Facile synthesis and enhanced photocatalytic H_2-evolution performance of NiS_2-modified g-C_3N_4 photocatalysts

NiS2 is a promising cocatalyst to improve the photocatalytic performance of g-C3N4 for the production of H2.However,the synthesis of the NiS2 cocatalyst usually requires harsh conditions,which risks destroying the microstructures of the g-C3N4 photocatalysts.In this study,a facile and low-temperature（80 ℃） impregnation method was developed to prepare NiS2/g-C3N4 photocatalysts.First,the g-C3N4 powders were processed by the hydrothermal method in order to introduce oxygen-containing functional groups（such as-OH and-C0NH-） to the surface of g-C3N4.Then,the Ni^2＋ ions could be adsorbed near the g-C3N4 via strong electrostatic interaction between g-C3N4 and Ni^2＋ ions upon the addition of Ni（NO3）2 solution.Finally,NiS2 nanoparticles were formed on the surface of g-C3N4 upon the addition of TAA.It was found that the NiS2 nanoparticles were solidly and homogeneously grafted on the surface of g-C3N4,resulting in greatly improved photocatalytic H2production.When the amount of NiS2 was 3 wt%,the resultant NiS2/g-C3N4 photocatalyst showed the highest H2 evolution rate（116.343 μmol h^-1 g^-1）,which is significantly higher than that of the pure g-C3N4（3 μmol h^-1 g^-1）.Moreover,the results of a recycling test for the NiS2/g-C3N4（3 wt%）sample showed that this sample could maintain a stable and effective photocatalytic H2-evolution performance under visible-light irradiation.Based on the above results,a possible mechanism of the improved photocatalytic performance was proposed for the presented NiS2/g-C3N4 photocatalysts,in which the photogenerated electrons of g-C3N4 can be rapidly transferred to the NiS2 nanoparticles via the close and continuous contact between them;then,the photogenerated electrons rapidly react with H2O adsorbed on the surface of NiS2,which has a surficial metallic character and high catalytic activity,to produce H2.Considering the mild and facile synthesis method,the presented low-cost and highly efficient NiS2-modified g-C3N4 photocatalysts would have great potential for practical use in photocatalytic H2 production.

Preparation and photocatalytic performance of porous ZnO microrods loaded with Ag

Porous silver-modified ZnO microrods photocatalysts were synthesized through direct thermal decomposition of the Ag-doped zinctartrate precursor,which was prepared by homogeneous precipitation method at 80 °C for 2 h.The obtained samples were characterized by XRD,FTIR,TG？DTA and UV-VIS absorption spectroscopy.The photocatalytic activity of the as-prepared porous Ag/ZnO microrods was tested with the photocatalytic degradation of methyl orange.The results indicate that doping Ag greatly improves the photocatalytic efficiency of ZnO and 3% Ag-doped（mole fraction） ZnO porous microrod photocatalyst exhibits the highest photocatalytic decolorization efficiency,leading to as much as 80% reduction of MO concentration in 120 min.Moreover,the 3% Ag-doped porous microrods also possess higher photocatalytic activity under the real sunlight irradiation.

Nanoparticle/Microsphere TiO_(2)/Bi_(2)WO_(6) Z-scheme Heterojunction with Excellent Visiblelight Photocatalytic Performance

Flower-like BiOBr/Bi_(2)WO_(6) Z-scheme heterojunction was prepared by a twostep solvothermal method.BiOBr microspheres were firstly synthesized through solvothermal method.Then the out part of the BiOBr microspheres was designed to react with Na2WO4 forming Bi_(2)WO_(6) nanosheets through ion exchange process.The BiOBr/Bi_(2)WO_(6) heterojunction has a larger BET surface area,smaller energy band gap,faster transfer of charge carriers and a much better visible-light photocatalytic performance than that of BiOBr and Bi_(2)WO_(6).It also has a better cycling stability than that of the BiOBr.Possible photocatalytic mechanism of the BiOBr/Bi_(2)WO_(6) heterojunction is proposed.

