The rapid recombination of photo-generated electron-hole pairs,insufficient active sites,and strong photocorrosion have considerably restricted the practical application of Cd S in photocatalytic fields.Herein,we desi...The rapid recombination of photo-generated electron-hole pairs,insufficient active sites,and strong photocorrosion have considerably restricted the practical application of Cd S in photocatalytic fields.Herein,we designed and constructed a 2D/2D/2D layered heterojunction photocatalyst with cascaded 2D coupling interfaces.Experiments using electron spin resonance spectroscopy,ultraviolet photoelectron spectroscopy,and in-situ irradiation X-ray photoelectron spectroscopy were conducted to confirm the 2D layered CdS/WO_(3) step-scheme(S-scheme)heterojunctions and CdS/MX ohmic junctions.Impressively,it was found that the strong interfacial electric fields in the S-scheme heterojunction photocatalysts could effectively promote spatially directional charge separation and transport between CdS and WO_(3) nanosheets.In addition,2D Ti_(3)C_(2) MXene nanosheets with a smaller work function and excellent metal conductivity when used as a co-catalyst could build ohmic junctions with Cd S nanosheets,thus providing a greater number of electron transfer pathways and hydrogen evolution sites.Results showed that the highest visible-light hydrogen evolution rate of the optimized MX-Cd S/WO_(3) layered multi-heterostructures could reach as high as 27.5 mmol/g/h,which was 11.0 times higher than that of pure CdS nanosheets.Notably,the apparent quantum efficiency reached 12.0% at 450 nm.It is hoped that this study offers a reliable approach for developing multifunctional photocatalysts by integrating S-scheme and ohmic-junction built-in electric fields and rationally designing a 2D/2D interface for efficient light-to-hydrogen fuel production.展开更多
Converting solar energy into clean and sustainable chemical fuels is a promising strategy for exploiting renewable energy.The application of photocatalytic water splitting technology in hydrogen production is importan...Converting solar energy into clean and sustainable chemical fuels is a promising strategy for exploiting renewable energy.The application of photocatalytic water splitting technology in hydrogen production is important for sustainable energy development and environmental protection.In this study,for the first time,2D Cu7S4 co-catalysts were coupled on the surface of a CdS nanosheet photocatalyst by a one-step ultrasonic-assisted electrostatic self-assembly method at room temperature.The as-fabricated 2D^-2D CdS/Cu7S4 layered heterojunctions were demonstrated to be advanced composite photocatalysts that enhance the water splitting efficiency toward hydrogen production.The highest hydrogen evolution rate of the 2D^-2D CdS/2%Cu7S4 binary heterojunction photocatalyst was up to 27.8 mmol g^-1 h^-1 under visible light irradiation,with an apparent quantum efficiency of 14.7%at 420 nm,which was almost 10.69 times and 2.65 times higher than those of pure CdS nanosheets(2.6 mmol g^-1 h^-1)and CdS-2%CuS(10.5 mmol g^-1 h^-1),respectively.The establishment of the CdS/Cu7S4 binary-layered heterojunction could not only enhance the separation of photogenerated electron-hole(e--h+)pairs,improve the transfer of photo-excited electrons,and prolong the life-span of photo-generated electrons,but also enhance the light absorption and hydrogen-evolution kinetics.All these factors are important for the enhancement of the photocatalytic activity.Expectedly,the 2D^-2D interface coupling strategy based on CdS NSs can be extensively exploited to improve the hydrogen-evolution activity over various kinds of conventional semiconductor NSs.展开更多
The development of low-cost semiconductor photocatalysts for highly efficient and durable photocatalytic H2 evolution under visible light is very challenging.In this study,we combine low-cost metallic Ni3C cocatalysts...The development of low-cost semiconductor photocatalysts for highly efficient and durable photocatalytic H2 evolution under visible light is very challenging.In this study,we combine low-cost metallic Ni3C cocatalysts with twin nanocrystal Zn0.5Cd0.5S(ZCS)solid solution homojunctions for an efficient visible-light-driven H2 production by a simple approach.As-synthesized Zn0.5Cd0.5S-1%Ni3C(ZCS-1)heterojunction/homojunction nanohybrid exhibited the highest photocatalytic H2-evolution rate of 783μmol h‒1 under visible light,which is 2.88 times higher than that of pristine twin nanocrystal ZCS solid solution.The apparent quantum efficiencies of ZCS and ZCS-1 are measured to be 6.13%and 19.25%at 420 nm,respectively.Specifically,the homojunctions between the zinc blende and wurtzite segments in twin nanocrystal ZCS solid solution can significantly improve the light absorption and separation of photogenerated electron-hole pairs.Furthermore,the heterojunction between ZCS and metallic Ni3C NP cocatalysts can efficiently trap excited electrons from ZCS solid solution and enhance the H2-evolution kinetics at the surface for improving catalytic activity.This study demonstrates a unique one-step strategy for constructing heterojunction/homojunction hybrid nanostructures for a more efficient photocatalytic H2 evolution compared to other noble metal photocatalytic systems.展开更多
