In this contribution, an efficient and simple two-step hybrid electrochemical-thermal route was developed for the synthesis of cubic shaped Zn_2SnO_4 (ZTO) nanoparticles using aqueous sodium bicarbonate(NaHCO_3) and s...In this contribution, an efficient and simple two-step hybrid electrochemical-thermal route was developed for the synthesis of cubic shaped Zn_2SnO_4 (ZTO) nanoparticles using aqueous sodium bicarbonate(NaHCO_3) and sodium stannate(Na_2SnO_3) electrolyte. The sacrificial Zn was used as anode and cathode in an undivided cell under galvanostatic mode at room temperature. The bath concentration and current density were respectively varied from 30 to 120 mmol and 0.05 to 1.5 A/dm^2. The electrochemically generated precursor was calcined for an hour at different range of temperature from 60 to 600. The crystallite sizes in the range of 24-53 nm were calculated based on Debye-Scherrer equation. Scanning electron microscope and transmission electron microscopy results reveal that all the particles have cubic morphology with diameter of40-50 nm. The as-prepared ZTO samples showed higher catalytic activity towards the degradation of methylene blue(MB) dye, and 90% degradation was found for the sample calcined at 600, which is greater than that of commercial TiO_2-P25 photocatalysts. The photodegradation efficiency of ZTO samples was found to be a function of exposure time and the dye solution p H value. These results indicate that the ZTO nanoparticles may be employed to remove dyes from wastewater.展开更多
Ag/TiO2/freeze-dried graphene nanocomposites have been prepared via a facile one-step solvothermal method for the photocatalytic degradation of Rh B under visible light irradiation. During the solvothermal process, re...Ag/TiO2/freeze-dried graphene nanocomposites have been prepared via a facile one-step solvothermal method for the photocatalytic degradation of Rh B under visible light irradiation. During the solvothermal process, reduction of graphene oxide and loading of Ag/TiO2nanoparticles on graphene sheets were achieved. Investigation of chemical state of products showed that covering of Ag/TiO2surface with higher weight ratio of graphene resulting in that Ag metals in Ag/TiO2were oxidized to Ag2 O in nanocomposite structure after solvothermal process. Degree of photocatalytic activity enhancement strongly depends on the coverage of Ag/TiO2surface by porous graphene. The sample of 1 wt% porous graphene hybridized Ag/TiO2showed the highest photocatalytic activity, which is related to high migration efficiency of photoinduced of electrons and reduction of electron–hole recombination rate due to high electrical conductivity of graphene. Expanding of absorption to visible light region was ascribed to surface plasmon resonance effect of Ag metals and presence of graphene. Investigation of photocatalytic performance of formic acid as a dye-less organic pollutant showed that dye sensitization effect of Rh B molecules during evaluation of photocatalytic performance was negligible.展开更多
First-principles plane-wave pseudopotential calculations are performed to study the geometrical structures, for- mation energies, and electronic and optical properties of Y-doped, N-doped, and （Y, N）-codoped Ti02. T...First-principles plane-wave pseudopotential calculations are performed to study the geometrical structures, for- mation energies, and electronic and optical properties of Y-doped, N-doped, and （Y, N）-codoped Ti02. The calculated results show that Y and N codoping leads to lattice distortion, easier separation of photogenerated electron-hole pairs and band gap narrowing. The optical absorption spectra indicate that an obvious red-shift occurs upon Y and N codoping, which enhances visible-light photocatalytic activity.展开更多
A novel Sr2CulnO3S oxysulfide p-type semiconductor photocatalyst has been prepared by solid state reaction method and it exhibits intriguing visible light absorption properties with a bandgap of 2.3 eV. The p-type sem...A novel Sr2CulnO3S oxysulfide p-type semiconductor photocatalyst has been prepared by solid state reaction method and it exhibits intriguing visible light absorption properties with a bandgap of 2.3 eV. The p-type semiconductor character of the synthesized Sr2CuInO3 S was confirmed by Hall efficient measurement and Mott-Schottky plot analysis. First-principles density functional theory calculations （DFT） and electrochem ical measurements were performed to elucidate the electronic structure and the energy band locations. It was found that the as-synthesized Sr2CuInO3S photocatalyst has appreciate conduction and valence band positions for hydrogen and oxygen evolution, respectively. Photocat alytic hydrogen production experiments under a visible light irradiation （A〉420 nm） were carried out by loading different metal and metal-like cocatalysts on Sr2CuInO3S and Rh was found to be the best one among the tested ones.展开更多
Building a covalently connected structure with accelerated photo-induced electrons and charge-carrier separation between semiconductors could enhance the photocatalytic performance.In this work,we report a facile and ...Building a covalently connected structure with accelerated photo-induced electrons and charge-carrier separation between semiconductors could enhance the photocatalytic performance.In this work,we report a facile and novel seed growth method to coat NH2-MIL-125 MOFs with crystalline and porous covalent organic frameworks(COFs)materials and form a range of NH2-MIL-125@TAPB-PDA nanocomposites with different thicknesses of COF shell.The introduction of appropriate content of COF could not only modify the intrinsic electronic and optical properties,but also enhance the photocatalytic activity distinctly.Especially,NH2-MIL-125@TAPB-PDA-3 with COF shell thickness of around 20nm exhibited the highest yield(94.7%)of benzaldehyde which is approximately 2.5 and 15.5 times as that of parental NH2-MIL-125 and COF,respectively.The promoted photocatalytic performance of hybrid materials was mainly owing to the enhanced photo-induced charge carriers transfer between the MOF and COF through the covalent bond.In addition,a possible mechanism to elucidate the process of photocatalysis was explored.Therefore,this kind of MOF-based photocatalysts possesses great potentials in future green organic synthesis.展开更多