Solvothermal fabrication of Bi_(2)MoO_(6) nanocrystals with tunable oxygen vacancies and excellent photocatalytic oxidation performance in quinoline production and antibiotics degradation

Novel Bi_(2)MoO_(6) nanocrystals with tunable oxygen vacancies have been developed via a facile low-cost approach with the assistance of a glyoxal reductant under solvothermal conditions.With the introduction of oxygen vacancies,the optical absorption of Bi_(2)MoO_(6) is extended and its bandgap narrowed.Oxygen vacancies not only lead to the appearance of a defect band level in the forbidden band but can also result in a minor up-shift of the valence band maximum,promoting the mobility of photogenerated holes.Moreover,oxygen vacancies can act as electron acceptors,temporarily capturing electrons excited by light and reducing the recombination of electrons and holes.At the same time,oxygen vacancies help to capture oxygen,which reacts with the captured photogenerated electrons to generate more superoxide radicals(·O_(2)-)to participate in the reaction,thereby significantly promoting the redox performance of the photocatalyst.From Bi_(2)MoO_(6) containing these oxygen vacancies(OVBMO),excellent photocatalytic performance has been obtained for the oxidation of 1,2,3,4-tetrahydroquinoline to produce quinoline and cause antibiotic degradation.The reaction mechanism of the oxidation of 1,2,3,4-tetrahydroquinoline to quinoline over the OVBMO materials is elucidated in terms of heterogeneous Catal.via a radical pathway.

Effects of Elemental Chemical State in NiFe2O4@TiO2 on the Photocatalytic Performance

The elemental chemical state of NiFe2O4@TiO2 was changed by the reduction in order to investigate its effects on the photocatalytic performance.The synthesized NiFe2O4@TiO2 samples were characterized by means of X-ray diffraction (XRD),high-resolution transmission electron microscopy (HRTEM),Fourier-transform infrared spectroscopy (FT-IR),X-ray photoelectron spectroscopy (XPS),magnetic and photocatalytic measurements.Unexpectedly,the reduction reaction does not produce oxygen vacancies Ov and TiOx in the TiO2 lattice.The optimal catalyst was obtained at the reducing temperature of 800℃,and its degradation efficiency De to the methylene blue and reaction rate constant Kapp are the highest,reaching 99.9% and 3×10^-2 min-1,respectively.The reason could not be explained by both the visible light absorption and the appropriate amount of Ov and TiOx.Instead,the lowest ratios of TiOH and Ti-O-Fe(Ni) may be responsible for the optimum photocatalytic performance.

Preparation and photocatalytic performance of ZnO/ZnGa_2O_4 composite microspheres

ZnO/ZnGa_2O_4 composite microspheres with heterojunction were successfully synthesized by one-pot hydrothermal method.These samples were characterized by TG/DTA,XRD,TEM,HRTEM,UV-vis DRS,FL and BET techniques.The results indicated the as-prepared samples showed better degree of crystalline and large specific surface area.The photocatalytic activity was evaluated by degradation of methyl orange with the concentration of 50 mg/L under the irradiation of simulated sunlight.The effects of molar ratio of Zn to Ga and calcination temperature on the photocatalytic activity were investigated in detail.The results showed that the highest photocatalytic degradation efficiency was observed at the molar ratio of Zn to Ga of 1:0.5 in the starting materials and the calcination temperature of 400 °C.The maximum photocatalytic degradation rate of MO was 97.1% within 60 min under the simulated sunlight irradiation,which is greatly higher than that of ZnO and ZnGa_2O_4.

Synthesis of a Novel TiO_(2)@Ag_(3)PO_(4)Core-Shell Structure with Enhanced Photocatalytic Performance

Ag_(3)PO_(4)exhibits a high photocatalytic activity if exposed to visible light,however,it displays bottlenecks such as poor cycle-stability and mediocre ability to degrade methyl orange(MO)because of limited adsorption of MO molecules onto its surface.In this study,nano TiO_(2)prepared by a one-step method was combined with Ag_(3)PO_(4)to form a TiO_(2)@Ag_(3)PO_(4)heterojunction in order to improve this material both in terms of photocatalysis and photostability.After adding a KH-570 silane coupling agent,the photocatalytic performance of TiO_(2)@Ag_(3)PO_(4)could be improved even further,with the degradation rate of MO maintained at more than 90%after three cycles of visible in light.

