Two-dimensional （2-D） BiVO4 nanosheets-graphene （GR） composites with different weight addition ratios of GR have been prepared via a facile wet chemistry process. X-ray diffraction （XRD）, Raman spectra, X-ray ph...Two-dimensional （2-D） BiVO4 nanosheets-graphene （GR） composites with different weight addition ratios of GR have been prepared via a facile wet chemistry process. X-ray diffraction （XRD）, Raman spectra, X-ray photoelectron spectra （XPS）, UV-vis diffuse reflectance spectra （DRS）, field-emission scanning electron microscopy （FE-SEM）, transmission electron microscopy （TEM）, nitrogen adsorption-desorption, transient photocurrent response and photoluminescence （PL） spectra were employed to determine the properties of the samples. It is found that BiVO4 nanosheets could pave well on the surface of graphene sheets. BiVO4 nanosheets-GR composites with a proper addition amount of GR exhibited higher photocatalytic activity than bare BiVO4 nanosheets toward liquid-phase degradation of rhodamine B （RhB） and methyl orange （MO） under visible light irradiation. The enhancement of photocatalytic activities of BiVO4 nanosheets-GR composites can be attributed to the effective separation of photoexcited electron-hole pairs. This work not only provides a simple strategy for fabricating specific 2-D semiconductor-2-D GR composites, but also opens a new window of such 2-D semiconductor-2-D GR composites as visible light photocatalysts toward an improved visible light photoactivity in purifying polluted water resources.展开更多
The conversion of biomass into valuable chemicals has promise for application in biorefineries.Light-driven photoredox catalysis,with the typical features of green route and operation under mild conditions,is consider...The conversion of biomass into valuable chemicals has promise for application in biorefineries.Light-driven photoredox catalysis,with the typical features of green route and operation under mild conditions,is considered a promising strategy for renewable biomass or biomass-derived intermediates conversion into high-value-added chemical feedstocks.In this review,we strongly emphasize the recent advances in photocatalytic valorization of lignin model compounds and biomassderived alcohols.We briefl y summarize the advances in photocatalytic cleavage of theβ-O-4 bond or C–C bond into usable chemicals in the lignin model.On the other hand,we clarify not only the hybrid system for cooperative biomass-relevant alcohols oxidation and hydrogen(H2)evolution but also the tunable accessibility to variation of the target products from the same alcohol reactant by catalyst design and optimization of reaction conditions.It is hoped that this review will inspire the rational design of photoredox catalysis-based systems toward efficient biomass-derived platform molecules valorization to obtain target-oriented valuable products.展开更多
The fabrication of efficient catalysts to reduce nitrogen(N_(2))to ammonia(NH3)is a significant challenge for artificial N_(2) fixation under mild conditions.In this work,we demonstrated that the simultaneous introduc...The fabrication of efficient catalysts to reduce nitrogen(N_(2))to ammonia(NH3)is a significant challenge for artificial N_(2) fixation under mild conditions.In this work,we demonstrated that the simultaneous introduction of oxygen vacancies(OVs)and Mo dopants into Bi_(5)O_(7)Br nanosheets can significantly increase the activity for photocatalytic N_(2) fixation.The 1 mol% Mo-doped Bi_(5)O_(7)Br nanosheets exhibited an optimal NH_(3) generation rate of 122.9μmol g^(-1) h^(-1) and durable stability,which is attributed to their optimized conduction band position,suitable absorption edge,large number of light-switchable OVs,and improved charge carrier separation.This work provides a promising approach to design photocatalysts with light-switchable OVs for N_(2) reduction to NH_(3) under mild conditions,highlighting the wide application scope of nanostructured BiOBr-based photocatalysts as effective N_(2) fixation systems.展开更多
CdS nanowires-nitrogen doped graphene （CdS NWs-NGR） nanocomposites have been fabricated by an electrostatic self-assembly strategy followed by a hydrothermal reduction. The CdS NWs-NGR exhibits higher photoactivity ...CdS nanowires-nitrogen doped graphene （CdS NWs-NGR） nanocomposites have been fabricated by an electrostatic self-assembly strategy followed by a hydrothermal reduction. The CdS NWs-NGR exhibits higher photoactivity for selective reduction of aromatic nitro organics in water under visible light irradiation than blank CdS nanowires （CdS NWs） and CdS nanowires-reduced graphene oxide （CdS NWs-RGO） nanocomposites. The enhanced photoactivity of CdS NWs-NGR can be attributed to the improved electronic conductivity due to the introduc- tion of nitrogen atoms, which thus enhances the separation and transfer of charge carriers photogenerated from CdS NWs. Our work could provide a facile method to synthesize NGR based one-dimensional （1D） semiconductor composites for selective organic transformations, and broaden the potential applications for NGR as a cocatalyst.展开更多