Photocatalysis is believed to be one of the best methods to realize sustainable H2 production. However, achieving this through heterogeneous photocatalysis still remains a great challenge owing to the absence of activ...Photocatalysis is believed to be one of the best methods to realize sustainable H2 production. However, achieving this through heterogeneous photocatalysis still remains a great challenge owing to the absence of active sites, sluggish surface reaction kinetics, insufficient charge separation, and a high thermodynamic barrier. Therefore, cocatalysts are necessary and of great significance in boosting photocatalytic H2 generation. This review will focus on the promising and appealing low-cost Ni-based H2-generation cocatalysts as the alternatives for the high-cost and low-abundance noble metal cocatalysts. Special emphasis has been placed on the design principle, modification strategies for further enhancing the activity and stability of Ni-based cocatalysts, and identification of the exact active sites and surface reaction mechanisms. Particularly, four types of modification strategies based on increased light harvesting, enhanced charge separation, strengthened interface interaction, and improved electrocatalytic activity have been thoroughly discussed and compared in detail. This review may open a new avenue for designing highly active and durable Ni-based cocatalysts for photocatalytic H2 generation.展开更多
Single-atom catalysts(SACs)have been widely used in heterogeneous catalysis owing to the maximum utilization of metal-active sites with controlled structures and well-defined locations.Upon tailored coordination with ...Single-atom catalysts(SACs)have been widely used in heterogeneous catalysis owing to the maximum utilization of metal-active sites with controlled structures and well-defined locations.Upon tailored coordination with nitrogen atom,the metal-nitrogen(M-N)-based SACs have demonstrated interesting physical,optical and electronic properties and have become intense in photocatalysis and electrocatalysis in the past decade.Despite substantial efforts in constructing various M–N-based SACs,the principles for modulating the intrinsic photocatalytic and electrocatalytic performance of their active sites and catalytic mechanism have not been sufficiently studied.Herein,the present review intends to shed some light on recent research made in studying the correlation between intrinsic electronic structure,catalytic mechanism,single-metal atom(SMA)confinement and their photocatalytic and electrocatalytic activities(conversion,selectivity,stability and etc).Based on the analysis of fundamentals of M–N-based SACs,theoretical calculations and experimental investigations,including synthetic methods and characterization techniques,are both included to provide an integral understanding of the underlying mechanisms behind improved coordination structure and observed activity.Finally,the challenges and perspectives for constructing highly active M–N based photocatalysis and electrocatalysis SACs are provided.In particular,extensive technical and mechanism aspects are thoroughly discussed,summarized and analyzed for promoting further advancement of M-N-based SACs in photocatalysis and electrocatalysis.展开更多
Conjugated covalent organic frameworks(COFs)hold great promise in photocatalytic hydrogen evolution owing to their high crystallinity,large surface area,and distinct structure.However,COFs exhibit poor charge separati...Conjugated covalent organic frameworks(COFs)hold great promise in photocatalytic hydrogen evolution owing to their high crystallinity,large surface area,and distinct structure.However,COFs exhibit poor charge separation.Therefore,investigating highly effective COF-based photocatalysts is crucial.For the first time,conjugated COF/perylene diimide urea polymer(PUP)all-organic heterostructure with S-scheme interfacial charge-transfer channels was successfully developed and manufactured via in situ coupling of the two-dimensional triazine-based imine-linked COF(denoted as TATF-COF)with PUP.The optimal photocatalytic hydrogen-evolution rate of 94.5 mmol h^(-1) g^(-1) for TATF-COF/PUP is 3.5 times that of pure TATF-COF and is comparable to or even higher than that of the previously reported COF-based photocatalysts,resulting in an apparent quantum efficiency of up to 19.7%at 420 nm.The improved directional S-scheme charge transfer driven by the tuned built-in electric field and enhanced oxidation and reduction reaction rates of the photogenerated carriers contribute synergistically to the boosted photocatalytic H_(2) evolution.Experiments and theoretical studies reveal plausible H_(2) evolution and spatial S-scheme charge-separation mechanisms under visible-light irradiation.This study provides advanced methods for constructing all-organic S-scheme high-efficiency photocatalysts by the modulation of band structures.展开更多
The development of efficient photocatalysts for hydrogen production is crucial in sustainable energy research.In this study,we designed and prepared a Covalent Triazine Framework(CTF)-Cu_(2)O@NC composite featuring an...The development of efficient photocatalysts for hydrogen production is crucial in sustainable energy research.In this study,we designed and prepared a Covalent Triazine Framework(CTF)-Cu_(2)O@NC composite featuring an S-scheme heterojunction structure aimed at enhancing the photocatalytic hydrogen production.The light absorption capacity,electron-hole separation efficiency and H_(2)-evolution activity of the composite were significantly enhanced due to the synergistic effects of the nitrogen-doped carbon(NC)layer and the S-scheme heterojunction.Structural and photoelectrochemical characterization of the system reveal that the S-scheme heterojunctions not only enhance the separation efficiency of photogenerated carriers but also maintain the strong redox capabilities to further promote the photocatalytic reactions.Moreover,the NC layer could simultaneously reduce the photocorrosion of Cu_(2)O and promote the electron transfer.Experimental results demonstrate that the CTF-7%Cu_(2)O@NC composite shows outstanding hydrogen-production performance under visible light,achieving 15645μmol∙g^(−1)∙h^(−1),significantly surpassing the photocatalytic activity of pure CTF(2673μmol∙g^(−1)∙h^(−1)).This study introduces a novel approach to the development of efficient and innovative photocatalytic materials,strongly supporting the advancement of sustainable hydrogen energy.展开更多