A supported TiO2/γ-Al2O3 photocatalyst has been prepared by γ-Al2O3 pellet-filled dielectric barrier discharges induced plasma CVD at atmospheric pressure and room temperature. The TiO2/γ-Al2O3 photocatalyst exhibi...A supported TiO2/γ-Al2O3 photocatalyst has been prepared by γ-Al2O3 pellet-filled dielectric barrier discharges induced plasma CVD at atmospheric pressure and room temperature. The TiO2/γ-Al2O3 photocatalyst exhibits higher photocatalytic activity than Degussa P25, and much higher photocatalytic activity than that prepared by thermal CVD.展开更多
Photocatalysis is an effective way to solve the problems of environmental pollution and energy shortage.Numerous photocatalysts have been developed and various strategies have been proposed to improve the photocatalyt...Photocatalysis is an effective way to solve the problems of environmental pollution and energy shortage.Numerous photocatalysts have been developed and various strategies have been proposed to improve the photocatalytic performance.Among them,Bi-based photocatalysts have become one of the most popular research topics due to their suitable band gaps,unique layered structures,and physicochemical properties.In this review,Bi-based photocatalysts(BiOX,BiVO_(4),Bi_(2)S_(3),Bi_(2)MoO_(6),and other Bi-based photocatalysts)have been summarized in the field of photocatalysis,including their applications of the removal of organic pollutants,hydrogen production,oxygen production etc.The preparation strategies on how to improve the photocatalytic performance and the possible photocatalytic mechanism are also summarized,which could supply new insights for fabricating high-efficient Bi-based photocatalysts.Finally,we summarize the current challenges and make a reasonable outlook on the future development direction of Bi-based photocatalysts.展开更多
COconversion via photocatalysis is a potential solution to address global warming and energy shortage.Photocatalysis can directly utilize the inexhaustible sunlight as an energy source to catalyze the reduction of COt...COconversion via photocatalysis is a potential solution to address global warming and energy shortage.Photocatalysis can directly utilize the inexhaustible sunlight as an energy source to catalyze the reduction of COto useful solar fuels such as CO, CH, CHOH, and CHOH. Among studied formulations, Cubased photocatalysts are the most attractive for COconversion because the Cu-based photocatalysts are low-cost and abundance comparing noble metal-based catalysts. In this literature review, a comprehensive summary of recent progress on Cu-based photocatalysts for COconversion, which includes metallic copper, copper alloy nanoparticles（NPs）, copper oxides, and copper sulfides photocatalysts, can be found. This review also included a detailed discussion on the correlations of morphology, structure, and performance for each type of Cu-based catalysts. The reaction mechanisms and possible pathways for productions of various solar fuels were analyzed, which provide insight into the nature of potential active sites for the catalysts. Finally, the current challenges and perspective future research directions were outlined, holding promise to advance Cu-based photocatalysts for COconversion with much-enhanced energy conversion efficiency and production rates.展开更多
NdZrO–ZrOnanocomposites were prepared via a facile process with propylene glycol as novel connecting agent and benzene tricarboxylic acid as a new complexing agent. The as-obtained NdZrO–ZrOnanocomposites were chara...NdZrO–ZrOnanocomposites were prepared via a facile process with propylene glycol as novel connecting agent and benzene tricarboxylic acid as a new complexing agent. The as-obtained NdZrO–ZrOnanocomposites were characterized by transmission electron microscopy（TEM）, UV–vis diffuse reflectance spectroscopy, energy dispersive X-ray microanalysis（EDX）, Fourier transform infrared（FT-IR）spectroscopy, field emission scanning electron microscopy（FESEM）, and X-ray diffraction（XRD）. According to the morphological studies of the as-synthesized nanocomposites, it was found that the shape and particle size of NdZrO–ZrOnanocomposites depended on the space-filling template type, dosage of space-filling template and tricarboxylic acid as complexing agent. NdZrO–ZrOnanocomposites with different shapes and grain sizes have been synthesized. The photocatalytic behavior of as-produced NdZrO–ZrOnanocomposites was also investigated through photodegradation of methylene blue dye and 2-naphthol as water pollutants.展开更多
In this paper, an N-doped titanium oxide （TiO2） photocatalyst is deposited by a plasma-enhanced atomic layer deposition （PEALD） system through the in-situ doping method. X-ray photoelectron spectroscopy （XPS） an...In this paper, an N-doped titanium oxide （TiO2） photocatalyst is deposited by a plasma-enhanced atomic layer deposition （PEALD） system through the in-situ doping method. X-ray photoelectron spectroscopy （XPS） analysis indicates that substitutional nitrogen atoms （-395.9 eV） with 1 atom% are effectively doped into TiO2 films. UV-VIS spectrometry shows that the in-situ nitrogen doping method indeed enhances the visible-activity of TiO2 films in the 425-550 nm range, and the results of the performance tests of the N-doped TiO2 films also imply that the photocatalysis activity is improved by in-situ doping. The in-situ doping mechanism of the N-doped TiO2 film is suggested according to the XPS results and the typical atomic layer deposition process.展开更多
Layered Aurivillius compound Bi_(5)Ti_(3)CrO_(15) has been synthesized by a hydrothermal method for the application as a photocatalyst to liberate hydrogen from water. Bi_(5)Ti_(3)CrO_(15) owns a narrow band gap (Eg ~...Layered Aurivillius compound Bi_(5)Ti_(3)CrO_(15) has been synthesized by a hydrothermal method for the application as a photocatalyst to liberate hydrogen from water. Bi_(5)Ti_(3)CrO_(15) owns a narrow band gap (Eg ~2.46 eV) and shows stable photocatalytic activity under both full range (λ ≥250 nm) and visible light illumination (λ ≥420 nm). A short hydrothermal reaction time is critical to achieve high photocatalytic activity as defects such as Cr^(6+) and Bi^(5+) can be avoided. An AQE as high as 3.66% at 420 nm ± 20 nm has been recorded, warranting promising application in the field of solar energy conversions. DFT calculation reveals the important role of Cr^(3+) cations for visible light sensitivity of Bi_(5)Ti_(3)CrO_(15).展开更多
