoroethylation of Alkynes： Synthesis of Allylic-CF3 Compounds by Visible-Light Photocatalysis

Two types of allylic trifluoromethylated compounds were synthesized by reacting alkynes with CF3CH2I using visible-light photocatalysis. Subtle differences in the catalytic system controlled the selectivity of iodotrifluoroethy- lation and hydrotrifluoroethylation. The iodotrifluoroethylated products were obtained in the presence of [Ru（bpy）3]C12 and TMEDA in CH3CN under visible-light irradiation, whereas hydrotrifluoroethylated products were synthesized usingfac-[Ir（ppy）3] and a mixture of DBU and K2CO3 in DMF. The iodotrifluoroethylation reac- tion worked particularly well, even at gram-scale, and the synthetic utility of iodotrifluoroethylated products was proved by their coupling reactions, providing complex CF3-containing products.

Synthesis and enhanced visible-light responsive of C,N,S-tridoped TiO_2 hollow spheres

C,N,S-tridoped TiO2 hollow spheres （labeled as C,N,S-THs） were synthesized using carbon spheres as template and C,N,S-tridoped TiO2 nanoparticles as building blocks. The structure and physicochemical properties of the catalysts were characterized by X- ray diffraction （XRD）, scanning electron microscopy （SEM）, UV-Vis diffuse reflectance spectrum （DRS）, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy （XPS） and Photoluminescence emission spectroscopy （PL）. The results showed that the hollow spheres had average diameter of about 200 nm and the shell thickness was about 20 nm. The tridoped TiO2 hollow spheres exhibited strong absorption in the visible-light region. C,N,S-tridoped could narrow the band gap of the THs by mixing the orbit O 2p with C 2p, N 2p and S 3p orbits and shift its optical response from ultraviolet （UV） to the visible-light region. PL analysis indicated that the electron-hole recombination rate of TiO2 hollow spheres had been effectively inhibited when doped with C, N and S elements. The photocatalytic activities of the samples were evaluated for the degradation of X-3B （Reactive Brilliant Red dye, C.I. Reactive Red 2） aqueous solution under visible-light （λ 〉 420 nm） irradiation. It was found that the C,N,S-tridoped TiO2 hollow spheres indicated higher photocatalytic activity than commercial P25 and the undoped counterpart photocatalyst.

Direct Introduction of EthoxycarbonyldifluoromethyI-Group to Heteroarenes with Ethyl Bromodifluoroacetate via Visible-Light Photocatalysis

A mild and versatile approach for the direct introduction of ethoxycarbonyldifluoromethyl-group to heteroarenes via visible-light photocatalysis has been developed. The new photoredox protocol has enabled the difluoromethylenation of heteroarenes containing a wide range of common functional groups under mild conditions.