Cadmium sulfide(Cd S)-based photocatalysts have attracted extensive attention owing to their strong visible light absorption,suitable band energy levels,and excellent electronic charge transportation properties.This r...Cadmium sulfide(Cd S)-based photocatalysts have attracted extensive attention owing to their strong visible light absorption,suitable band energy levels,and excellent electronic charge transportation properties.This review focuses on the recent progress related to the design,modification,and construction of Cd S-based photocatalysts with excellent photocatalytic H2 evolution performances.First,the basic concepts and mechanisms of photocatalytic H2 evolution are briefly introduced.Thereafter,the fundamental properties,important advancements,and bottlenecks of Cd S in photocatalytic H2 generation are presented in detail to provide an overview of the potential of this material.Subsequently,various modification strategies adopted for Cd S-based photocatalysts to yield solar H2 are discussed,among which the effective approaches aim at generating more charge carriers,promoting efficient charge separation,boosting interfacial charge transfer,accelerating charge utilization,and suppressing charge-induced self-photocorrosion.The critical factors governing the performance of the photocatalyst and the feasibility of each modification strategy toward shaping future research directions are comprehensively discussed with examples.Finally,the prospects and challenges encountered in developing nanostructured Cd S and Cd S-based nanocomposites in photocatalytic H2 evolution are presented.展开更多
Owing to their unique physicochemical,optical and electrical properties,two-dimensional(2D)MoS_(2) cocatalysts have been widely applied in designing and developing highly efficient composite photocatalysts for hydroge...Owing to their unique physicochemical,optical and electrical properties,two-dimensional(2D)MoS_(2) cocatalysts have been widely applied in designing and developing highly efficient composite photocatalysts for hydrogen generation under suitable light irradiation.In this review,we first elaborated on the fundamental aspects of 2D MoS_(2) cocatalysts to include the structural design principles,synthesis strategies,strengths and challenges.Subsequently,we thoroughly highlighted and discussed the modification strategies of 2D MoS_(2) H2-evolution cocatalysts,including doping heteroatoms(e.g.metals,non-metals,and co-doping),designing interfacial coupling morphologies,controlling the physical properties(e.g.thickness,size,structural defects or pores),exposing the reactive facets or edge sites,constructing cocatalyst heterojunctions,engineering the interfacial bonds and confinement effects.In the future,the forefront challenges in understanding and in precise controlling of the active sites at molecular level or atomic level should be carefully studied,while various potential mechanisms of photogenerated-electrons interactions should be proposed.The applications of MoS_(2) cocatalyst in the overall water splitting are also expected.This review may offer new inspiration for designing and constructing novel and efficient MoS_(2)-based composite photocatalysts for highly efficient photocatalytic hydrogen evolution.展开更多
Nowadays,conjugated polymers have garnered numerous attention as a new class of organic photocatalysts due to their tunable electronic properties,low cost,excellent stability and sufficient light-absorption performanc...Nowadays,conjugated polymers have garnered numerous attention as a new class of organic photocatalysts due to their tunable electronic properties,low cost,excellent stability and sufficient light-absorption performance.In particular,pyrene-benzothiadiazole-based conjugated polymer(PBBP)has been considered to be a new type of conjugated polymers for photocatalytic H_(2)evolution.However,the poor charge separation seriously limits its practical application in H_(2)evolution.In this work,a PBBP-based polymer/CdS 2D/2D organic/inorganic S-scheme heterojunction photocatalyst with a strong internal electric field is,for the first time,prepared for efficient photo-catalytic hydrogen evolution.The pyrene-benzothiadiazole-based conjugated polymers(PBBP)are synthesized by the Suzuki-Miyaura reactions.Then,the hybrid heterojunction photocatalysts are fabricated by coupling CdS with it through the ultrasonic mixing method.As a result,the highest H_(2)-production rate of 15.83 mmolh^(-1)g^(-1)is achieved on 20%PBBP/CdS composite under visible-light irradiation,nearly 2.7 times higher than that of pure CdS.The apparent quantum efficiency(AQE)of 20%PBBP/CdS composite could reach 8.66%atλ=420 nm.The enhanced activity could be attributed to the construction of S-scheme heterojunction,which accelerates the recombination of carriers with weaker redox ability and maintains the strong reducibility of electrons in CdS.This work provides a protocol for pyrene-benzothiadiazole-based conjugated polymers to prepare S-scheme heterojunction photocatalysts based on organic/inorganic coupling.展开更多
