Ag3PO4has good potential for use in photocatalytic degradation of organic contaminants.However,the activity and stability of Ag3PO4is hard to sustain because of photocorrosion and the positive potential of the conduct...Ag3PO4has good potential for use in photocatalytic degradation of organic contaminants.However,the activity and stability of Ag3PO4is hard to sustain because of photocorrosion and the positive potential of the conduction band of Ag3PO4.In this study,A composite consisting of Bi2WO6nanosheets and Ag3PO4was developed to curb recombination of charge carriers and enhance the activity and stability of the catalyst.Formation of a Ag3PO4/Bi2WO6composite was confirmed using X‐ray diffraction,energy‐dispersive X‐ray spectroscopy,and X‐ray photoelectron spectroscopy.Photoluminescence spectroscopy provided convincing evidence that compositing Bi2WO6with Ag3PO4effectively reduced photocorrosion of Ag3PO4.The Ag3PO4/Bi2WO6composite gave a high photocatalytic performance in photodegradation of methylene blue.A degradation rate of0.61min?1was achieved;this is1.3and6.0times higher than those achieved using Ag3PO4(0.47min?1)and Bi2WO6(0.10min?1),respectively.Reactive species trapping experiments using the Ag3PO4/Bi2WO6composite showed that holes,?OH,and?O2?all played specific roles in the photodegradation process.The photocatalytic mechanism was investigated and a Z‐scheme was proposed as a plausible mechanism.展开更多
Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high...Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high energy barrier for CO_(2) photoreduction on the surface of photocatalysts com‐promise the catalytic performance.Herein,a 2D/2D Bi_(2)MoO_(6)/BiOI composite was fabricated to achieve improved CO_(2) photoreduction efficiency.Charge transfer in the composite was facilitated by the van der Waals heterojunction with a large‐area interface.Work function calculation demon‐strated that S‐scheme charge transfer is operative in the composite,and effective charge separation and strong redox capability were revealed by time‐resolved photoluminescence and electron para‐magnetic resonance spectroscopy.Moreover,the intermediates of CO_(2) photoreduction were identi‐fied based on the in situ diffuse reflectance infrared Fourier‐transform spectra.Density functional theory calculations showed that CO_(2) hydrogenation is the rate‐determining step for yielding CH_(4) and CO.Introducing Bi_(2)MoO_(6) into the composite further decreased the energy barrier for CO_(2) photoreduction on BiOI by 0.35 eV.This study verifies the synergistic effect of the S‐scheme heterojunction and van der Waals heterojunction in the 2D/2D composite.展开更多
The inorganic-organic S-scheme heterojunction photocatalyst demonstrates exceptional light absorption capacity,high photogenerated charge separation efficiency,and remarkable redox ability,while also inheriting divers...The inorganic-organic S-scheme heterojunction photocatalyst demonstrates exceptional light absorption capacity,high photogenerated charge separation efficiency,and remarkable redox ability,while also inheriting diverse advantages of both inorganic and organic semiconductors.This paper provides a comprehensive review of recent advances in photocatalysis in relation to the inorganic-organic S-scheme heterojunction photocatalyst.Firstly,the fundamental aspects and benefits of the S-scheme heterojunction photocatalyst are outlined,followed by a discussion of several synthetic techniques for producing the inorganic-organic S-scheme heterojunction photocatalyst,as well as various advanced characterization methods that can verify the S-scheme heterojunction photocatalyst in both steady-state and transient processes.The impact of the inorganic-organic S-scheme heterojunction photocatalyst is illustrated with examples in fields such as carbon dioxide reduction,water splitting for hydrogen production,hydrogen peroxide synthesis,nitrogen fixation,organic pollutant degradation,organic transformation,and sterilization.Finally,suggestions are presented for designing the inorganic-organic S-scheme heterojunction photocatalyst and enhancing its photocatalytic performance.Undoubtedly,the inorganic-organic Sscheme heterojunction photocatalyst has emerged as a prominent and promising technology in the field of photocatalysis.展开更多