The simultaneous utilization of photogenerated electrons and holes in one cooperative photoredox system for the dehydrocoupling of thiols into value-added disulfides and clean hydrogen(H_(2))fuel meets the development...The simultaneous utilization of photogenerated electrons and holes in one cooperative photoredox system for the dehydrocoupling of thiols into value-added disulfides and clean hydrogen(H_(2))fuel meets the development criteria of green chemistry.Herein,we report the synthesis and application of cocatalyst PdS decorated ZnIn_(2)S_(4)(PdS-ZIS)composites for photocatalytic coupling of thiols into disulfides and H2 evolution under visible light irradiation.The superior photocatalytic performance over PdS-ZIS composites compared with blank ZIS is attributed to the function of PdS as oxidation cocatalyst,which dramatically promotes the separation and transfer of photogenerated charge carriers due to its excellent hole trapping ability.In-situ Fourier transform infrared spectra reveal the dynamic variation of reactants on the catalyst surface.Electron paramagnetic resonance technology confirms that sulfur-centered radicals are the key reaction intermediates in this coupling process.Moreover,the application of PdS-ZIS composites to the dehydrocoupling of various thiols with different substituent groups into the corresponding S-S coupling products has been demonstrated to be practicable.This work is expected to offer insights into the rational design of cocatalyst-decorated semiconductor photocatalysts with efficient utilization of photogenerated electrons and holes for the co-production of high-value chemicals and clean H2 energy in a cooperative photoredox catalysis process.展开更多
Ternary composites of reduced graphene oxide(GR)-CdS-Pd have been successfully synthesized via solvothermal and photodeposition methods for photocatalytic selective conversion of benzyl alcohol(BA)coupled with hydroge...Ternary composites of reduced graphene oxide(GR)-CdS-Pd have been successfully synthesized via solvothermal and photodeposition methods for photocatalytic selective conversion of benzyl alcohol(BA)coupled with hydrogen(H_(2))production, which exhibit significantly improved photoactivity and selectivity than bare CdS. Mechanistic studies unveil that the cooperative effect of the close interface contact and matched energy level alignment between electrical conducting GR nanosheets(NSs) and CdS nanoparticles(NPs) in GR-CdS-Pd composite not only benefits the separation and transfer of photogenerated carriers but also improves the photocorrosion resistance of CdS. The photodeposited Pd NPs further promote the photogenerated charge separation and accelerate the formation of intermediate products(α-hydroxybenzyl radicals), thereby contributing to enhanced conversion of BA. This work would facilitate the rational design of GR as cocatalyst to construct an efficient and stable CdS-based composite photocatalyst for cooperative coupling of fine chemical synthesis and H_(2) evolution.展开更多
Semiconductor quantum dots have been emerging as one of the most ideal materials for artificial photosynthesis.Here,we report the assembled ZnS-CdS hybrid heterostructure for efficient coupling cooperative redox catal...Semiconductor quantum dots have been emerging as one of the most ideal materials for artificial photosynthesis.Here,we report the assembled ZnS-CdS hybrid heterostructure for efficient coupling cooperative redox catalysis toward the oxidation of 1-phenylethanol to acetophenone/2,3-diphenyl-2,3-butanediol(pinacol)integrated with the reduction of protons to H2.The strong interaction and typical type-I band-position alignment between CdS quantum dots and ZnS quantum dots result in efficient separation and transfer of electron-hole pairs,thus distinctly enhancing the coupled photocatalyzed-redox activity and stability.The optimal ZnS-CdS hybrid also delivers a superior performance for various aromatic alcohol coupling photoredox reaction,and the ratio of electrons and holes consumed in such redox reaction is close to 1.0,indicating a high atom economy of cooperative coupling catalysis.In addition,by recycling the scattered light in the near field of a SiO_(2)sphere,the SiO_(2)-supported ZnS-CdS(denoted as ZnS-CdS/SiO_(2))catalyst can further achieve a 3.5-fold higher yield than ZnS-CdS hybrid.Mechanistic research clarifies that the oxidation of 1-phenylethanol proceeds through the pivotal radical intermediates of•C(CH_(3))(OH)Ph.This work is expected to promote the rational design of semiconductor quantum dots-based heterostructured catalysts for coupling photoredox catalysis in organic synthesis and clean fuels production.展开更多