Covalent organic frameworks(COFs)with high crystallinity and flexible designability have been consid-ered as promising candidates for photocatalytic hydrogen evolution.However,the existence of unpropi-tious exciton ef...Covalent organic frameworks(COFs)with high crystallinity and flexible designability have been consid-ered as promising candidates for photocatalytic hydrogen evolution.However,the existence of unpropi-tious exciton effects in COFs leads to poor charge separation,and thus results in low photocatalytic effi-ciency.Herein,to improve the photoelectron migration efficiency,we designed a 2D/2D organic/inorganic direct Z-scheme COF-based heterojunction(TpTAP/CdS),by the in-situ growing of CdS nanosheets on the COF copolymerized via 2,4,6-tris(4-aminophenyl)-1,3,5-triazine(TAP)and 1,3,5-triformylphloroglucinol(Tp).The femtosecond transient absorption(fs-TA)decay kinetics of TpTAP-COF and TpTAP/CdS further reveal the processes of shallow electron trapping and the recombination of the free photogenerated electron-hole pairs.In particular,the transient absorption traces for TpTAP-COF and TpTAP/CdS normal-ized to the photoinduced absorption peak can effectively verify the Z-scheme charge transfer between TpTAP-COF and CdS,which could enhance the charge mobility and separation,thus reducing the pho-tocorrosion of CdS.Additionally,ultraviolet photoelectron spectroscopy(UPS),in-situ X-ray photoelec-tron spectroscopy(XPS),transient photovoltage measurements,and electron spin resonance(ESR)spec-troscopy further confirm the establishment of the internal electric field(IEF).This work demonstrates the important role of COFs in the construction of 2D/2D organic/inorganic direct Z-scheme heterojunctions and offers a new avenue to explain the criticality of dynamics of the photogenerated carriers for the construction of Z-scheme heterojunctions.展开更多
The separation efficiency of electrons and holes and the enhancement of the surface reductive reaction in the metal sulfide semiconductor photocatalysts are important factors in boosting photocatalytic H_(2)evolution ...The separation efficiency of electrons and holes and the enhancement of the surface reductive reaction in the metal sulfide semiconductor photocatalysts are important factors in boosting photocatalytic H_(2)evolution from water.The control of both interface morphology and the charge-carrier utilization of metal sulfide-based photocatalysts can effectively improve the separation efficiency of electrons and holes and increase the surface reaction active sites,which are considered to be effective methods to improve the photocatalytic activity of semiconductors.Here,the Ti_(3)C_(2)(Mxene)modified all-sulfide 2D/2D Sscheme heterojunction Ti_(3)C_(2)/Zn In_(2)S_(4)(ZIS)/CdS composite material was firstly synthesized by a two-step solvothermal method.The formation of all-sulfide S-scheme heterojunction improves the efficiency of electron-hole separation.The intimate 2D/2D van der Waals structure provides a strong interaction force and a large contact area to enhance charge transfer.The addition of 2D Ti_(3)C_(2)forms the accumulation layer,reducing the recombination of electrons and holes.Under the synergistic promotion,the highest hydrogen production of the prepared Ti_(3)C_(2)/ZIS/CdS composite photocatalyst could reach 8.93 mmol/h/g.This work not only enriches the photocatalytic systems through integrating the ohmic junction and the 2D/2D all-sulfide S-scheme heterojunction,but also provides a satisfactory design strategy for engineering interfacial morphology and charge-carrier utilization.展开更多
Photocatalytic hydrogen evolution through water splitting holds tremendous promise for converting solar energy into a clean and renewable fuel source.However,the efficiency of photocatalysis is often hindered by poor ...Photocatalytic hydrogen evolution through water splitting holds tremendous promise for converting solar energy into a clean and renewable fuel source.However,the efficiency of photocatalysis is often hindered by poor light absorption,insufficient charge separation,and slow reaction kinetics of the photocatalysts.In this study,we designed and synthesized a novel S-scheme heterojunction comprising Ti_(3)C_(2)MXene,CdS nanorods,and nitrogen-doped carbon coated Cu_(2)O(Cu_(2)O@NC)core-shell nanoparticles.Ti_(3)C_(2)MXene as a cocatalyst enhances the light absorption and charge transfer of CdS nanorods.Simultaneously,the core-shell Cu_(2)O@NC nanoparticles establish a pathway for transferring photogenerated electrons and create a favorable band alignment for efficient hydrogen evolution.The synergistic effects of Ti_(3)C_(2)MXene and Cu_(2)O@NC on CdS nanorods result in multiple charge transfer channels and improved photocatalytic performance.The optimal hydrogen evolution rate of the Ti_(3)C_(2)-CdS-Cu_(2)O@NC S-scheme heterojunction photocatalyst is 7.4 times higher than that of pure CdS.Experimental techniques and DFT calculations were employed to explore the structure,morphology,optical properties,charge dynamics,and band structure of the heterojunction.The results revealed that the S-scheme mechanism effectively suppresses the recombination of photogenerated carriers and facilitates the separation and migration of photo-generated electrons and holes to the reaction sites.Furthermore,Ti_(3)C_(2)MXene provides abundant active sites essential for accelerating the surface H_(2)-evolution reaction kinetics.The Cu_(2)O@NC core-shell nanoparticles with a large surface area and high stability are closely adhered to CdS nanorods and establish an S-scheme internal electric field with CdS nanorods to drive charge separation.This investigation provides valuable insights into the rational design of CdS-based photocatalysts,enabling efficient hydrogen production by harnessing the robust kinetic driving force provided by the S-scheme heterojunctions.展开更多