Hierarchically assembled SnO_2 microflowers were synthesized by a facile hydrothermal process.Field emission scanning electron microscope results showed these hierarchical nanostructures were built from two dimensiona...Hierarchically assembled SnO_2 microflowers were synthesized by a facile hydrothermal process.Field emission scanning electron microscope results showed these hierarchical nanostructures were built from two dimensional nanosheets with the thicknesses of about 50 nm. Photoluminescence spectrum of the asobtained products demonstrated a strong visual emission peak at 564 nm. The photochemical measurement results indicated that the as-prepared sample exhibits excellent photocatalytic performance. These three dimensional SnO_2 hierarchical nanostructures may have potential applications in waste water purification.展开更多
Polyimide(PI) is an organic polymer material with good stability and diverse sources that has attracted widespread attention in the field of photocatalysis. In this study, a series of PI photocatalysts were synthesize...Polyimide(PI) is an organic polymer material with good stability and diverse sources that has attracted widespread attention in the field of photocatalysis. In this study, a series of PI photocatalysts were synthesized by a thermal polymerization approach using pyromellitic dianhydride(PMDA) and various diamine monomers(melamine(MA), 4,4′-oxydianiline, and melem) as the precursors as well as different heating rates. The effects of the diamine precursor and heating rate on the structure, composition, morphology, and optical properties of the as-prepared PI materials were systematically investigated by various characterization techniques. The selective photo-oxidation of benzylamine was used as a model reaction to evaluate the photocatalytic activities of the resulting PI samples for the oxidation of amines to imines. The results revealed that the PI sample prepared using MA and PMDA as the precursors and a heating rate of 7 ℃/min(MA-PI-7) exhibited the best catalytic performance, with 98% benzylamine conversion and 98% selectivity for N-benzylidene benzylamine after 4 h of irradiation. Several benzylamine derivatives and heterocyclic amines also underwent the photo-oxidation reaction over the MA-PI-7 catalyst to afford the corresponding imines with good activity. In addition, MA-PI-7 exhibited good stability over four successive photocatalytic cycles.展开更多
Understanding the processes of charge generation, transfer and capture is important for the design and synthesis of efficient photocatalysts. In this work, light-induced charge separation and effect of O_(2) on electr...Understanding the processes of charge generation, transfer and capture is important for the design and synthesis of efficient photocatalysts. In this work, light-induced charge separation and effect of O_(2) on electron transfer processes in SrTiO_(3) were investigated by electron paramagnetic resonance(EPR). It was found that photoinduced electron transfer from O_(2)- to Ti^(4+) produced Ti^(3+) and O- redox radical pairs under vacuum condition. Under oxygen atmosphere, however, surface bound superoxide radicals O_(2)-were formed by electron reduction of adsorbed oxygen at initial photoirradiation stage, and quenched by the reverse electron transfer to Ti^(4+) upon further photoirradiation. Formation of long-lived charge separation associated [Ti^(3+)---O-] species and the reversibility of surface bound superoxide radicals mediating the processes of photogenerated electrons may be accountable for the high activity of SrTiO_(3) in photocatalytic water splitting reaction.展开更多
A novel Ag3PO4-CaO composite photocatalyst with enhanced photocatalytic activity was synthesized and utilized for degradation of ammonia from aqueous solution under sunlight. Ag3PO4 was prepared by pre- cipitation met...A novel Ag3PO4-CaO composite photocatalyst with enhanced photocatalytic activity was synthesized and utilized for degradation of ammonia from aqueous solution under sunlight. Ag3PO4 was prepared by pre- cipitation method, and the composite of AgjPO4-CaO was prepared via impregnation method. Utilization of eggshell for CaO synthesis provided a cost-effective and environmental friendly way for the hetero- geneous catalyst production. The as-prepared photocatalysts were characterized by FT-IR, FE-SEM, TEM, EDX, UV-vis and PL Results show that the Ag3PO4-CaO samples have excellent photocatalytic perfor- mances in the wide visible-light region. The effect of operating parameters like the content of Ag3PO4 in composite, initial ammonia concentration, pH of solution, catalyst dosage and oxygen supply was investi- gated. The photoeatalyst with 60 wt% content of Ag3PO4 had a high photocatalytic performance, because a low content of Ag3PO4 causes weak light absorption, and the excess amount of it results in serious electron-hole recombination due to the aggregation of AgjPO4 particles. The maximum ammonia degra- dation （about 70%） was achieved in 340 mg/L of ammonia, pH 11, and 1.25 g/L of catalyst in the presence of pure oxygen. In comparison to Ag3PO4, 60 wt% AgjPO4-CaO had a good stability and it could have been easily separated from the solution for recycling.展开更多
In this study, the Ag/Ag Cl/WO3 plasmonic Z-scheme photocatalysts with different contents of Ag/Ag Cl nanoparticles（NPs） were prepared through a facile ultrasonic precipitation method in geothermal water,wherein the...In this study, the Ag/Ag Cl/WO3 plasmonic Z-scheme photocatalysts with different contents of Ag/Ag Cl nanoparticles（NPs） were prepared through a facile ultrasonic precipitation method in geothermal water,wherein the geothermal water served as the chlorine source. Then the photocatalytic activity was investigated by degradation of 4-Aminobenzoic acid（4-ABA） under visible-light irradiation. It was found that the as-prepared 50 wt% Ag/Ag Cl/WO3 photocatalyst showed the highest photocatalytic efficiency with 25.12 and 3.53 times higher than those of pure WO3 and Ag/Ag Cl, respectively. The active species trapping experiments indicated that h＋and ·O2-were key factors in 4-ABA photodegradation process. The possible plasmonic Z-scheme photocatalytic mechanism of photocatalytic reaction for 4-ABA degradation was proposed based on systematical characterizations. We hope this paper could give new ideas for further exploiting geothermal energy to design and fabricate highly efficient visible-light-driven photocatalysts for environmental remediation.展开更多