Photocatalyzed organic transformations have spurred immense interest in synthetic chemistry for the efficient conversion of solar energy into chemical energy.However,the crucial roles of support,which fixes catalytic ...Photocatalyzed organic transformations have spurred immense interest in synthetic chemistry for the efficient conversion of solar energy into chemical energy.However,the crucial roles of support,which fixes catalytic sites and improves the light-harvesting ability,are often ignored in photoredox transformations.Herein,we report the utilization of spherical SiO2 support to engineer AuPd alloy particles(denoted as AuPd/SiO2),conceptually different from traditional methods for tuning optical absorption of plasmonic Au or AuPd particles,to manipulate light-harvesting ability of AuPd particles for highly selective and efficient photocatalytic Suzuki cross-coupling reactions.In this deliberately designed system,typically without the size and shape alternation of AuPd particles,the supported AuPd particles recycle the scattering light from spherical SiO2 support and achieve the significant broad light-harvesting ability instead of the surface plasmon resonance peak.The engineered AuPd/SiO2 composites by the use of near-field scattering-promoted optical absorption showcase the remarkably enhanced activity for visible-light-induced photocatalytic Suzuki cross-coupling reactions in comparison with that using commercial SiO2 support,highlighting the spherical-support-effect induced efficient utilization of scattered light.This work highlights the feasibility of manipulating the light-harvesting capability of bimetallic particles by the near-field scattering-promoted optical absorption model toward efficient photo-driven Suzuki cross-coupling reaction and other C-C coupling organic synthesis to produce high value-added chemicals.展开更多
Photocatalytic hydrogen(H_(2))production coupled with selective oxidation of organic compounds into high-value-added organic intermediates has expansive prospects in the utilization and transformation of solar energy,...Photocatalytic hydrogen(H_(2))production coupled with selective oxidation of organic compounds into high-value-added organic intermediates has expansive prospects in the utilization and transformation of solar energy,which meets the development requirements of green chemistry.In this work,high-efficiency hole cocatalyst PdS-decorated In_(2)S_(3) flower-like microspheres are fabricated for the effective visible-lightdriven C-N coupling of amines to imines coupled with H_(2) evolution.Owing to the establishment of the internal electric field,which further boosts the transfer of photoexcited holes to PdS,PdS-In_(2)S_(3) exhibits distinctly enhanced photocatalytic redox performance,which is 39.8 times higher for H_(2) and 14.3 times higher for N-benzylidenebenzylamine than that of the blank In_(2)S_(3),along with high selectivity and stability.Furthermore,the practicability of dehydrogenation coupling of various aromatic amines to the corresponding C-N coupling products on PdS-In_(2)S_(3) has been demonstrated and a plausible reaction mechanism has been proposed.This work is anticipated to stimulate further interest in establishing an innovative photoredox platform for selective organic synthesis coupled with H2 evolution in a green and sustainable way.展开更多
基金supported by the National Natural Science Foundation of China(NSFC)(20903022,20903023,21173045)the Award Program for Minjiang Scholar Professorship+1 种基金the Science and Technology Development of Foundation of Fuzhou University(2009-XQ-10)the Open Fund of Photocatalysis of Fuzhou University(0380038004)
文摘Two-dimensional （2-D） BiVO4 nanosheets-graphene （GR） composites with different weight addition ratios of GR have been prepared via a facile wet chemistry process. X-ray diffraction （XRD）, Raman spectra, X-ray photoelectron spectra （XPS）, UV-vis diffuse reflectance spectra （DRS）, field-emission scanning electron microscopy （FE-SEM）, transmission electron microscopy （TEM）, nitrogen adsorption-desorption, transient photocurrent response and photoluminescence （PL） spectra were employed to determine the properties of the samples. It is found that BiVO4 nanosheets could pave well on the surface of graphene sheets. BiVO4 nanosheets-GR composites with a proper addition amount of GR exhibited higher photocatalytic activity than bare BiVO4 nanosheets toward liquid-phase degradation of rhodamine B （RhB） and methyl orange （MO） under visible light irradiation. The enhancement of photocatalytic activities of BiVO4 nanosheets-GR composites can be attributed to the effective separation of photoexcited electron-hole pairs. This work not only provides a simple strategy for fabricating specific 2-D semiconductor-2-D GR composites, but also opens a new window of such 2-D semiconductor-2-D GR composites as visible light photocatalysts toward an improved visible light photoactivity in purifying polluted water resources.