文摘The rapid recombination of photo-generated electron-hole pairs,insufficient active sites,and strong photocorrosion have considerably restricted the practical application of Cd S in photocatalytic fields.Herein,we designed and constructed a 2D/2D/2D layered heterojunction photocatalyst with cascaded 2D coupling interfaces.Experiments using electron spin resonance spectroscopy,ultraviolet photoelectron spectroscopy,and in-situ irradiation X-ray photoelectron spectroscopy were conducted to confirm the 2D layered CdS/WO_(3) step-scheme(S-scheme)heterojunctions and CdS/MX ohmic junctions.Impressively,it was found that the strong interfacial electric fields in the S-scheme heterojunction photocatalysts could effectively promote spatially directional charge separation and transport between CdS and WO_(3) nanosheets.In addition,2D Ti_(3)C_(2) MXene nanosheets with a smaller work function and excellent metal conductivity when used as a co-catalyst could build ohmic junctions with Cd S nanosheets,thus providing a greater number of electron transfer pathways and hydrogen evolution sites.Results showed that the highest visible-light hydrogen evolution rate of the optimized MX-Cd S/WO_(3) layered multi-heterostructures could reach as high as 27.5 mmol/g/h,which was 11.0 times higher than that of pure CdS nanosheets.Notably,the apparent quantum efficiency reached 12.0% at 450 nm.It is hoped that this study offers a reliable approach for developing multifunctional photocatalysts by integrating S-scheme and ohmic-junction built-in electric fields and rationally designing a 2D/2D interface for efficient light-to-hydrogen fuel production.
基金the National Natural Science Foundation of China(21975084,51672089)Special Funding on Applied Science and Technology in Guangdong(2017B020238005)+2 种基金the State Key Laboratory of Advanced Technology for Material Synthesis and Processing(Wuhan University of Technology)(2015-KF-7)State Scholarship Fund of China Scholarship Council(200808440114)the Ding Ying Talent Project of South China Agricultural University for their support
文摘Converting solar energy into clean and sustainable chemical fuels is a promising strategy for exploiting renewable energy.The application of photocatalytic water splitting technology in hydrogen production is important for sustainable energy development and environmental protection.In this study,for the first time,2D Cu7S4 co-catalysts were coupled on the surface of a CdS nanosheet photocatalyst by a one-step ultrasonic-assisted electrostatic self-assembly method at room temperature.The as-fabricated 2D^-2D CdS/Cu7S4 layered heterojunctions were demonstrated to be advanced composite photocatalysts that enhance the water splitting efficiency toward hydrogen production.The highest hydrogen evolution rate of the 2D^-2D CdS/2%Cu7S4 binary heterojunction photocatalyst was up to 27.8 mmol g^-1 h^-1 under visible light irradiation,with an apparent quantum efficiency of 14.7%at 420 nm,which was almost 10.69 times and 2.65 times higher than those of pure CdS nanosheets(2.6 mmol g^-1 h^-1)and CdS-2%CuS(10.5 mmol g^-1 h^-1),respectively.The establishment of the CdS/Cu7S4 binary-layered heterojunction could not only enhance the separation of photogenerated electron-hole(e--h+)pairs,improve the transfer of photo-excited electrons,and prolong the life-span of photo-generated electrons,but also enhance the light absorption and hydrogen-evolution kinetics.All these factors are important for the enhancement of the photocatalytic activity.Expectedly,the 2D^-2D interface coupling strategy based on CdS NSs can be extensively exploited to improve the hydrogen-evolution activity over various kinds of conventional semiconductor NSs.
文摘The development of low-cost semiconductor photocatalysts for highly efficient and durable photocatalytic H2 evolution under visible light is very challenging.In this study,we combine low-cost metallic Ni3C cocatalysts with twin nanocrystal Zn0.5Cd0.5S(ZCS)solid solution homojunctions for an efficient visible-light-driven H2 production by a simple approach.As-synthesized Zn0.5Cd0.5S-1%Ni3C(ZCS-1)heterojunction/homojunction nanohybrid exhibited the highest photocatalytic H2-evolution rate of 783μmol h‒1 under visible light,which is 2.88 times higher than that of pristine twin nanocrystal ZCS solid solution.The apparent quantum efficiencies of ZCS and ZCS-1 are measured to be 6.13%and 19.25%at 420 nm,respectively.Specifically,the homojunctions between the zinc blende and wurtzite segments in twin nanocrystal ZCS solid solution can significantly improve the light absorption and separation of photogenerated electron-hole pairs.Furthermore,the heterojunction between ZCS and metallic Ni3C NP cocatalysts can efficiently trap excited electrons from ZCS solid solution and enhance the H2-evolution kinetics at the surface for improving catalytic activity.This study demonstrates a unique one-step strategy for constructing heterojunction/homojunction hybrid nanostructures for a more efficient photocatalytic H2 evolution compared to other noble metal photocatalytic systems.
