In this study,the truncated octahedral CeO_(2)(CeO_(2)-to)with special morphology was prepared by the solvothermal method with oleic acid(OA)and oleamine(OM)as the morphology-directing agents.High-resolution transmiss...In this study,the truncated octahedral CeO_(2)(CeO_(2)-to)with special morphology was prepared by the solvothermal method with oleic acid(OA)and oleamine(OM)as the morphology-directing agents.High-resolution transmission electron microscopy(HRTEM)results show that CeO_(2)-to exposes composite{100}and{111}facets,while CeO_(2)cubic(CeO_(2)-c)and CeO_(2)octahedral(CeO_(2)-o)only expose single crystal facets of{100}plane and{111}plane,respectively.Interestingly,this CeO_(2)-to photocatalyst exhibits remarkable photooxidation performance of gaseous acetaldehyde(CH_(3)CHO)degradation,in which CO_(2)generation value reaches 1.78 and 7.97-times greater than that of CeO_(2)-c and CeO_(2)-o,respectively.In addition,the active species trapping experiment signifies that superoxide(·O_(2)^(-))and holes(h^(+))are the main reactive substances during the CH_(3)CHO degradation process,and the electron paramagnetic resonance(EPR)spectra indicates that the former is the major contributor.Notably,the electron transfer mechanism between CeO_(2)-to{100}and{111}facets and the surface oxygen adsorption ability are revealed via density functional theory(DFT)calculations.It is also confirmed that{100}facets are more conducive to the absorption of acetaldehyde than{111}facets.Finally,a reasonable mechanism for improved photocatalytic CH_(3)CHO degradation on CeO_(2)-to is proposed based on relevant experiments and DFT calculations.This study demonstrates that the systematic development of surface homojunction structured photocatalysts can efficiently increase the degradation activity for volatile organic compounds(VOCs).It also offers additional direction for optimizing the photocatalytic activity of other ceriumbased photocatalysts.展开更多
Polymer carbon nitride(PCN)is widely used in photocatalysis.However,pristine PCN has disadvantages such as insufficient visible light absorption and low photogenerated carrier separation efficiency that greatly limite...Polymer carbon nitride(PCN)is widely used in photocatalysis.However,pristine PCN has disadvantages such as insufficient visible light absorption and low photogenerated carrier separation efficiency that greatly limited the photocatalytic efficiency.As a non-toxic metal,gallium has the potential to solve the defects of PCN.Gallium ions coordinated with nitrogen in carbon nitride to form Ga-N active sites and improved the photocatalytic activity.The doped potassium ions form a transmission channel for charge redistribution and transfer between adjacent layers,which is beneficial for better separation of photoexcited carriers.In this study,a series of PCN co-doped with gallium and potassium(Ga-K-PCN)were prepared.The experimental results indicated photocatalytic generation of hydrogen peroxide proceeds through the 2e−oxygen reduction reaction pathway.Notably,Nyquist plots and photocurrent results further proved that the presence of Ga-N sites and potassium ion doping could significantly improve the separation/transfer of intra-planar and interlayer charge carriers and thus enhance photocatalytic efficiency.The Ga10-K3-PCN photocatalysts promoted yield of H_(2)O_(2),with reactivity at 28.2μmol/(g·h)and solar-to-chemical conversion efficiency at 0.64%,surpassed that of a typical photo-catalyst based on PCN(0.18%).展开更多
Suppression of photogenerated charge recombination is crucial for efficient photocatalytic hydrogen production.Homojunctions have garnered more attention than heterojunctions due to their superior crystal binding and ...Suppression of photogenerated charge recombination is crucial for efficient photocatalytic hydrogen production.Homojunctions have garnered more attention than heterojunctions due to their superior crystal binding and band structure matching.However,most homojunctions suffer from redox interference caused by continuous oxidizing and reducing phases that impede the ability to improve photocatalytic activity.Consequently,the preparation of homojunction photocatalysts with completely spatial separation of both in charge and redox phases remains challenging.Here,the preparation of a two-dimensional(2D)homojunction CeO_(2) with a back-to-back geometry and fully separated oxidizing and reducing phases is reported.The prepared CeO_(2) is composed of nanosheets with twocontrasting smooth and rough surfaces.Experimental and theoretical results indicate that the rough surface contains more highly reducing CeO_(2){220}and strongly visiblelight-absorbing CeO_(2){200}facets than the smooth surface.The 2D homojunction CeO_(2) produces three-times more hydrogen than normal CeO_(2) nanosheets,and even more than that of CeO_(2) nanosheets loaded with gold nanoparticles.This work presents a new homojunction photocatalyst model with completely spatial separation of both in charge and redox phases that is expected to inspire further research into homojunction photocatalysts.展开更多