S-scheme heterojunctions have promising applications in photocatalytic CO_(2) reduction due to their unique structure and interfacial interactions,but improving their carrier separation efficiency and CO_(2) adsorptio...S-scheme heterojunctions have promising applications in photocatalytic CO_(2) reduction due to their unique structure and interfacial interactions,but improving their carrier separation efficiency and CO_(2) adsorption capacity remains a challenge.In this work,highly dispersed MOF-BiOBr/Mn_(0.2) Cd_(0.8) S(MOF-BiOBr/MCS)S-scheme heterojunctions with high photocatalytic CO_(2) reduction performance were constructed.The intimate contact between the MCS nano-spheres and the nanosheet-assembled MOF-BiOBr rods,driven by the internal electric field,accelerates the charge transfer along the S-scheme pathway.Moreover,the high specific surface area of MOFs is preserved to provide abundant active sites for reaction/adsorption.The formation of MOF-BiOBr/MCS S-scheme heterojunction is confirmed by theoretical calculations.The optimum MOF-BiOBr/MCS shows excellent activity in CO_(2) reduction,affording a high CO evolution rate of 60.59µmol h^(−1) g^(−1).The present work can inspire the exploration for the construction of effective heterostructure photocatalysts for photoreduction CO_(2).展开更多
Harnessing solar energy for photocatalytic hydrogen peroxide(H_(2)O_(2))synthesis represents a pinnacle of environmentally-sensitive and sustainable methodologies.While single-layer crystalline triazine-based organic ...Harnessing solar energy for photocatalytic hydrogen peroxide(H_(2)O_(2))synthesis represents a pinnacle of environmentally-sensitive and sustainable methodologies.While single-layer crystalline triazine-based organic frameworks(CTFs)are known for their prodigious photocatalytic potential in H_(2)O_(2)generation,ramifications of the connecting group within the triazine ring(TR)on underlying photocatalytic mechanism warrant deeper exploration.In this study,we simulate three distinct CTFs characterized by different TR linkers:CTF-1(benzene group(BG)),CTF-2(horizontally-oriented naphthyl group(NGH)),and CTF-DCN(vertically-oriented naphthyl group(NGV)).These diverse TR linkers profoundly modulate the absorption band edge of CTFs,subsequently dictating the orientation and constitution of the frontier orbitals.Such modulation plays a decisive role in determining the requisite energy for photoexcitation in CTFs,orchestrating the generation and distribution of photo-induced electrons and holes.Remarkably,the NGV linkage imparts CTF-DCN with unparalleled light ab-sorption,superior charge separation efficiency,and the lowest energy barrier for associated reactions.Through this investigation,we illuminate the pivotal influence of TR linkers in sculpting the photocatalytic dynamics of CTFs,providing fresh perspectives for architecting CTFs with amplified photocatalytic prowess in H_(2)O_(2)synthesis.展开更多
Converting solar energy into chemical energy by artificial photosynthesis is promising in addressing the issues of the greenhouse effect and fossil fuel crisis.Herein,a novel photocatalyst,i.e.CdS/TiO_(2) hollow micro...Converting solar energy into chemical energy by artificial photosynthesis is promising in addressing the issues of the greenhouse effect and fossil fuel crisis.Herein,a novel photocatalyst,i.e.CdS/TiO_(2) hollow microspheres(HS),were dedicatedly designed to boost overall photocatalytic efficiency.TiO_(2) nanoparticles were in-situ decorated on the inside and outside the shell of Cd S HS,ensuring close contact between TiO_(2) and CdS.The CdS/TiO2 HS with abundant mesopores inside of the shell boost the light absorption via multiscattering effect as well as accessible to reactions in all directions.The heterojunction was scrutinized and the charge transfer across it was revealed by in-situ irradiated X-ray photoelectron spectroscopy(ISI-XPS).Ultimately,the charge transfer in this composite was determined to follow stepscheme mechanism,which not only facilitates the separation of charge carriers but also preserves strong redox ability.Benefited from the intimate linkage between Cd S and TiO_(2) and the favorable step-scheme heterojunction,enhanced photocatalytic CO_(2) reduction activity was accomplished.The CH4 yield rate of CdS/TiO_(2) reaches 27.85μmol g^(–1) h^(–1),which is 145.6 and 3.8 times higher than those of pristine CdS and TiO_(2),respectively.This work presents a novel insight into constructing step-scheme photocatalytic system with desirable performance.展开更多