基金supprted by the National Natural Science Foundation of China(51672089,51672099)Specical Funding on Applied Science and Technology in Guangdong(2017B020238005)the State Key Laboratory of Advanced Technology for Material Synthesis and Processing(Wuhan University of Technology)(2015-KF-7)~~
文摘Photocatalysis is believed to be one of the best methods to realize sustainable H2 production. However, achieving this through heterogeneous photocatalysis still remains a great challenge owing to the absence of active sites, sluggish surface reaction kinetics, insufficient charge separation, and a high thermodynamic barrier. Therefore, cocatalysts are necessary and of great significance in boosting photocatalytic H2 generation. This review will focus on the promising and appealing low-cost Ni-based H2-generation cocatalysts as the alternatives for the high-cost and low-abundance noble metal cocatalysts. Special emphasis has been placed on the design principle, modification strategies for further enhancing the activity and stability of Ni-based cocatalysts, and identification of the exact active sites and surface reaction mechanisms. Particularly, four types of modification strategies based on increased light harvesting, enhanced charge separation, strengthened interface interaction, and improved electrocatalytic activity have been thoroughly discussed and compared in detail. This review may open a new avenue for designing highly active and durable Ni-based cocatalysts for photocatalytic H2 generation.
文摘Single-atom catalysts(SACs)have been widely used in heterogeneous catalysis owing to the maximum utilization of metal-active sites with controlled structures and well-defined locations.Upon tailored coordination with nitrogen atom,the metal-nitrogen(M-N)-based SACs have demonstrated interesting physical,optical and electronic properties and have become intense in photocatalysis and electrocatalysis in the past decade.Despite substantial efforts in constructing various M–N-based SACs,the principles for modulating the intrinsic photocatalytic and electrocatalytic performance of their active sites and catalytic mechanism have not been sufficiently studied.Herein,the present review intends to shed some light on recent research made in studying the correlation between intrinsic electronic structure,catalytic mechanism,single-metal atom(SMA)confinement and their photocatalytic and electrocatalytic activities(conversion,selectivity,stability and etc).Based on the analysis of fundamentals of M–N-based SACs,theoretical calculations and experimental investigations,including synthetic methods and characterization techniques,are both included to provide an integral understanding of the underlying mechanisms behind improved coordination structure and observed activity.Finally,the challenges and perspectives for constructing highly active M–N based photocatalysis and electrocatalysis SACs are provided.In particular,extensive technical and mechanism aspects are thoroughly discussed,summarized and analyzed for promoting further advancement of M-N-based SACs in photocatalysis and electrocatalysis.
文摘Conjugated covalent organic frameworks(COFs)hold great promise in photocatalytic hydrogen evolution owing to their high crystallinity,large surface area,and distinct structure.However,COFs exhibit poor charge separation.Therefore,investigating highly effective COF-based photocatalysts is crucial.For the first time,conjugated COF/perylene diimide urea polymer(PUP)all-organic heterostructure with S-scheme interfacial charge-transfer channels was successfully developed and manufactured via in situ coupling of the two-dimensional triazine-based imine-linked COF(denoted as TATF-COF)with PUP.The optimal photocatalytic hydrogen-evolution rate of 94.5 mmol h^(-1) g^(-1) for TATF-COF/PUP is 3.5 times that of pure TATF-COF and is comparable to or even higher than that of the previously reported COF-based photocatalysts,resulting in an apparent quantum efficiency of up to 19.7%at 420 nm.The improved directional S-scheme charge transfer driven by the tuned built-in electric field and enhanced oxidation and reduction reaction rates of the photogenerated carriers contribute synergistically to the boosted photocatalytic H_(2) evolution.Experiments and theoretical studies reveal plausible H_(2) evolution and spatial S-scheme charge-separation mechanisms under visible-light irradiation.This study provides advanced methods for constructing all-organic S-scheme high-efficiency photocatalysts by the modulation of band structures.
基金the National Natural Science Foundation of China(22378148,21975084,51672089)the Natural Science Foundation of Guangdong Province(2021A1515010075)for their supports。
文摘The development of efficient photocatalysts for hydrogen production is crucial in sustainable energy research.In this study,we designed and prepared a Covalent Triazine Framework(CTF)-Cu_(2)O@NC composite featuring an S-scheme heterojunction structure aimed at enhancing the photocatalytic hydrogen production.The light absorption capacity,electron-hole separation efficiency and H_(2)-evolution activity of the composite were significantly enhanced due to the synergistic effects of the nitrogen-doped carbon(NC)layer and the S-scheme heterojunction.Structural and photoelectrochemical characterization of the system reveal that the S-scheme heterojunctions not only enhance the separation efficiency of photogenerated carriers but also maintain the strong redox capabilities to further promote the photocatalytic reactions.Moreover,the NC layer could simultaneously reduce the photocorrosion of Cu_(2)O and promote the electron transfer.Experimental results demonstrate that the CTF-7%Cu_(2)O@NC composite shows outstanding hydrogen-production performance under visible light,achieving 15645μmol∙g^(−1)∙h^(−1),significantly surpassing the photocatalytic activity of pure CTF(2673μmol∙g^(−1)∙h^(−1)).This study introduces a novel approach to the development of efficient and innovative photocatalytic materials,strongly supporting the advancement of sustainable hydrogen energy.