Ag3PO4 Microcrystals Synthesized by Room-Temperature Solid State Reaction:Enhanced Photocatalytic Activity and Photoelectronchemistry Performance

Ag3PO4 microcrystals with highly enhanced visible light photocatalytic activity are prepared by a facile and simple solid state reaction at room temperature. The composition, morphology and optical properties of the asprepared Ag3PO4 microcrystMs are characterized by x-ray diffraction, scanning electron microscopy and UV-vis diffuse reflectance spectra. The photocatalytie properties of Ag3PO4 are investigated by the degradation of both methylene blue and methyl orange dyes under visible light irradiation. The as-prepared Ag3PO4 microcrystals possess high photocatalytic oxygen production with the rate of 673μmolh-1g-1. Moreover, the as-prepared Ag3PO4 microcrystals show an enhanced photoelectrochemistry performance under irradiation of visible light.

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.

Solvent-assisted synthesis of porous g-C_3N_4 with efficient visible-light photocatalvtic performance for NO removal

Graphitic carbon nitride（g-C3N4） with efficient photocatalytic activity was synthesized through thermal polymerization of thiourea with the addition of water（CN-W） or ethanol（CN-E） at 550 ℃for 2 h.The physicochemical properties of the g-C3N4 were investigated by X-ray diffraction,transmission electron microscopy,ultraviolet-visible spectroscopy,photoluminescence spectroscopy,diffuse-reflection spectroscopy,BET and BJH surface area characterization,and elemental analysis.The carbon content was found to have self-doped into the g-C3N4 matrix during the thermal polymerization of thiourea and ethanol.CN-W and CN-E showed considerably enhanced visible-light photocatalytic activity,with NO removal percentages of 37.2%and 48.3%,respectively.Compared with pure g-C3N4,both the short and long lifetimes of the charge carriers in CN-W and CN-E were found to be prolonged.The mechanism of improved visible-light photocatalytic activity was deduced.The present work may provide a facile route to optimize the microstructure of g-C3N4photocatalysts for high-performance environmental and energy applications.

CdS-modified one-dimensional g-C_3N_4 porous nanotubes for efficient visible-light photocatalytic conversion

A heterojunction photocatalyst based on porous tubular g-C3N4 decorated with CdS nanoparticles was fabricated by a facile hydrothermal co-deposition method.The one-dimensional porous structure of g-C3N4 provides a higher specific surface area,enhanced light absorption,and better separation and transport performance of charge carriers along the longitudinal direction,all of which synergistically contribute to the superior photocatalytic activity observed.The significantly enhanced catalytic efficiency is also a benefit originating from the fast transfer of photogenerated electrons and holes between g-C3N4 and CdS through a built-in electric field,which was confirmed by investigating the morphology,structure,optical properties,electrochemical properties,and photocatalytic activities.Photocatalytic degradation of rhodamine B(RhB)and photocatalytic hydrogen evolution reaction were also carried out to investigate its photocatalytic performance.RhB can be degraded completely within 60 min,and the optimum H2 evolution rate of tubular g-C3N4/CdS composite is as high as 71.6μmol h^–1,which is about 16.3 times higher than that of pure bulk g-C3N4.The as-prepared nanostructure would be suitable for treating environmental pollutants as well as for water splitting.

Highly efficient visible-light photocatalytic H2 evolution over 2D–2D Cd S/Cu7S4 layered heterojunctions

Converting solar energy into clean and sustainable chemical fuels is a promising strategy for exploiting renewable energy.The application of photocatalytic water splitting technology in hydrogen production is important for sustainable energy development and environmental protection.In this study,for the first time,2D Cu7S4 co-catalysts were coupled on the surface of a CdS nanosheet photocatalyst by a one-step ultrasonic-assisted electrostatic self-assembly method at room temperature.The as-fabricated 2D^-2D CdS/Cu7S4 layered heterojunctions were demonstrated to be advanced composite photocatalysts that enhance the water splitting efficiency toward hydrogen production.The highest hydrogen evolution rate of the 2D^-2D CdS/2%Cu7S4 binary heterojunction photocatalyst was up to 27.8 mmol g^-1 h^-1 under visible light irradiation,with an apparent quantum efficiency of 14.7%at 420 nm,which was almost 10.69 times and 2.65 times higher than those of pure CdS nanosheets(2.6 mmol g^-1 h^-1)and CdS-2%CuS(10.5 mmol g^-1 h^-1),respectively.The establishment of the CdS/Cu7S4 binary-layered heterojunction could not only enhance the separation of photogenerated electron-hole(e--h+)pairs,improve the transfer of photo-excited electrons,and prolong the life-span of photo-generated electrons,but also enhance the light absorption and hydrogen-evolution kinetics.All these factors are important for the enhancement of the photocatalytic activity.Expectedly,the 2D^-2D interface coupling strategy based on CdS NSs can be extensively exploited to improve the hydrogen-evolution activity over various kinds of conventional semiconductor NSs.