Utilizing solar energy to achieve artificial photosynthesis of chemical fuel is prevalent in tackling excessive CO_(2)emission and fossil fuel depletion.Grievous charge recombination and weak redox capability aggravat...Utilizing solar energy to achieve artificial photosynthesis of chemical fuel is prevalent in tackling excessive CO_(2)emission and fossil fuel depletion.Grievous charge recombination and weak redox capability aggravate the CO_(2)photoreduction performance.Engineering tailored morphology and constructing matched heterostructure are two significant schemes to ameliorate the CO_(2)photoconversion efficiency of g-C_(3)N_(4)-based composite.Herein,a novel S-scheme ultrathin porous g-C_(3)N_(4)(UPCN)/Ag_(2)MoO_(4)(AMO)composite was designed by in-situ growing tetragonalα-AMO nanoparticles(NPs)(5-30 nm)on UPCN nanosheets(NSs).The S-scheme charge transfer route endows UPCN/AMO with fast charge separation and strong redox capability,demonstrated by X-ray photoelectron spectroscopy(XPS),photoelectrochemical tests,steady-state and time-resolved photoluminescence(PL)spectra,and DFT calculations.The UPCN/AMO composite exhibits elevated CO_(2)photoreduction performance with CO and CH_(4)yield rates of 6.98 and 0.38μmol g^(-1)h^(-1),which are 3.5 and 2.9 folds higher than that of pristine UPCN,respectively.Finally,the CO_(2)photoreduction intermediates are analyzed,and the CO_(2)photoreduction mechanism is discussed.This work provides a reference for various g-C_(3)N_(4)-based composites applied in artificial photosynthesis.展开更多
基金supported by the National Natural Science Foundation of China(51572103,51502106)the Foundation for Young Talents in College of Anhui Province(gxyqZD201751)~~
文摘Ag3PO4has good potential for use in photocatalytic degradation of organic contaminants.However,the activity and stability of Ag3PO4is hard to sustain because of photocorrosion and the positive potential of the conduction band of Ag3PO4.In this study,A composite consisting of Bi2WO6nanosheets and Ag3PO4was developed to curb recombination of charge carriers and enhance the activity and stability of the catalyst.Formation of a Ag3PO4/Bi2WO6composite was confirmed using X‐ray diffraction,energy‐dispersive X‐ray spectroscopy,and X‐ray photoelectron spectroscopy.Photoluminescence spectroscopy provided convincing evidence that compositing Bi2WO6with Ag3PO4effectively reduced photocorrosion of Ag3PO4.The Ag3PO4/Bi2WO6composite gave a high photocatalytic performance in photodegradation of methylene blue.A degradation rate of0.61min?1was achieved;this is1.3and6.0times higher than those achieved using Ag3PO4(0.47min?1)and Bi2WO6(0.10min?1),respectively.Reactive species trapping experiments using the Ag3PO4/Bi2WO6composite showed that holes,?OH,and?O2?all played specific roles in the photodegradation process.The photocatalytic mechanism was investigated and a Z‐scheme was proposed as a plausible mechanism.
文摘Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high energy barrier for CO_(2) photoreduction on the surface of photocatalysts com‐promise the catalytic performance.Herein,a 2D/2D Bi_(2)MoO_(6)/BiOI composite was fabricated to achieve improved CO_(2) photoreduction efficiency.Charge transfer in the composite was facilitated by the van der Waals heterojunction with a large‐area interface.Work function calculation demon‐strated that S‐scheme charge transfer is operative in the composite,and effective charge separation and strong redox capability were revealed by time‐resolved photoluminescence and electron para‐magnetic resonance spectroscopy.Moreover,the intermediates of CO_(2) photoreduction were identi‐fied based on the in situ diffuse reflectance infrared Fourier‐transform spectra.Density functional theory calculations showed that CO_(2) hydrogenation is the rate‐determining step for yielding CH_(4) and CO.Introducing Bi_(2)MoO_(6) into the composite further decreased the energy barrier for CO_(2) photoreduction on BiOI by 0.35 eV.This study verifies the synergistic effect of the S‐scheme heterojunction and van der Waals heterojunction in the 2D/2D composite.