SrTiO3 is a promising candidate photocatalyst for overall water splitting.Loading suitable cocatalysts,such as NiOx,the mixture of Ni and NiO,remarkably improve the photocatalytic activity.However,spatial locations an...SrTiO3 is a promising candidate photocatalyst for overall water splitting.Loading suitable cocatalysts,such as NiOx,the mixture of Ni and NiO,remarkably improve the photocatalytic activity.However,spatial locations and functions of components in NiOx/SrTiO3 are under debate.Here,using first-principles density functional theory(DFT)calculations,we investigate the initial growth of Nin(n=1–4)and(NiO)n(n=1,2 and 4)clusters on stoichiometric(100)surfaces of SrTiO3,and explore interfacial and electronic structures of composite photocatalysts.It is found that Nin clusters are easier to undergo aggregation on SrO-termination than on TiO2-termination.The adsorption of Nincluster on(100)surfaces elevates the Fermi level towards the conduction band,which may benefit the occurrence of hydrogen evolution reaction.The structural similarity between(NiO)n cluster and surface has an essential effect on the most stable adsorption configuration.For(NiO)n/SrTiO3 systems,the occupied states of(NiO)n cluster well overlap with those of(100)surfaces in the valence band maximum,which is in favor of the separation of photogenerated electrons and holes to SrTiO3 support and(NiO)n cluster,respectively.The detailed DFT analysis provides important insights into the growth of NiOx on surfaces of SrTiO3and presents an explanation on the different models of NiOx/SrTiO3 photocatalyst proposed by experimental groups.Our calculations build a basis for further investigations on the mechanism of photocatalytic water-splitting reaction in NiOx/SrTiO3composite system.展开更多
Photocatalytic water splitting has gained increasing attention, since it utilizes renewable resources, such as water and solar energy, to produce hydrogen. Using the first-principles density functional theory, we inve...Photocatalytic water splitting has gained increasing attention, since it utilizes renewable resources, such as water and solar energy, to produce hydrogen. Using the first-principles density functional theory, we investigate the properties of the single layer C_2N which was successfully synthesized. We reveal that monolayer C_2N has a substantial direct band gap of 2.45 eV. To regulate its band gap, four different nonmetal elements（B, O, P, and S） on the cation and anion sites are considered. Among them, B-doped N site is the most effective one, with the lowest formation energy and a band gap of 2.01 eV. P-doped N site is the next, with a band gap of 2.08 eV, though its formation energy is higher. The band alignments with respect to the water redox levels show that, for these two dopings, the thermodynamic criterion for the overall water splitting is satisfied. We therefore predict that B-or P-doped C_2N, with an appropriate band gap and an optimal band-edge position, would be a promising photocatalyst for visible-light water splitting.展开更多
In the present study, we investigated the effect of cerium and erbium doping of the zirconium dioxide matrix. We synthesized doped samples using hydrothermal process. The amounts of dopant used were 0.5%, 1% and 5% mo...In the present study, we investigated the effect of cerium and erbium doping of the zirconium dioxide matrix. We synthesized doped samples using hydrothermal process. The amounts of dopant used were 0.5%, 1% and 5% molar(rare earth oxide over zirconium dioxide) respectively. The samples have been studied via X-ray Diffraction measurements for the structural characterization. UV visible diffuse reflectance was used for the optical analysis, Brunauer-Emmett-Teller(BET) model for the measurement of the surface area. Finally the samples have been analysed via electron paramagnetic resonance(EPR) for the electronic characterization. Then we tested the new synthetized materials to determine their photocatalytic activity in the reaction of degradation of methylene blue performed under irradiation by diodes(LEDs) emitting exclusively visible light.展开更多
The hybridization between the outmost s orbitals of metal(Bi^(3+),Sn^(2+),Pb^(2+),Ag^(+))and O 2 p orbitals has been widely employed to develop innovative semiconductors with upshift valence band as well as extended v...The hybridization between the outmost s orbitals of metal(Bi^(3+),Sn^(2+),Pb^(2+),Ag^(+))and O 2 p orbitals has been widely employed to develop innovative semiconductors with upshift valence band as well as extended visible light response,but it is still challenging to obtain photocatalyst with absorption edge of above 550 nm.Here we report a novel Sn^(2+)-based oxyfluoride Sn_(2)TiNbO_6 F(STNOF)photocatalyst with a pyrochlore structure to exhibit an extended absorption edge to 650 nm and dual functionalities of both water reduction and oxidation.Density functional theory calculations suggest that the unprecedented broad-spectrum response of STNOF is mainly ascribed to the strengthened hybridization between O 2 p and Sn 5 s orbitals remarkably upshifting the valence band,which is caused by the distortion and compressive strain in the Sn06 F2 dodecahedron with second-order Jahn-Teller effect due to partial fluorine substitution.The structural distortion and compressive strain are experimentally confirmed by the Fourier-transformed extended X-ray absorption fine spectra.As probe tests of the photocatalytic functionalities,water reduction and oxidation half reactions were examined to see obvious H_(2)and O_(2)evolution under visible light irradiation.This work may provide an alternative strategy of developing extended visible light responsive semiconductors for promising solar energy conversion.展开更多
文摘In this contribution, an efficient and simple two-step hybrid electrochemical-thermal route was developed for the synthesis of cubic shaped Zn_2SnO_4 (ZTO) nanoparticles using aqueous sodium bicarbonate(NaHCO_3) and sodium stannate(Na_2SnO_3) electrolyte. The sacrificial Zn was used as anode and cathode in an undivided cell under galvanostatic mode at room temperature. The bath concentration and current density were respectively varied from 30 to 120 mmol and 0.05 to 1.5 A/dm^2. The electrochemically generated precursor was calcined for an hour at different range of temperature from 60 to 600. The crystallite sizes in the range of 24-53 nm were calculated based on Debye-Scherrer equation. Scanning electron microscope and transmission electron microscopy results reveal that all the particles have cubic morphology with diameter of40-50 nm. The as-prepared ZTO samples showed higher catalytic activity towards the degradation of methylene blue(MB) dye, and 90% degradation was found for the sample calcined at 600, which is greater than that of commercial TiO_2-P25 photocatalysts. The photodegradation efficiency of ZTO samples was found to be a function of exposure time and the dye solution p H value. These results indicate that the ZTO nanoparticles may be employed to remove dyes from wastewater.