基金This work was supported by the National Natural Science Foundation of China(Nos.21872029,20903023,U1463204 and 21173045)the Program for Leading Talents of Fujian Universities,the Natural Science Foundation of Fujian Province for the Distinguished Young Investigator Rolling Grant(No.2017J07002)+1 种基金the 1st Program of Fujian Province for Top Creative Young Talents,the Natural Science Foundation of Fujian Province(No.2019J0106)the Award Program for Minjiang Scholar Professorship is gratefully acknowledged.
文摘The conversion of biomass into valuable chemicals has promise for application in biorefineries.Light-driven photoredox catalysis,with the typical features of green route and operation under mild conditions,is considered a promising strategy for renewable biomass or biomass-derived intermediates conversion into high-value-added chemical feedstocks.In this review,we strongly emphasize the recent advances in photocatalytic valorization of lignin model compounds and biomassderived alcohols.We briefl y summarize the advances in photocatalytic cleavage of theβ-O-4 bond or C–C bond into usable chemicals in the lignin model.On the other hand,we clarify not only the hybrid system for cooperative biomass-relevant alcohols oxidation and hydrogen(H2)evolution but also the tunable accessibility to variation of the target products from the same alcohol reactant by catalyst design and optimization of reaction conditions.It is hoped that this review will inspire the rational design of photoredox catalysis-based systems toward efficient biomass-derived platform molecules valorization to obtain target-oriented valuable products.
文摘The fabrication of efficient catalysts to reduce nitrogen(N_(2))to ammonia(NH3)is a significant challenge for artificial N_(2) fixation under mild conditions.In this work,we demonstrated that the simultaneous introduction of oxygen vacancies(OVs)and Mo dopants into Bi_(5)O_(7)Br nanosheets can significantly increase the activity for photocatalytic N_(2) fixation.The 1 mol% Mo-doped Bi_(5)O_(7)Br nanosheets exhibited an optimal NH_(3) generation rate of 122.9μmol g^(-1) h^(-1) and durable stability,which is attributed to their optimized conduction band position,suitable absorption edge,large number of light-switchable OVs,and improved charge carrier separation.This work provides a promising approach to design photocatalysts with light-switchable OVs for N_(2) reduction to NH_(3) under mild conditions,highlighting the wide application scope of nanostructured BiOBr-based photocatalysts as effective N_(2) fixation systems.
基金supported by the National Natural Science Foundation of China(NSFC)(20903022,20903023,21173045)the Award Program for Minjiang Scholar Professorship+2 种基金the Science and Technology Development of Foundation of Fuzhou University(2009-XQ-10)the Open Fund of Photocatalysis of Fuzhou University(0380038004)the Program for Returned High-Level Overseas Chinese Scholars of Fujian Province
文摘CdS nanowires-nitrogen doped graphene （CdS NWs-NGR） nanocomposites have been fabricated by an electrostatic self-assembly strategy followed by a hydrothermal reduction. The CdS NWs-NGR exhibits higher photoactivity for selective reduction of aromatic nitro organics in water under visible light irradiation than blank CdS nanowires （CdS NWs） and CdS nanowires-reduced graphene oxide （CdS NWs-RGO） nanocomposites. The enhanced photoactivity of CdS NWs-NGR can be attributed to the improved electronic conductivity due to the introduc- tion of nitrogen atoms, which thus enhances the separation and transfer of charge carriers photogenerated from CdS NWs. Our work could provide a facile method to synthesize NGR based one-dimensional （1D） semiconductor composites for selective organic transformations, and broaden the potential applications for NGR as a cocatalyst.