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.

Regulating the crystal phase of bismuth-based semiconductors for promoted photocatalytic performance

Numerous bismuth-based semiconductors(BBSs)with sophisticated and desirable structures used as photocatalysts for efficient photocatalytic degradation of water organic contaminants have attracted considerable attention.However,regulating the crystal phases and phase transition of BBSs for promoted photocatalytic performance is ignored.Herein,the unique crystal structure and band structure features of each typical BBSs,and the vital roles on phase controlling of each phase were systematically presented based on the classification of BBSs.Notably,the critical factors for the phase transition of BBSs and intrinsic driving forces endowed by phases of BBSs for enhanced photocatalytic performance of organic contaminants removal were also elucidated.This review will provide systematical guidelines and horizons for regulating the crystal phase and phase transition of BBSs,promoting photocatalytic degradation and mineralization of organic contaminants.

Enhancing visible-light photocatalytic activity of α-Bi_2O_3 via non-metal N and S doping

In recent years, some important research indicated that the visible-light activity of photocatalysts could be enhanced via incorporating p-block non-metal elements into the lattice. In this paper, we investigated the electronic structures of pure and different non-metal （C, N, S, F, Cl, and Br） doped α-Bi2O3 using first-principles calculations based on the density functional theory. The band structures, the electronic densities of states, and the effective masses of electrons and holes for doped α-Bi2O3 were obtained and analyzed. The N and S dopings narrowed the band gap and reduced the effective mass of the carriers, which are beneficial for the photocatalytic performance. The theoretical predication was further confirmed by the experimental results.

Rare Earth Ion Yb^3+ Doping of Bi2WO6 with Excellent Visible-light Photocatalytic Activity

The rare earth ion Yb^3+ doped Bi2WO6 photocatalysts were synthesized by hydrothermal method.Moreover,XRD,XPS,FESEM,TEM,Ramam,N2 adsorption-desorption isotherm measurements and UV-vis diffusion reflectance spectra were used to characterize the Yb^3+ doped Bi2WO6 photocatalysts.The morphology,specific surface area,and pore volume distribution were greatly affected after Yb3+ ions doping.Photocatalytic performance of Bi2WO6 was effectively enhanced after Yb3+ ions doping,6% Yb^3+ doped Bi2WO6 had the best photocatalytic performance,and 96.2% Rhodamine B was degradated after irradiated 30 min,which was 1.29 times that of the pristine one.The enhanced photocatalytic performance was due to the increased specific surface area,decreased energy band gap and inhibition of photoelectron-hole recombination after Yb3+ ions doping.

Structural engineering of 3D hierarchical Cd0.8Zn0.2S for selective photocatalytic CO2 reduction

The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is highly intriguing and challenging to promote the selectivity and efficiency of visible-light-responsive photocatalysts that favor the adsorption of CO2 in photoreduction processes.In this work,three-dimensional hierarchical Cd0.8Zn0.2S flowers(C8Z2S-F)with ultrathin petals were successfully synthesized through an in-situ self-assembly growth process using sodium citrate as a morphology director.The flower-like Cd0.8Zn0.2S solid solution exhibited remarkable photocatalytic performance in the reduction of CO2,generating CO up to 41.4μmol g^−1 under visible-light illumination for 3 h;this was nearly three times greater than that of Cd0.8Zn0.2S nanoparticles(C8Z2S-NP)(14.7μmol g^−1).Particularly,a comparably high selectivity of 89.9%for the conversion of CO2 to CO,with a turnover number of 39.6,was obtained from the solar-driven C8Z2S-F system in the absence of any co-catalyst or sacrificial agent.Terahertz time-domain spectroscopy indicated that the introduction of flower structures enhanced the light-harvesting capacity of C8Z2S-F.The in situ diffuse reflectance infrared Fourier transform spectroscopy unveiled the existence of surface-adsorbed species and the conversion of photoreduction intermediates during the photocatalytic process.Empirical characterizations and predictions of the photocatalytic mechanism demonstrated that the flower-like Cd0.8Zn0.2S solid solution possessed desirable CO2 adsorption properties and an enhanced charge-transfer capability,thus providing a highly effective photocatalytic reduction of CO2.