文摘Ag/TiO2/freeze-dried graphene nanocomposites have been prepared via a facile one-step solvothermal method for the photocatalytic degradation of Rh B under visible light irradiation. During the solvothermal process, reduction of graphene oxide and loading of Ag/TiO2nanoparticles on graphene sheets were achieved. Investigation of chemical state of products showed that covering of Ag/TiO2surface with higher weight ratio of graphene resulting in that Ag metals in Ag/TiO2were oxidized to Ag2 O in nanocomposite structure after solvothermal process. Degree of photocatalytic activity enhancement strongly depends on the coverage of Ag/TiO2surface by porous graphene. The sample of 1 wt% porous graphene hybridized Ag/TiO2showed the highest photocatalytic activity, which is related to high migration efficiency of photoinduced of electrons and reduction of electron–hole recombination rate due to high electrical conductivity of graphene. Expanding of absorption to visible light region was ascribed to surface plasmon resonance effect of Ag metals and presence of graphene. Investigation of photocatalytic performance of formic acid as a dye-less organic pollutant showed that dye sensitization effect of Rh B molecules during evaluation of photocatalytic performance was negligible.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 10647008, 50971099, and 21176199)the Research Fund for the Doctoral Program of Higher Education, China (Grant Nos. 20096101110017 and 20096101110013)+1 种基金the Key Project of the Natural Science Foundation of Shaanxi Province, China (Grant Nos. 2010JZ002 and 2011JM1001)the Graduate Innovation Fund of Northwest University, China (Grant No. 10YZZ38)
文摘First-principles plane-wave pseudopotential calculations are performed to study the geometrical structures, for- mation energies, and electronic and optical properties of Y-doped, N-doped, and （Y, N）-codoped Ti02. The calculated results show that Y and N codoping leads to lattice distortion, easier separation of photogenerated electron-hole pairs and band gap narrowing. The optical absorption spectra indicate that an obvious red-shift occurs upon Y and N codoping, which enhances visible-light photocatalytic activity.
基金financially supported by the National Natural Science Foundation of China(Grant No.21090341 and 21361140346)the National Basic Research Program(973 Program)of the Ministry of Science and Technology of China(Grant No.2014CB239401)
文摘A novel Sr2CulnO3S oxysulfide p-type semiconductor photocatalyst has been prepared by solid state reaction method and it exhibits intriguing visible light absorption properties with a bandgap of 2.3 eV. The p-type semiconductor character of the synthesized Sr2CuInO3 S was confirmed by Hall efficient measurement and Mott-Schottky plot analysis. First-principles density functional theory calculations （DFT） and electrochem ical measurements were performed to elucidate the electronic structure and the energy band locations. It was found that the as-synthesized Sr2CuInO3S photocatalyst has appreciate conduction and valence band positions for hydrogen and oxygen evolution, respectively. Photocat alytic hydrogen production experiments under a visible light irradiation （A〉420 nm） were carried out by loading different metal and metal-like cocatalysts on Sr2CuInO3S and Rh was found to be the best one among the tested ones.
基金the National Key Research and Development Program of China(No.2016YFB0701100)the National Natural Science Foundation of China(Nos.51802015 and 51890893)Fundamental Research Funds for the Central Universities(FRFTP-16-028A1)。
文摘Building a covalently connected structure with accelerated photo-induced electrons and charge-carrier separation between semiconductors could enhance the photocatalytic performance.In this work,we report a facile and novel seed growth method to coat NH2-MIL-125 MOFs with crystalline and porous covalent organic frameworks(COFs)materials and form a range of NH2-MIL-125@TAPB-PDA nanocomposites with different thicknesses of COF shell.The introduction of appropriate content of COF could not only modify the intrinsic electronic and optical properties,but also enhance the photocatalytic activity distinctly.Especially,NH2-MIL-125@TAPB-PDA-3 with COF shell thickness of around 20nm exhibited the highest yield(94.7%)of benzaldehyde which is approximately 2.5 and 15.5 times as that of parental NH2-MIL-125 and COF,respectively.The promoted photocatalytic performance of hybrid materials was mainly owing to the enhanced photo-induced charge carriers transfer between the MOF and COF through the covalent bond.In addition,a possible mechanism to elucidate the process of photocatalysis was explored.Therefore,this kind of MOF-based photocatalysts possesses great potentials in future green organic synthesis.
文摘A supported TiO2/γ-Al2O3 photocatalyst has been prepared by γ-Al2O3 pellet-filled dielectric barrier discharges induced plasma CVD at atmospheric pressure and room temperature. The TiO2/γ-Al2O3 photocatalyst exhibits higher photocatalytic activity than Degussa P25, and much higher photocatalytic activity than that prepared by thermal CVD.