文摘The simultaneous utilization of photogenerated electrons and holes in one cooperative photoredox system for the dehydrocoupling of thiols into value-added disulfides and clean hydrogen(H_(2))fuel meets the development criteria of green chemistry.Herein,we report the synthesis and application of cocatalyst PdS decorated ZnIn_(2)S_(4)(PdS-ZIS)composites for photocatalytic coupling of thiols into disulfides and H2 evolution under visible light irradiation.The superior photocatalytic performance over PdS-ZIS composites compared with blank ZIS is attributed to the function of PdS as oxidation cocatalyst,which dramatically promotes the separation and transfer of photogenerated charge carriers due to its excellent hole trapping ability.In-situ Fourier transform infrared spectra reveal the dynamic variation of reactants on the catalyst surface.Electron paramagnetic resonance technology confirms that sulfur-centered radicals are the key reaction intermediates in this coupling process.Moreover,the application of PdS-ZIS composites to the dehydrocoupling of various thiols with different substituent groups into the corresponding S-S coupling products has been demonstrated to be practicable.This work is expected to offer insights into the rational design of cocatalyst-decorated semiconductor photocatalysts with efficient utilization of photogenerated electrons and holes for the co-production of high-value chemicals and clean H2 energy in a cooperative photoredox catalysis process.
基金supported by the Natural Science Foundation of China (Nos. 22172030, 22072023, 21872029, U1463204 and 21173045)the Program for National Science and Technology Innovation Leading Talents (No. 00387072)+2 种基金the Program for Leading Talents of Fujian Universitiesthe 1st Program of Fujian Province for Top Creative Young Talentsthe Natural Science Foundation of Fujian Province (Nos. 2017J07002 and 2019J01631)。
文摘Ternary composites of reduced graphene oxide(GR)-CdS-Pd have been successfully synthesized via solvothermal and photodeposition methods for photocatalytic selective conversion of benzyl alcohol(BA)coupled with hydrogen(H_(2))production, which exhibit significantly improved photoactivity and selectivity than bare CdS. Mechanistic studies unveil that the cooperative effect of the close interface contact and matched energy level alignment between electrical conducting GR nanosheets(NSs) and CdS nanoparticles(NPs) in GR-CdS-Pd composite not only benefits the separation and transfer of photogenerated carriers but also improves the photocorrosion resistance of CdS. The photodeposited Pd NPs further promote the photogenerated charge separation and accelerate the formation of intermediate products(α-hydroxybenzyl radicals), thereby contributing to enhanced conversion of BA. This work would facilitate the rational design of GR as cocatalyst to construct an efficient and stable CdS-based composite photocatalyst for cooperative coupling of fine chemical synthesis and H_(2) evolution.
基金The support from the NSFC(22072023,22172030,21872029,U1463204,and 21173045)the Program for National Science and Technology Innovation Leading Talents(00387072)the Award Program for Minjiang Scholar Professorship,the Program for Leading Talents of Fujian Universities,the First Program of Fujian Province for Top Creative Young Talents,and the NSF of Fujian Province(2019J01631 and 2017J07002)is gratefully acknowledged.