Anatase titanium(IV)oxide(TiO_(2))particles with exposed{001}and{101}facets were prepared by hydrothermal treatment of amorphous TiO_(2) with H_(2)O_(2)-NH_(3) solution.Crystal phase,shape,and size of TiO_(2) particle...Anatase titanium(IV)oxide(TiO_(2))particles with exposed{001}and{101}facets were prepared by hydrothermal treatment of amorphous TiO_(2) with H_(2)O_(2)-NH_(3) solution.Crystal phase,shape,and size of TiO_(2) particles are found to be greatly dependent on the ratio of H_(2)O_(2)-NH_(3) solution.The prepared TiO_(2) particles with specific exposed crystal faces show higher photocatalytic activity for acetaldehyde decomposition than commercial spherical TiO_(2) particles.This result implies that recombination is prevented by spatial separation of redox sites in the particles because of selective migration of electrons and positive holes to specific exposed crystal faces and/or different reactivity of electrons and positive holes on the specific exposed crystal face.展开更多
Luminescent polystyrene microspheres were easily fabricated from poly(styrene-co-methacrylic acid)and aqueous RE(III) chloride solution(RE=Eu, Tb) in the presence of 2,20-bipyridine as second ligand. The negative char...Luminescent polystyrene microspheres were easily fabricated from poly(styrene-co-methacrylic acid)and aqueous RE(III) chloride solution(RE=Eu, Tb) in the presence of 2,20-bipyridine as second ligand. The negative charges of carboxyl groups on the surface of microspheres coordinated with rare earth ions at first, such as complexes covalently linked to 2,20-bipyridine, resulting in strong photoluminescence. Various methods, including transmission electron microscope(TEM), scanning electron microscope(SEM), energy dispersive spectroscopy(EDS),Fourier transform infrared spectroscopy(FT-IR), and fluorescence spectrophotometer, were used to characterize the resultant polystyrene composite microspheres. This work highlights the idea that it is facile to synthesis luminescent microspheres by surface-modified method directly.展开更多
Graphitic carbon nitride(g-C3N4)was synthesized by heating melamine and was then treated with sodium hydroxide solution under a hydrothermal condition to obtain g-C3N4 with a large specific surface area(HSSA).HSSA sho...Graphitic carbon nitride(g-C3N4)was synthesized by heating melamine and was then treated with sodium hydroxide solution under a hydrothermal condition to obtain g-C3N4 with a large specific surface area(HSSA).HSSA shows higher photocatalytic activity for decomposition of acetaldehyde than that of original g-C3N4.HSSA was modified with RuO2 as a co-catalyst by the impregnation method.HSSA loaded with 0.05 wt%RuO2 shows the highest photocatalytic activity for acetaldehyde decomposition under visible light(k=455 nm).展开更多
Our previous studies suggested that redox reaction proceeded separately on specific exposed crystal faces of TiO2 nanoparticles. Site-selective deposition of metal or metal oxide on TiO2 specific exposed crystal faces...Our previous studies suggested that redox reaction proceeded separately on specific exposed crystal faces of TiO2 nanoparticles. Site-selective deposition of metal or metal oxide on TiO2 specific exposed crystal faces successfully proceeded using the unique reactivity properties on the surface of TiO2 nanoparticles under photoexcitation. A remarkable improvement ofphotocatalytic activity of shape- controlled brookite and rutile TiO2 nanorods with modification of Fe^3＋ compounds was observed under visible light. Crystal face-selective metal compound modification on exposed crystal faces of TiO2 nanorods with brookite and futile phases was successfully prepared. Brookite and rutile TiO2 nanorods prepared by site-selective modification with metal compounds should be ideal visible-light responsive TiO2 photocatalysts because of the remarkable suppression of back electron transfer from TiO2 to oxidized metal com- pounds on the surface of the TiO2 nanorod with a brookite or rutile phase. In this paper, the development of exposed crystal face-controlled TiO2 nanorods with rutile and brookite phases was described. The obtained rutile and brookite TiO2 nanorod, showing remarkably high activity for degra- dation of organic compounds compared with the photocatalytic activities of anatase fine particles （ST-01）, is one of the most active commercially available photocatalysts for environmental cleanup in Japan. The technology of visiblelight responsive treatment for morphology-controlled rutile and brookite TiO2 nanorods by crystal face-selective modification of Fe^3＋ compounds was also discussed in this paper. The Fe^3＋ compound-modified rutile and brookite TiO2 nanorods show much higher activity than conventional visible-light responsive N-doped TiO2, which is commercially available in Japan.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21805191 and 22205084)Project funded by China Postdoctoral Science Foundation(No.2023M741039)+3 种基金Project funded by National&Local Joint Engineering Research Center for Mineral Salt Deep Utilization(SF202303)Project Funded by Yangzhou University(137013308),Guangdong Basic and Applied Basic Research Foundation(No.2020A1515010982)Shenzhen Stable Support Project(No.20200812122947002),the Innovative Science and Technology Platform Project of Cooperation between Yangzhou City and Yangzhou UniversityPostgraduate Research&Practice Innovation Program of Jiangsu Province(Yangzhou University,No.XKYCX20_014)。