Hydrothermal Synthesis of H_3PW_(12)O_(40)/TiO_2 Nanometer Photocatalyst and Its Catalytic Performance for Methyl Orange

H3PW12O40/TiO2 nanometer photocatalyst was prepared by one step hydrothermal synthesis from H3PW12O40·nH20 and Ti（OBu）4, simultaneously realizing the load and modification of H3PW12O40. The catalyst was characterized by Fourier transform infrared spectroscopy（FTIR）, powder X-ray diffraction（XRD）, nitrogen adsorp- tion-desorption analysis and scanning electron microscopy（SEM）. The results show that the catalyst is Keggin struc- ture and crystallized in anatase structure, the diameter and specific area of the prepared catalyst are 3.8 nm and 177.9 m^2/g, respectively, and its dispersity is better. The photocatalytic properties were compared for TiO2H3PW12O40/TiO2 prepared by impregnation and H3PW12O40/TiO2 prepared by hydrothermal method with methyl orange as a probe. The effects of H3PW12O40 loadings, crystallization method, initial pH and concentration of dye solution on the degradation of methyl orange were investigated.

Design of(GO/TiO2)N one-dimensional photonic crystal photocatalysts with improved photocatalytic activity for tetracycline degradation

(GO/TiO2)N(GO represents graphene oxide,and N represents the period number of alternate superposition of two dielectrics)onedimensional photonic crystal with different lattice constants was prepared via the sol–gel technique,and its transmission characteristics for photocatalysis were tested.The results show that the lattice constant,filling ratio,number of periodic layers,and incident angle had effects on the band gap.When the lattice constant,filling ratio,number of periodic layers,and incident angle were set to 125 nm,0.45,21,and 0°,respectively,a gap width of 53 nm appeared at the central wavelength(322 nm).The absorption peak of the photocatalyst at 357 nm overlapped the blue edge of the photonic band gap.A slow photon effect region above 96%reflectivity appeared.The degradation rate of tetracycline in(GO/TiO2)N photonic crystal was enhanced to 64%within 60 min.Meanwhile,the degradation efficiency of(GO/TiO2)N one-dimensional photonic crystal was effectively improved compared with those of the GO/TiO2 composite film and GO/TiO2 powder.

Studies of Photocatalytic Kinetics on the Degradation of Bisphenol A （BPA） by Immobilized ZnO Nanoparticles in Aerated Photoreactors

The photocatalytic kinetics of BPA （4, 4＇-isopropylidenediphenol）, a representative endocrine disruptor, was explored using immobilized ZnO nanoparticles as a photocatalyst in a laboratory scale photocatalytic reactor. The conditions of photocatalytic degradation were optimized. Direct photocatalytic degradation of BPA was undertaken in an aqueous solution containing ZnO nanoparticles under the optimized experimental conditions. The effects of various factors, such as initial BPA concentrations, initial pH values and various anions （CI, NO3, COa2, SO42-, HCO3＂） were investigated. In the case of the nanoparticles derived films, the photocatalytic efficiency was found not to be remarkably related with the calcination temperature employed in the coating process. Screen-printed ZnO nanoparticles films obtained in the optimal processing conditions showed that the photocatalytic activity is comparable to ZnO nanoparticles in aqueous suspensions. Over 90% degradation efficiency of BPA was achieved under the optimum conditions. The degradation rates in all photocatalytic experiments were linear with the degradation efficiencies of BPA by regression analysis （r ≥ 0.99）. The results showed that the degradation kinetics of BPA in the reactor with immobilized nano-ZnO film as photocatalyst was in agreement with a pseudo-first order rate law.