文摘Semiconductor quantum dots have been emerging as one of the most ideal materials for artificial photosynthesis.Here,we report the assembled ZnS-CdS hybrid heterostructure for efficient coupling cooperative redox catalysis toward the oxidation of 1-phenylethanol to acetophenone/2,3-diphenyl-2,3-butanediol(pinacol)integrated with the reduction of protons to H2.The strong interaction and typical type-I band-position alignment between CdS quantum dots and ZnS quantum dots result in efficient separation and transfer of electron-hole pairs,thus distinctly enhancing the coupled photocatalyzed-redox activity and stability.The optimal ZnS-CdS hybrid also delivers a superior performance for various aromatic alcohol coupling photoredox reaction,and the ratio of electrons and holes consumed in such redox reaction is close to 1.0,indicating a high atom economy of cooperative coupling catalysis.In addition,by recycling the scattered light in the near field of a SiO_(2)sphere,the SiO_(2)-supported ZnS-CdS(denoted as ZnS-CdS/SiO_(2))catalyst can further achieve a 3.5-fold higher yield than ZnS-CdS hybrid.Mechanistic research clarifies that the oxidation of 1-phenylethanol proceeds through the pivotal radical intermediates of•C(CH_(3))(OH)Ph.This work is expected to promote the rational design of semiconductor quantum dots-based heterostructured catalysts for coupling photoredox catalysis in organic synthesis and clean fuels production.
基金the National Natural Science Foundation of China(Nos.22172030,22072023,21872029,and U1463204)the Program for National Science and Technology Innovation Leading Talents(No.00387072)+1 种基金the 1st Program of Fujian Province for Top Creative Young Talents,the Award Program for Minjiang Scholar Professorship,the Natural Science Foundation(No.2019J0106)of Fujian Provincethe Natural Science Foundation of Fujian Province for Distinguished Young Investigator Rolling Grant(No.2017J07002)is gratefully acknowledged.
文摘Photocatalyzed organic transformations have spurred immense interest in synthetic chemistry for the efficient conversion of solar energy into chemical energy.However,the crucial roles of support,which fixes catalytic sites and improves the light-harvesting ability,are often ignored in photoredox transformations.Herein,we report the utilization of spherical SiO2 support to engineer AuPd alloy particles(denoted as AuPd/SiO2),conceptually different from traditional methods for tuning optical absorption of plasmonic Au or AuPd particles,to manipulate light-harvesting ability of AuPd particles for highly selective and efficient photocatalytic Suzuki cross-coupling reactions.In this deliberately designed system,typically without the size and shape alternation of AuPd particles,the supported AuPd particles recycle the scattering light from spherical SiO2 support and achieve the significant broad light-harvesting ability instead of the surface plasmon resonance peak.The engineered AuPd/SiO2 composites by the use of near-field scattering-promoted optical absorption showcase the remarkably enhanced activity for visible-light-induced photocatalytic Suzuki cross-coupling reactions in comparison with that using commercial SiO2 support,highlighting the spherical-support-effect induced efficient utilization of scattered light.This work highlights the feasibility of manipulating the light-harvesting capability of bimetallic particles by the near-field scattering-promoted optical absorption model toward efficient photo-driven Suzuki cross-coupling reaction and other C-C coupling organic synthesis to produce high value-added chemicals.
基金the National Natural Science Foundation of China(21872029,22172030,22072023,U1463204,and 21173045)the Program for National Science and Technology Innovation Leading Talents(00387072)+2 种基金the Program for Leading Talents of Fujian Universitiesthe First Program of Fujian Province for Top Creative Young Talentsthe Natural Science Foundation of Fujian Province(2017J07002 and 2019J01631).
文摘Photocatalytic hydrogen(H_(2))production coupled with selective oxidation of organic compounds into high-value-added organic intermediates has expansive prospects in the utilization and transformation of solar energy,which meets the development requirements of green chemistry.In this work,high-efficiency hole cocatalyst PdS-decorated In_(2)S_(3) flower-like microspheres are fabricated for the effective visible-lightdriven C-N coupling of amines to imines coupled with H_(2) evolution.Owing to the establishment of the internal electric field,which further boosts the transfer of photoexcited holes to PdS,PdS-In_(2)S_(3) exhibits distinctly enhanced photocatalytic redox performance,which is 39.8 times higher for H_(2) and 14.3 times higher for N-benzylidenebenzylamine than that of the blank In_(2)S_(3),along with high selectivity and stability.Furthermore,the practicability of dehydrogenation coupling of various aromatic amines to the corresponding C-N coupling products on PdS-In_(2)S_(3) has been demonstrated and a plausible reaction mechanism has been proposed.This work is anticipated to stimulate further interest in establishing an innovative photoredox platform for selective organic synthesis coupled with H2 evolution in a green and sustainable way.