基金We gratefully acknowledge the support of this research by the National Natural Science Foundation of China(52172206,21871078)the Heilongjiang Province Natural Science Foundation of China(JQ2019B001)+4 种基金the Shandong Province Natural Science Foundation(ZR2021MB016)the Heilongjiang Provincial Institutions of Higher Learning Basic Research Funds Basic Research Projects(2021-KYYWF-0007)the Heilongjiang Postdoctoral Startup Fund(LBH-Q14135)the Heilongjiang University Science Fund for Distinguished Young Scholars(JCL201802)the Development plan of Youth Innovation Team in Colleges and Universities of Shandong Province.
文摘Photocatalysis is an effective way to solve the problems of environmental pollution and energy shortage.Numerous photocatalysts have been developed and various strategies have been proposed to improve the photocatalytic performance.Among them,Bi-based photocatalysts have become one of the most popular research topics due to their suitable band gaps,unique layered structures,and physicochemical properties.In this review,Bi-based photocatalysts(BiOX,BiVO_(4),Bi_(2)S_(3),Bi_(2)MoO_(6),and other Bi-based photocatalysts)have been summarized in the field of photocatalysis,including their applications of the removal of organic pollutants,hydrogen production,oxygen production etc.The preparation strategies on how to improve the photocatalytic performance and the possible photocatalytic mechanism are also summarized,which could supply new insights for fabricating high-efficient Bi-based photocatalysts.Finally,we summarize the current challenges and make a reasonable outlook on the future development direction of Bi-based photocatalysts.
基金financial supports from the National 1000 Young Talents Program of Chinathe National Nature Science Foundation of China (21603078)+1 种基金the National Materials Genome Project (2016YFB0700600)financial support from Research and Education in eNergy, Environment and Water (RENEW)Institute at the University at Buffalo, SUNY
文摘COconversion via photocatalysis is a potential solution to address global warming and energy shortage.Photocatalysis can directly utilize the inexhaustible sunlight as an energy source to catalyze the reduction of COto useful solar fuels such as CO, CH, CHOH, and CHOH. Among studied formulations, Cubased photocatalysts are the most attractive for COconversion because the Cu-based photocatalysts are low-cost and abundance comparing noble metal-based catalysts. In this literature review, a comprehensive summary of recent progress on Cu-based photocatalysts for COconversion, which includes metallic copper, copper alloy nanoparticles（NPs）, copper oxides, and copper sulfides photocatalysts, can be found. This review also included a detailed discussion on the correlations of morphology, structure, and performance for each type of Cu-based catalysts. The reaction mechanisms and possible pathways for productions of various solar fuels were analyzed, which provide insight into the nature of potential active sites for the catalysts. Finally, the current challenges and perspective future research directions were outlined, holding promise to advance Cu-based photocatalysts for COconversion with much-enhanced energy conversion efficiency and production rates.
基金the council of Iran National Science FoundationUniversity of Kashan for supporting this work by Grant No(159271/7579)
文摘NdZrO–ZrOnanocomposites were prepared via a facile process with propylene glycol as novel connecting agent and benzene tricarboxylic acid as a new complexing agent. The as-obtained NdZrO–ZrOnanocomposites were characterized by transmission electron microscopy（TEM）, UV–vis diffuse reflectance spectroscopy, energy dispersive X-ray microanalysis（EDX）, Fourier transform infrared（FT-IR）spectroscopy, field emission scanning electron microscopy（FESEM）, and X-ray diffraction（XRD）. According to the morphological studies of the as-synthesized nanocomposites, it was found that the shape and particle size of NdZrO–ZrOnanocomposites depended on the space-filling template type, dosage of space-filling template and tricarboxylic acid as complexing agent. NdZrO–ZrOnanocomposites with different shapes and grain sizes have been synthesized. The photocatalytic behavior of as-produced NdZrO–ZrOnanocomposites was also investigated through photodegradation of methylene blue dye and 2-naphthol as water pollutants.
基金supported by the National Science and Technology Major Project of China(No.2009ZX02037-003)China Postdoctoral Science Foundation(No.2011M500996)the Opening Project of Key Laboratory of Microelectronics Devices&Integrated Technology,Institute of Microelectronics,Chinese Academy of Sciences
文摘In this paper, an N-doped titanium oxide （TiO2） photocatalyst is deposited by a plasma-enhanced atomic layer deposition （PEALD） system through the in-situ doping method. X-ray photoelectron spectroscopy （XPS） analysis indicates that substitutional nitrogen atoms （-395.9 eV） with 1 atom% are effectively doped into TiO2 films. UV-VIS spectrometry shows that the in-situ nitrogen doping method indeed enhances the visible-activity of TiO2 films in the 425-550 nm range, and the results of the performance tests of the N-doped TiO2 films also imply that the photocatalysis activity is improved by in-situ doping. The in-situ doping mechanism of the N-doped TiO2 film is suggested according to the XPS results and the typical atomic layer deposition process.
基金This work was supported by the National Natural Science Foundation of China(No.51972233)the Natural Science Foundation of Shanghai(No.19ZR1459200)+1 种基金the Shanghai Science and Technology Commission(No.14DZ2261100)the Fundamental Research Funds for the Central Universities.We also thank Prof.Hongying Zhao for EPR analysis.
文摘Layered Aurivillius compound Bi_(5)Ti_(3)CrO_(15) has been synthesized by a hydrothermal method for the application as a photocatalyst to liberate hydrogen from water. Bi_(5)Ti_(3)CrO_(15) owns a narrow band gap (Eg ~2.46 eV) and shows stable photocatalytic activity under both full range (λ ≥250 nm) and visible light illumination (λ ≥420 nm). A short hydrothermal reaction time is critical to achieve high photocatalytic activity as defects such as Cr^(6+) and Bi^(5+) can be avoided. An AQE as high as 3.66% at 420 nm ± 20 nm has been recorded, warranting promising application in the field of solar energy conversions. DFT calculation reveals the important role of Cr^(3+) cations for visible light sensitivity of Bi_(5)Ti_(3)CrO_(15).