文摘In this study,the truncated octahedral CeO_(2)(CeO_(2)-to)with special morphology was prepared by the solvothermal method with oleic acid(OA)and oleamine(OM)as the morphology-directing agents.High-resolution transmission electron microscopy(HRTEM)results show that CeO_(2)-to exposes composite{100}and{111}facets,while CeO_(2)cubic(CeO_(2)-c)and CeO_(2)octahedral(CeO_(2)-o)only expose single crystal facets of{100}plane and{111}plane,respectively.Interestingly,this CeO_(2)-to photocatalyst exhibits remarkable photooxidation performance of gaseous acetaldehyde(CH_(3)CHO)degradation,in which CO_(2)generation value reaches 1.78 and 7.97-times greater than that of CeO_(2)-c and CeO_(2)-o,respectively.In addition,the active species trapping experiment signifies that superoxide(·O_(2)^(-))and holes(h^(+))are the main reactive substances during the CH_(3)CHO degradation process,and the electron paramagnetic resonance(EPR)spectra indicates that the former is the major contributor.Notably,the electron transfer mechanism between CeO_(2)-to{100}and{111}facets and the surface oxygen adsorption ability are revealed via density functional theory(DFT)calculations.It is also confirmed that{100}facets are more conducive to the absorption of acetaldehyde than{111}facets.Finally,a reasonable mechanism for improved photocatalytic CH_(3)CHO degradation on CeO_(2)-to is proposed based on relevant experiments and DFT calculations.This study demonstrates that the systematic development of surface homojunction structured photocatalysts can efficiently increase the degradation activity for volatile organic compounds(VOCs).It also offers additional direction for optimizing the photocatalytic activity of other ceriumbased photocatalysts.
基金The support of Mitsubishi Chemical Corporation and the Japan Society for the Promotion of Science Grant-in-Aid for Scientific Research B(No.20H02847)the Support for Pioneering Research Initiated by the Next Generation program for Japan Science and Technology Agency(No.JPMJSP2154)the National Natural Science Foundation of China(No.52103008)are greatly acknowledged.
文摘Polymer carbon nitride(PCN)is widely used in photocatalysis.However,pristine PCN has disadvantages such as insufficient visible light absorption and low photogenerated carrier separation efficiency that greatly limited the photocatalytic efficiency.As a non-toxic metal,gallium has the potential to solve the defects of PCN.Gallium ions coordinated with nitrogen in carbon nitride to form Ga-N active sites and improved the photocatalytic activity.The doped potassium ions form a transmission channel for charge redistribution and transfer between adjacent layers,which is beneficial for better separation of photoexcited carriers.In this study,a series of PCN co-doped with gallium and potassium(Ga-K-PCN)were prepared.The experimental results indicated photocatalytic generation of hydrogen peroxide proceeds through the 2e−oxygen reduction reaction pathway.Notably,Nyquist plots and photocurrent results further proved that the presence of Ga-N sites and potassium ion doping could significantly improve the separation/transfer of intra-planar and interlayer charge carriers and thus enhance photocatalytic efficiency.The Ga10-K3-PCN photocatalysts promoted yield of H_(2)O_(2),with reactivity at 28.2μmol/(g·h)and solar-to-chemical conversion efficiency at 0.64%,surpassed that of a typical photo-catalyst based on PCN(0.18%).
基金financially supported by the National Natural Science Foundation of China (Nos.22205084 and21805191)the Start-Up Funding of Jiangsu University of Science and Technology (No.1112932203)+2 种基金Guangdong Basic and Applied Basic Research Foundation (No.2020A1515010982)Shenzhen Stable Support Project (No.20200812122947002)Shenzhen Peacock Plan (No.20210802524B)。
文摘Suppression of photogenerated charge recombination is crucial for efficient photocatalytic hydrogen production.Homojunctions have garnered more attention than heterojunctions due to their superior crystal binding and band structure matching.However,most homojunctions suffer from redox interference caused by continuous oxidizing and reducing phases that impede the ability to improve photocatalytic activity.Consequently,the preparation of homojunction photocatalysts with completely spatial separation of both in charge and redox phases remains challenging.Here,the preparation of a two-dimensional(2D)homojunction CeO_(2) with a back-to-back geometry and fully separated oxidizing and reducing phases is reported.The prepared CeO_(2) is composed of nanosheets with twocontrasting smooth and rough surfaces.Experimental and theoretical results indicate that the rough surface contains more highly reducing CeO_(2){220}and strongly visiblelight-absorbing CeO_(2){200}facets than the smooth surface.The 2D homojunction CeO_(2) produces three-times more hydrogen than normal CeO_(2) nanosheets,and even more than that of CeO_(2) nanosheets loaded with gold nanoparticles.This work presents a new homojunction photocatalyst model with completely spatial separation of both in charge and redox phases that is expected to inspire further research into homojunction photocatalysts.