基金the National Natural Science Foundation of China(21975084 and 51672089)the Ding Ying Talent Project of South China Agricultural University for their support+1 种基金the Hong Kong Research Grant Council(RGC)General Research Fund GRF1305419 for financial supportthe National Natural Science Foundation of China(51972287 and 51502269)。
文摘Cadmium sulfide(Cd S)-based photocatalysts have attracted extensive attention owing to their strong visible light absorption,suitable band energy levels,and excellent electronic charge transportation properties.This review focuses on the recent progress related to the design,modification,and construction of Cd S-based photocatalysts with excellent photocatalytic H2 evolution performances.First,the basic concepts and mechanisms of photocatalytic H2 evolution are briefly introduced.Thereafter,the fundamental properties,important advancements,and bottlenecks of Cd S in photocatalytic H2 generation are presented in detail to provide an overview of the potential of this material.Subsequently,various modification strategies adopted for Cd S-based photocatalysts to yield solar H2 are discussed,among which the effective approaches aim at generating more charge carriers,promoting efficient charge separation,boosting interfacial charge transfer,accelerating charge utilization,and suppressing charge-induced self-photocorrosion.The critical factors governing the performance of the photocatalyst and the feasibility of each modification strategy toward shaping future research directions are comprehensively discussed with examples.Finally,the prospects and challenges encountered in developing nanostructured Cd S and Cd S-based nanocomposites in photocatalytic H2 evolution are presented.
基金the National Natural Science Foundation of China(Nos.21975084 and 51672089)the Guangdong Provincial Applied Science and Technology Research and Development Program(No.2017B020238005)+2 种基金the Ding Ying Talent Project of South China Agricultural University for their supportthe Hong Kong Research Grant Council(RGC)General Research Fund(No.GRF1305419)for financial supportthe National Natural Science Foundation of China(Nos.51972287 and 51502269)。
文摘Owing to their unique physicochemical,optical and electrical properties,two-dimensional(2D)MoS_(2) cocatalysts have been widely applied in designing and developing highly efficient composite photocatalysts for hydrogen generation under suitable light irradiation.In this review,we first elaborated on the fundamental aspects of 2D MoS_(2) cocatalysts to include the structural design principles,synthesis strategies,strengths and challenges.Subsequently,we thoroughly highlighted and discussed the modification strategies of 2D MoS_(2) H2-evolution cocatalysts,including doping heteroatoms(e.g.metals,non-metals,and co-doping),designing interfacial coupling morphologies,controlling the physical properties(e.g.thickness,size,structural defects or pores),exposing the reactive facets or edge sites,constructing cocatalyst heterojunctions,engineering the interfacial bonds and confinement effects.In the future,the forefront challenges in understanding and in precise controlling of the active sites at molecular level or atomic level should be carefully studied,while various potential mechanisms of photogenerated-electrons interactions should be proposed.The applications of MoS_(2) cocatalyst in the overall water splitting are also expected.This review may offer new inspiration for designing and constructing novel and efficient MoS_(2)-based composite photocatalysts for highly efficient photocatalytic hydrogen evolution.
基金the National Natural Science Foundation of China(21975084,51672089)Natural Science Foundation of Guangdong Province(2021A1515010075)for their support。
文摘Nowadays,conjugated polymers have garnered numerous attention as a new class of organic photocatalysts due to their tunable electronic properties,low cost,excellent stability and sufficient light-absorption performance.In particular,pyrene-benzothiadiazole-based conjugated polymer(PBBP)has been considered to be a new type of conjugated polymers for photocatalytic H_(2)evolution.However,the poor charge separation seriously limits its practical application in H_(2)evolution.In this work,a PBBP-based polymer/CdS 2D/2D organic/inorganic S-scheme heterojunction photocatalyst with a strong internal electric field is,for the first time,prepared for efficient photo-catalytic hydrogen evolution.The pyrene-benzothiadiazole-based conjugated polymers(PBBP)are synthesized by the Suzuki-Miyaura reactions.Then,the hybrid heterojunction photocatalysts are fabricated by coupling CdS with it through the ultrasonic mixing method.As a result,the highest H_(2)-production rate of 15.83 mmolh^(-1)g^(-1)is achieved on 20%PBBP/CdS composite under visible-light irradiation,nearly 2.7 times higher than that of pure CdS.The apparent quantum efficiency(AQE)of 20%PBBP/CdS composite could reach 8.66%atλ=420 nm.The enhanced activity could be attributed to the construction of S-scheme heterojunction,which accelerates the recombination of carriers with weaker redox ability and maintains the strong reducibility of electrons in CdS.This work provides a protocol for pyrene-benzothiadiazole-based conjugated polymers to prepare S-scheme heterojunction photocatalysts based on organic/inorganic coupling.
基金X.Li thanks the National Natural Science Foundation of China(Nos.21975084,51672089)the Natural Science Foundation of Guangdong Province(No.2021A1515010075)for their support+1 种基金G.Liang thanks the Key Research and Development Plan of Hubei Province(No.2021BGE037)the Teacher Research Ability Cul-tivation Foundation of Hubei University of Arts and Science(No.2020kypytd001)for their support.