基金supported by the National Key R&D Program of China(2022YFE0126500)the National Natural Science Foundation of China(22278169,22150610467,52372253,51973078)+6 种基金the Excellent Scientific Research and Innovation Team of the Education Department of Anhui Province(2022AH010028)the Major projects of Education Department of Anhui Province(2022AH040068)the Key Foundation of Educational Commission of Anhui Province(2022AH050396,2022AH050376)Anhui Provincial Quality Engineering Project(2022sx13)the Innovation Fund for Postgraduates of Huaibei Normal University(CX2023038)Surplus Funds to Expand Research Projects of Huaibei Normal University(2023ZK045)the Open Project from the Key Laboratory of Green and Precise Synthetic Chemistry and Applications(2020KF07)。
基金the National Natural Science Foundation of China(Nos.22278169 and 51973078)the Excellent scientific research and innovation team of the Education Department of Anhui Province(No.2022AH010028)the Major projects of the Education Department of Anhui Province(No.2022AH040068).
文摘The inorganic-organic S-scheme heterojunction photocatalyst demonstrates exceptional light absorption capacity,high photogenerated charge separation efficiency,and remarkable redox ability,while also inheriting diverse advantages of both inorganic and organic semiconductors.This paper provides a comprehensive review of recent advances in photocatalysis in relation to the inorganic-organic S-scheme heterojunction photocatalyst.Firstly,the fundamental aspects and benefits of the S-scheme heterojunction photocatalyst are outlined,followed by a discussion of several synthetic techniques for producing the inorganic-organic S-scheme heterojunction photocatalyst,as well as various advanced characterization methods that can verify the S-scheme heterojunction photocatalyst in both steady-state and transient processes.The impact of the inorganic-organic S-scheme heterojunction photocatalyst is illustrated with examples in fields such as carbon dioxide reduction,water splitting for hydrogen production,hydrogen peroxide synthesis,nitrogen fixation,organic pollutant degradation,organic transformation,and sterilization.Finally,suggestions are presented for designing the inorganic-organic S-scheme heterojunction photocatalyst and enhancing its photocatalytic performance.Undoubtedly,the inorganic-organic Sscheme heterojunction photocatalyst has emerged as a prominent and promising technology in the field of photocatalysis.
基金supported by the National Natural Science Foundation of China(Nos.22278169 and 51973078)the Excellent scientific research and innovation team of Education Department of Anhui Province(No.2022AH010028)+1 种基金the Major projects of Education Department of Anhui Province(No.2022AH040068)the Key Foundation of Educational Commission of Anhui Province(No.2022AH050396).
文摘S-scheme heterojunctions have promising applications in photocatalytic CO_(2) reduction due to their unique structure and interfacial interactions,but improving their carrier separation efficiency and CO_(2) adsorption capacity remains a challenge.In this work,highly dispersed MOF-BiOBr/Mn_(0.2) Cd_(0.8) S(MOF-BiOBr/MCS)S-scheme heterojunctions with high photocatalytic CO_(2) reduction performance were constructed.The intimate contact between the MCS nano-spheres and the nanosheet-assembled MOF-BiOBr rods,driven by the internal electric field,accelerates the charge transfer along the S-scheme pathway.Moreover,the high specific surface area of MOFs is preserved to provide abundant active sites for reaction/adsorption.The formation of MOF-BiOBr/MCS S-scheme heterojunction is confirmed by theoretical calculations.The optimum MOF-BiOBr/MCS shows excellent activity in CO_(2) reduction,affording a high CO evolution rate of 60.59µmol h^(−1) g^(−1).The present work can inspire the exploration for the construction of effective heterostructure photocatalysts for photoreduction CO_(2).
基金supported by the National Natural Science Foundation of China(22278169 and 51973078)the Excellent Scientific Research and Innovation Team of Education Department of Anhui Province(2022AH010028)+2 种基金the Major Projects of Education Department of Anhui Province(2022AH040068)the Key Foundation of Educational Commission of Anhui Province(2022AH050396 and 2022AH050376)Anhui Provincial Quality Engineering Project(2022sx134).