基金supported by the Foundation for Key Project of Ministry of Education, China (No. 211046)Program for New Century Excellent Talents in Heilongjiang Provincial University (1252-NCET-018)+1 种基金the Scientific Research Fund of Heilongjiang Provincial Education Department (12531179)Program for Scientific and Technological Innovation Team Construction in Universities of Heilongjiang (No. 2011TD010)
文摘Hierarchically assembled SnO_2 microflowers were synthesized by a facile hydrothermal process.Field emission scanning electron microscope results showed these hierarchical nanostructures were built from two dimensional nanosheets with the thicknesses of about 50 nm. Photoluminescence spectrum of the asobtained products demonstrated a strong visual emission peak at 564 nm. The photochemical measurement results indicated that the as-prepared sample exhibits excellent photocatalytic performance. These three dimensional SnO_2 hierarchical nanostructures may have potential applications in waste water purification.
基金the Opening Project of Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan(Grant number:LZJ2101)the Fundamental Research Funds of China West Normal University(Grant number:19D038).
文摘Polyimide(PI) is an organic polymer material with good stability and diverse sources that has attracted widespread attention in the field of photocatalysis. In this study, a series of PI photocatalysts were synthesized by a thermal polymerization approach using pyromellitic dianhydride(PMDA) and various diamine monomers(melamine(MA), 4,4′-oxydianiline, and melem) as the precursors as well as different heating rates. The effects of the diamine precursor and heating rate on the structure, composition, morphology, and optical properties of the as-prepared PI materials were systematically investigated by various characterization techniques. The selective photo-oxidation of benzylamine was used as a model reaction to evaluate the photocatalytic activities of the resulting PI samples for the oxidation of amines to imines. The results revealed that the PI sample prepared using MA and PMDA as the precursors and a heating rate of 7 ℃/min(MA-PI-7) exhibited the best catalytic performance, with 98% benzylamine conversion and 98% selectivity for N-benzylidene benzylamine after 4 h of irradiation. Several benzylamine derivatives and heterocyclic amines also underwent the photo-oxidation reaction over the MA-PI-7 catalyst to afford the corresponding imines with good activity. In addition, MA-PI-7 exhibited good stability over four successive photocatalytic cycles.
基金financially supported by the National Key R&D Program of China under contact No.2017YFA0204804the National Natural Science Foundation of China under contact Nos.21761142018,21473189 and 22088102 for supporting Fundamental Research Center of Artificial Photosynthesis(FRe CAP)。
文摘Understanding the processes of charge generation, transfer and capture is important for the design and synthesis of efficient photocatalysts. In this work, light-induced charge separation and effect of O_(2) on electron transfer processes in SrTiO_(3) were investigated by electron paramagnetic resonance(EPR). It was found that photoinduced electron transfer from O_(2)- to Ti^(4+) produced Ti^(3+) and O- redox radical pairs under vacuum condition. Under oxygen atmosphere, however, surface bound superoxide radicals O_(2)-were formed by electron reduction of adsorbed oxygen at initial photoirradiation stage, and quenched by the reverse electron transfer to Ti^(4+) upon further photoirradiation. Formation of long-lived charge separation associated [Ti^(3+)---O-] species and the reversibility of surface bound superoxide radicals mediating the processes of photogenerated electrons may be accountable for the high activity of SrTiO_(3) in photocatalytic water splitting reaction.
文摘A novel Ag3PO4-CaO composite photocatalyst with enhanced photocatalytic activity was synthesized and utilized for degradation of ammonia from aqueous solution under sunlight. Ag3PO4 was prepared by pre- cipitation method, and the composite of AgjPO4-CaO was prepared via impregnation method. Utilization of eggshell for CaO synthesis provided a cost-effective and environmental friendly way for the hetero- geneous catalyst production. The as-prepared photocatalysts were characterized by FT-IR, FE-SEM, TEM, EDX, UV-vis and PL Results show that the Ag3PO4-CaO samples have excellent photocatalytic perfor- mances in the wide visible-light region. The effect of operating parameters like the content of Ag3PO4 in composite, initial ammonia concentration, pH of solution, catalyst dosage and oxygen supply was investi- gated. The photoeatalyst with 60 wt% content of Ag3PO4 had a high photocatalytic performance, because a low content of Ag3PO4 causes weak light absorption, and the excess amount of it results in serious electron-hole recombination due to the aggregation of AgjPO4 particles. The maximum ammonia degra- dation （about 70%） was achieved in 340 mg/L of ammonia, pH 11, and 1.25 g/L of catalyst in the presence of pure oxygen. In comparison to Ag3PO4, 60 wt% AgjPO4-CaO had a good stability and it could have been easily separated from the solution for recycling.
基金the financial support by the National Natural Science Foundation of China (grant no. 51272107 and 51372118)the Doctor Discipline Special Research Foundation of Chinese Ministry of Education (grant no. 20133219110015)
文摘In this study, the Ag/Ag Cl/WO3 plasmonic Z-scheme photocatalysts with different contents of Ag/Ag Cl nanoparticles（NPs） were prepared through a facile ultrasonic precipitation method in geothermal water,wherein the geothermal water served as the chlorine source. Then the photocatalytic activity was investigated by degradation of 4-Aminobenzoic acid（4-ABA） under visible-light irradiation. It was found that the as-prepared 50 wt% Ag/Ag Cl/WO3 photocatalyst showed the highest photocatalytic efficiency with 25.12 and 3.53 times higher than those of pure WO3 and Ag/Ag Cl, respectively. The active species trapping experiments indicated that h＋and ·O2-were key factors in 4-ABA photodegradation process. The possible plasmonic Z-scheme photocatalytic mechanism of photocatalytic reaction for 4-ABA degradation was proposed based on systematical characterizations. We hope this paper could give new ideas for further exploiting geothermal energy to design and fabricate highly efficient visible-light-driven photocatalysts for environmental remediation.