基金financially supported by the Programs of Japan Science and Technology Agency:Promoting Individual Research to Nature the Seeds of Future Innovation and Organizing the Unique and Innovative Network,and Advanced Catalytic Transformation Program for Carbon Utilization
文摘Anatase titanium(IV)oxide(TiO_(2))particles with exposed{001}and{101}facets were prepared by hydrothermal treatment of amorphous TiO_(2) with H_(2)O_(2)-NH_(3) solution.Crystal phase,shape,and size of TiO_(2) particles are found to be greatly dependent on the ratio of H_(2)O_(2)-NH_(3) solution.The prepared TiO_(2) particles with specific exposed crystal faces show higher photocatalytic activity for acetaldehyde decomposition than commercial spherical TiO_(2) particles.This result implies that recombination is prevented by spatial separation of redox sites in the particles because of selective migration of electrons and positive holes to specific exposed crystal faces and/or different reactivity of electrons and positive holes on the specific exposed crystal face.
基金financially supported by the National Natural Science Fundation of China (No.50873085)
文摘Luminescent polystyrene microspheres were easily fabricated from poly(styrene-co-methacrylic acid)and aqueous RE(III) chloride solution(RE=Eu, Tb) in the presence of 2,20-bipyridine as second ligand. The negative charges of carboxyl groups on the surface of microspheres coordinated with rare earth ions at first, such as complexes covalently linked to 2,20-bipyridine, resulting in strong photoluminescence. Various methods, including transmission electron microscope(TEM), scanning electron microscope(SEM), energy dispersive spectroscopy(EDS),Fourier transform infrared spectroscopy(FT-IR), and fluorescence spectrophotometer, were used to characterize the resultant polystyrene composite microspheres. This work highlights the idea that it is facile to synthesis luminescent microspheres by surface-modified method directly.
基金financially supported by the Programs of Japan Science and Technology Agency:Promoting Individual Research to Nature the Seeds of Future Innovation and Organizing the Unique and Innovative Network,and Advanced Catalytic Transformation Program for Carbon Utilization
文摘Graphitic carbon nitride(g-C3N4)was synthesized by heating melamine and was then treated with sodium hydroxide solution under a hydrothermal condition to obtain g-C3N4 with a large specific surface area(HSSA).HSSA shows higher photocatalytic activity for decomposition of acetaldehyde than that of original g-C3N4.HSSA was modified with RuO2 as a co-catalyst by the impregnation method.HSSA loaded with 0.05 wt%RuO2 shows the highest photocatalytic activity for acetaldehyde decomposition under visible light(k=455 nm).
基金financially supported by the Advanced Catalytic Transformation Program for Carbon Utilization(ACT-C)Japan Science and Technology Agency(JST)
文摘Our previous studies suggested that redox reaction proceeded separately on specific exposed crystal faces of TiO2 nanoparticles. Site-selective deposition of metal or metal oxide on TiO2 specific exposed crystal faces successfully proceeded using the unique reactivity properties on the surface of TiO2 nanoparticles under photoexcitation. A remarkable improvement ofphotocatalytic activity of shape- controlled brookite and rutile TiO2 nanorods with modification of Fe^3＋ compounds was observed under visible light. Crystal face-selective metal compound modification on exposed crystal faces of TiO2 nanorods with brookite and futile phases was successfully prepared. Brookite and rutile TiO2 nanorods prepared by site-selective modification with metal compounds should be ideal visible-light responsive TiO2 photocatalysts because of the remarkable suppression of back electron transfer from TiO2 to oxidized metal com- pounds on the surface of the TiO2 nanorod with a brookite or rutile phase. In this paper, the development of exposed crystal face-controlled TiO2 nanorods with rutile and brookite phases was described. The obtained rutile and brookite TiO2 nanorod, showing remarkably high activity for degra- dation of organic compounds compared with the photocatalytic activities of anatase fine particles （ST-01）, is one of the most active commercially available photocatalysts for environmental cleanup in Japan. The technology of visiblelight responsive treatment for morphology-controlled rutile and brookite TiO2 nanorods by crystal face-selective modification of Fe^3＋ compounds was also discussed in this paper. The Fe^3＋ compound-modified rutile and brookite TiO2 nanorods show much higher activity than conventional visible-light responsive N-doped TiO2, which is commercially available in Japan.