文摘Harnessing solar energy for photocatalytic hydrogen peroxide(H_(2)O_(2))synthesis represents a pinnacle of environmentally-sensitive and sustainable methodologies.While single-layer crystalline triazine-based organic frameworks(CTFs)are known for their prodigious photocatalytic potential in H_(2)O_(2)generation,ramifications of the connecting group within the triazine ring(TR)on underlying photocatalytic mechanism warrant deeper exploration.In this study,we simulate three distinct CTFs characterized by different TR linkers:CTF-1(benzene group(BG)),CTF-2(horizontally-oriented naphthyl group(NGH)),and CTF-DCN(vertically-oriented naphthyl group(NGV)).These diverse TR linkers profoundly modulate the absorption band edge of CTFs,subsequently dictating the orientation and constitution of the frontier orbitals.Such modulation plays a decisive role in determining the requisite energy for photoexcitation in CTFs,orchestrating the generation and distribution of photo-induced electrons and holes.Remarkably,the NGV linkage imparts CTF-DCN with unparalleled light ab-sorption,superior charge separation efficiency,and the lowest energy barrier for associated reactions.Through this investigation,we illuminate the pivotal influence of TR linkers in sculpting the photocatalytic dynamics of CTFs,providing fresh perspectives for architecting CTFs with amplified photocatalytic prowess in H_(2)O_(2)synthesis.
基金financially supported by the National Natural Science Foundation of China(NSFC)(Nos.51872220,51932007,51961135303,21871217,U1905215 and U1705251)the National Key Research and Development Program of China(No.2018YFB1502001)the Fundamental Research Funds for the Central Universities(No.WUT:2019IVB050)。
文摘Converting solar energy into chemical energy by artificial photosynthesis is promising in addressing the issues of the greenhouse effect and fossil fuel crisis.Herein,a novel photocatalyst,i.e.CdS/TiO_(2) hollow microspheres(HS),were dedicatedly designed to boost overall photocatalytic efficiency.TiO_(2) nanoparticles were in-situ decorated on the inside and outside the shell of Cd S HS,ensuring close contact between TiO_(2) and CdS.The CdS/TiO2 HS with abundant mesopores inside of the shell boost the light absorption via multiscattering effect as well as accessible to reactions in all directions.The heterojunction was scrutinized and the charge transfer across it was revealed by in-situ irradiated X-ray photoelectron spectroscopy(ISI-XPS).Ultimately,the charge transfer in this composite was determined to follow stepscheme mechanism,which not only facilitates the separation of charge carriers but also preserves strong redox ability.Benefited from the intimate linkage between Cd S and TiO_(2) and the favorable step-scheme heterojunction,enhanced photocatalytic CO_(2) reduction activity was accomplished.The CH4 yield rate of CdS/TiO_(2) reaches 27.85μmol g^(–1) h^(–1),which is 145.6 and 3.8 times higher than those of pristine CdS and TiO_(2),respectively.This work presents a novel insight into constructing step-scheme photocatalytic system with desirable performance.
基金supported by the National Natural Science Foundation of China(51572103 and 51973078)the Distinguished Young Scholar of Anhui Province(1808085J14)+1 种基金the Major Projects of Education Department of Anhui Province(KJ2020ZD005)the Key Foundation of Educational Commission of Anhui Province(KJ2019A0595)。
文摘Utilizing solar energy to achieve artificial photosynthesis of chemical fuel is prevalent in tackling excessive CO_(2)emission and fossil fuel depletion.Grievous charge recombination and weak redox capability aggravate the CO_(2)photoreduction performance.Engineering tailored morphology and constructing matched heterostructure are two significant schemes to ameliorate the CO_(2)photoconversion efficiency of g-C_(3)N_(4)-based composite.Herein,a novel S-scheme ultrathin porous g-C_(3)N_(4)(UPCN)/Ag_(2)MoO_(4)(AMO)composite was designed by in-situ growing tetragonalα-AMO nanoparticles(NPs)(5-30 nm)on UPCN nanosheets(NSs).The S-scheme charge transfer route endows UPCN/AMO with fast charge separation and strong redox capability,demonstrated by X-ray photoelectron spectroscopy(XPS),photoelectrochemical tests,steady-state and time-resolved photoluminescence(PL)spectra,and DFT calculations.The UPCN/AMO composite exhibits elevated CO_(2)photoreduction performance with CO and CH_(4)yield rates of 6.98 and 0.38μmol g^(-1)h^(-1),which are 3.5 and 2.9 folds higher than that of pristine UPCN,respectively.Finally,the CO_(2)photoreduction intermediates are analyzed,and the CO_(2)photoreduction mechanism is discussed.This work provides a reference for various g-C_(3)N_(4)-based composites applied in artificial photosynthesis.