文摘Covalent organic frameworks(COFs)with high crystallinity and flexible designability have been consid-ered as promising candidates for photocatalytic hydrogen evolution.However,the existence of unpropi-tious exciton effects in COFs leads to poor charge separation,and thus results in low photocatalytic effi-ciency.Herein,to improve the photoelectron migration efficiency,we designed a 2D/2D organic/inorganic direct Z-scheme COF-based heterojunction(TpTAP/CdS),by the in-situ growing of CdS nanosheets on the COF copolymerized via 2,4,6-tris(4-aminophenyl)-1,3,5-triazine(TAP)and 1,3,5-triformylphloroglucinol(Tp).The femtosecond transient absorption(fs-TA)decay kinetics of TpTAP-COF and TpTAP/CdS further reveal the processes of shallow electron trapping and the recombination of the free photogenerated electron-hole pairs.In particular,the transient absorption traces for TpTAP-COF and TpTAP/CdS normal-ized to the photoinduced absorption peak can effectively verify the Z-scheme charge transfer between TpTAP-COF and CdS,which could enhance the charge mobility and separation,thus reducing the pho-tocorrosion of CdS.Additionally,ultraviolet photoelectron spectroscopy(UPS),in-situ X-ray photoelec-tron spectroscopy(XPS),transient photovoltage measurements,and electron spin resonance(ESR)spec-troscopy further confirm the establishment of the internal electric field(IEF).This work demonstrates the important role of COFs in the construction of 2D/2D organic/inorganic direct Z-scheme heterojunctions and offers a new avenue to explain the criticality of dynamics of the photogenerated carriers for the construction of Z-scheme heterojunctions.
基金financially supported by the National Natural Science Foundation of China(Nos.21975084 and 51672089)the Ding Ying Talent Project of South China Agricultural University for their support。
文摘The separation efficiency of electrons and holes and the enhancement of the surface reductive reaction in the metal sulfide semiconductor photocatalysts are important factors in boosting photocatalytic H_(2)evolution from water.The control of both interface morphology and the charge-carrier utilization of metal sulfide-based photocatalysts can effectively improve the separation efficiency of electrons and holes and increase the surface reaction active sites,which are considered to be effective methods to improve the photocatalytic activity of semiconductors.Here,the Ti_(3)C_(2)(Mxene)modified all-sulfide 2D/2D Sscheme heterojunction Ti_(3)C_(2)/Zn In_(2)S_(4)(ZIS)/CdS composite material was firstly synthesized by a two-step solvothermal method.The formation of all-sulfide S-scheme heterojunction improves the efficiency of electron-hole separation.The intimate 2D/2D van der Waals structure provides a strong interaction force and a large contact area to enhance charge transfer.The addition of 2D Ti_(3)C_(2)forms the accumulation layer,reducing the recombination of electrons and holes.Under the synergistic promotion,the highest hydrogen production of the prepared Ti_(3)C_(2)/ZIS/CdS composite photocatalyst could reach 8.93 mmol/h/g.This work not only enriches the photocatalytic systems through integrating the ohmic junction and the 2D/2D all-sulfide S-scheme heterojunction,but also provides a satisfactory design strategy for engineering interfacial morphology and charge-carrier utilization.
基金National Natural Science Foundation of China(21975084,51672089)Natural Science Foundation of Guangdong Province(2021A1515010075)for their support
文摘Photocatalytic hydrogen evolution through water splitting holds tremendous promise for converting solar energy into a clean and renewable fuel source.However,the efficiency of photocatalysis is often hindered by poor light absorption,insufficient charge separation,and slow reaction kinetics of the photocatalysts.In this study,we designed and synthesized a novel S-scheme heterojunction comprising Ti_(3)C_(2)MXene,CdS nanorods,and nitrogen-doped carbon coated Cu_(2)O(Cu_(2)O@NC)core-shell nanoparticles.Ti_(3)C_(2)MXene as a cocatalyst enhances the light absorption and charge transfer of CdS nanorods.Simultaneously,the core-shell Cu_(2)O@NC nanoparticles establish a pathway for transferring photogenerated electrons and create a favorable band alignment for efficient hydrogen evolution.The synergistic effects of Ti_(3)C_(2)MXene and Cu_(2)O@NC on CdS nanorods result in multiple charge transfer channels and improved photocatalytic performance.The optimal hydrogen evolution rate of the Ti_(3)C_(2)-CdS-Cu_(2)O@NC S-scheme heterojunction photocatalyst is 7.4 times higher than that of pure CdS.Experimental techniques and DFT calculations were employed to explore the structure,morphology,optical properties,charge dynamics,and band structure of the heterojunction.The results revealed that the S-scheme mechanism effectively suppresses the recombination of photogenerated carriers and facilitates the separation and migration of photo-generated electrons and holes to the reaction sites.Furthermore,Ti_(3)C_(2)MXene provides abundant active sites essential for accelerating the surface H_(2)-evolution reaction kinetics.The Cu_(2)O@NC core-shell nanoparticles with a large surface area and high stability are closely adhered to CdS nanorods and establish an S-scheme internal electric field with CdS nanorods to drive charge separation.This investigation provides valuable insights into the rational design of CdS-based photocatalysts,enabling efficient hydrogen production by harnessing the robust kinetic driving force provided by the S-scheme heterojunctions.