基金financially supported by the National Natural Science Foundation of China under Grant 21473183
文摘SrTiO3 is a promising candidate photocatalyst for overall water splitting.Loading suitable cocatalysts,such as NiOx,the mixture of Ni and NiO,remarkably improve the photocatalytic activity.However,spatial locations and functions of components in NiOx/SrTiO3 are under debate.Here,using first-principles density functional theory(DFT)calculations,we investigate the initial growth of Nin(n=1–4)and(NiO)n(n=1,2 and 4)clusters on stoichiometric(100)surfaces of SrTiO3,and explore interfacial and electronic structures of composite photocatalysts.It is found that Nin clusters are easier to undergo aggregation on SrO-termination than on TiO2-termination.The adsorption of Nincluster on(100)surfaces elevates the Fermi level towards the conduction band,which may benefit the occurrence of hydrogen evolution reaction.The structural similarity between(NiO)n cluster and surface has an essential effect on the most stable adsorption configuration.For(NiO)n/SrTiO3 systems,the occupied states of(NiO)n cluster well overlap with those of(100)surfaces in the valence band maximum,which is in favor of the separation of photogenerated electrons and holes to SrTiO3 support and(NiO)n cluster,respectively.The detailed DFT analysis provides important insights into the growth of NiOx on surfaces of SrTiO3and presents an explanation on the different models of NiOx/SrTiO3 photocatalyst proposed by experimental groups.Our calculations build a basis for further investigations on the mechanism of photocatalytic water-splitting reaction in NiOx/SrTiO3composite system.
基金supported by the National Natural Science Foundation of China(Grant No.11574167)
文摘Photocatalytic water splitting has gained increasing attention, since it utilizes renewable resources, such as water and solar energy, to produce hydrogen. Using the first-principles density functional theory, we investigate the properties of the single layer C_2N which was successfully synthesized. We reveal that monolayer C_2N has a substantial direct band gap of 2.45 eV. To regulate its band gap, four different nonmetal elements（B, O, P, and S） on the cation and anion sites are considered. Among them, B-doped N site is the most effective one, with the lowest formation energy and a band gap of 2.01 eV. P-doped N site is the next, with a band gap of 2.08 eV, though its formation energy is higher. The band alignments with respect to the water redox levels show that, for these two dopings, the thermodynamic criterion for the overall water splitting is satisfied. We therefore predict that B-or P-doped C_2N, with an appropriate band gap and an optimal band-edge position, would be a promising photocatalyst for visible-light water splitting.
基金supported by the CARIPLO Foundation with the Advanced Materials Grant 2013 "Development of second generation photocatalysts for energy and environment"the Local Funding of the University of Torino call_2014_L2_126
文摘In the present study, we investigated the effect of cerium and erbium doping of the zirconium dioxide matrix. We synthesized doped samples using hydrothermal process. The amounts of dopant used were 0.5%, 1% and 5% molar(rare earth oxide over zirconium dioxide) respectively. The samples have been studied via X-ray Diffraction measurements for the structural characterization. UV visible diffuse reflectance was used for the optical analysis, Brunauer-Emmett-Teller(BET) model for the measurement of the surface area. Finally the samples have been analysed via electron paramagnetic resonance(EPR) for the electronic characterization. Then we tested the new synthetized materials to determine their photocatalytic activity in the reaction of degradation of methylene blue performed under irradiation by diodes(LEDs) emitting exclusively visible light.
基金financially supported by the National Natural Science Foundation of China(NSFC)(22088102)supported by the National Natural Science Foundation of China(21633009,21633010,21925206)+4 种基金the Cooperation Fund of Dalian National Laboratory for Clean Energy(DNL201913)International Partnership Program of Chinese Academy of Sciences(121421KYSB20190025)the DICP foundation of innovative research(DICPI201927)Strategic Priority Research Pro-gram of Chinese Academy of Sciences(XDB17000000)support from Liaoning Revitalization Talents Program(XLYC1807241)。
文摘The hybridization between the outmost s orbitals of metal(Bi^(3+),Sn^(2+),Pb^(2+),Ag^(+))and O 2 p orbitals has been widely employed to develop innovative semiconductors with upshift valence band as well as extended visible light response,but it is still challenging to obtain photocatalyst with absorption edge of above 550 nm.Here we report a novel Sn^(2+)-based oxyfluoride Sn_(2)TiNbO_6 F(STNOF)photocatalyst with a pyrochlore structure to exhibit an extended absorption edge to 650 nm and dual functionalities of both water reduction and oxidation.Density functional theory calculations suggest that the unprecedented broad-spectrum response of STNOF is mainly ascribed to the strengthened hybridization between O 2 p and Sn 5 s orbitals remarkably upshifting the valence band,which is caused by the distortion and compressive strain in the Sn06 F2 dodecahedron with second-order Jahn-Teller effect due to partial fluorine substitution.The structural distortion and compressive strain are experimentally confirmed by the Fourier-transformed extended X-ray absorption fine spectra.As probe tests of the photocatalytic functionalities,water reduction and oxidation half reactions were examined to see obvious H_(2)and O_(2)evolution under visible light irradiation.This work may provide an alternative strategy of developing extended visible light responsive semiconductors for promising solar energy conversion.
