This work describes the use of TiO_(2)nanotubes-based electrodes(TNT)modified with Cu_(2)O nanostructures and gold nanoparticles for the photoelectroreduction of CO_(2)to produce value-added compounds.A thin layer of ...This work describes the use of TiO_(2)nanotubes-based electrodes(TNT)modified with Cu_(2)O nanostructures and gold nanoparticles for the photoelectroreduction of CO_(2)to produce value-added compounds.A thin layer of polydopamine was used as both an adherent agent and an electron transfer mediator,due to itsπ-conjugated electron system.The highest production yield was achieved using a TNT@PDA/Nc/Au40%electrode,with Faradaic efficiencies of 47.4%(110.5μM cm^(-2))and 27.8%(50.4μM cm^(-2))for methanol and methane,respectively.The performance of the photoelectrodes was shown to be Cu_(2)O facet-dependent,with cubic structures leading to greater conversion of CO_(2)to methanol(43%)and methane(27%),compared to the octahedral morphology,while a higher percentage of metallic gold on the nanostructured Cu_(2)O surface was mainly important for CH4production.Density functional theory(DFT)calculations supported these findings,attributing the superior photoelectrocatalytic performance of the TNT@PDA/Nc/Au40%electrode for CH4generation to the formation of an OCH3intermediate bonded to Au atoms.Studies using isotope-labeling and analysis by gas chromatograph-mass(GC-MS)demonstrated that13CO_(2)was the source for photoelectrocatalytic generation of13CH3OH and13CH313CH2OH.展开更多
Photocatalysis is critically important for environmental remediation and renewable energy technologies.The ability to objectively characterize photocatalyst properties and photocatalysis processes is paramount for mea...Photocatalysis is critically important for environmental remediation and renewable energy technologies.The ability to objectively characterize photocatalyst properties and photocatalysis processes is paramount for meaningful performance evaluation and fundamental studies to guide the design and development of high-performance photocatalysts and photocatalysis systems.Photocatalysis is essentially an electron transfer process,and photoelectrocatalysis(PEC)principles can be used to directly quantify transferred electrons to determine the intrinsic properties of photocatalysts and photocatalysis processes in isolation,without interference from counter reactions due to physically separated oxidation and reduction half-reactions.In this review,we discuss emphatically the PEC-based principles for characterizing intrinsic properties of photocatalysts and important processes of photocatalysis,with a particular focus on their environmental applications in the degradation of pollutants,disinfection,and detection of chemical oxygen demand(COD).An outlook towards the potential applications of PEC technique is given.展开更多
Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a nov...Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a novel photoelectrocatalytic catalyst for the selective reduction of CO2 to methanol,comprising a copper catalyst modified with flower-like cerium oxide nanoparticles(CeO2 NPs)(a n-type semiconductor)and copper oxide nanoparticles(CuO NPs)(a p-type semiconductor).At an applied potential of−1.0 V(vs SCE)under visible light irradiation,the CeO2 NPs/CuO NPs/Cu catalyst yielded methanol at a rate of 3.44μmol cm^−2 h^−1,which was approximately five times higher than that of a CuO NPs/Cu catalyst(0.67μmol cm^−2 h^−1).The carrier concentration increased by^108 times when the flower-like CeO2 NPs were deposited on the CuO NPs/Cu catalyst,due to synergistic transfer of photoexcited electrons from the conduction band of CuO to that of CeO2,which enhanced both photocatalytic and photoelectrocatalytic CO2 reduction on the CeO2 NPs.The facile migration of photoexcited electrons and holes across the p–n heterojunction that formed between the CeO2 and CuO components was thus critical to excellent light-induced CO2 reduction properties of the CeO2 NPs/CuO NPs/Cu catalyst.Results encourage the wider application of composite semiconductor electrodes in carbon dioxide reduction.展开更多
The inhibition effect of tert-butyl alcohol(TBA), identified as the·OH radical inhibitor, on the TiO_2 nano assays(TNA) photoelectrocatalytic oxidation of different organics such as glucose and phthalate was repo...The inhibition effect of tert-butyl alcohol(TBA), identified as the·OH radical inhibitor, on the TiO_2 nano assays(TNA) photoelectrocatalytic oxidation of different organics such as glucose and phthalate was reported. The adsorption performance of these organics on the TNA photoelectrode was investigated by using the instantaneous photocurrent value, and the degradation property was examined by using the exhausted reaction. The results showed that glucose exhibited the poor adsorption and easy degradation performance, phthalate showed the strong adsorption and harddegradation, but TBA showed the weak adsorption and was the most difficult to be degraded. The degradation of both glucose and phthalate could be inhibited evidently by TBA. But the effect on glucose was more obvious. The different inhibition effects of TBA on different organics could be attributed to the differences in the adsorption and the degradation property. For instance, phthalate of the strong adsorption property could avoid from the capture of·OH radicals by TBA in TNA photoelectrocatalytic process.展开更多
Developing an efficient artificial photosynthetic system for transforming carbon dioxide and storing solar energy in the form of chemical bonds is one of the greatest challenges in modern chemistry.However,the limited...Developing an efficient artificial photosynthetic system for transforming carbon dioxide and storing solar energy in the form of chemical bonds is one of the greatest challenges in modern chemistry.However,the limited choice of catalysts with wide light absorption range,long-term stability and excellent selectivity for CO_(2) reduction makes the process sluggish.Here,a core-shell-structured nonnoble-metal Ni@In co-catalyst loaded p-type silicon nanowire arrays(SiNWs)for efficient CO_(2) reduction to formate is demonstrated.The formation rate and Faradaic efficiency of formate over the Ni@In/SiNWs catalyst reach 58μmol h^(-1) cm^(-2) and 87% under the irradiation of one simulated sunlight(AM 1.5 G,100 mW cm^(-2)),respectively,which are about 24 and 12 times those over the pristine SiNWs.The enhanced photoelectrocatalytic performance for CO_(2) reduction is attributed to the rational combination of Ni capable of effectively extracting the photogenerated electrons and In responsible for the selective activation of CO_(2).展开更多
Traditional conversion of alcohols into carbonyl compounds exists a few drawbacks such as harsh reaction conditions,production of large amounts of hazardous wastes,and poor selectivity.The newly emerging conversion ap...Traditional conversion of alcohols into carbonyl compounds exists a few drawbacks such as harsh reaction conditions,production of large amounts of hazardous wastes,and poor selectivity.The newly emerging conversion approaches via photo-,electro-,and photoelectro-catalysis to oxidize alcohols into high value-added corresponding carbonyl compounds as well as the possible simultaneous production of clean fuel hydrogen(H_(2))under mild conditions are promising to substitute the traditional approach to form greener and sustainable reaction systems and thus have aroused tremendous investigations.In this review,the state-of-the-art photocatalytic,electrocatalytic,and photoelectrocatalytic strategies for selective oxidation of different types of alcohols(aromatic and aliphatic alcohols,single alcohol,and polyols,etc.)as well as the simultaneous production of H_(2) in certain systems are discussed.The design of photocatalysts,electrocatalysts,and photoelectrocatalysts as well as reaction mechanism is summarized and discussed in detail.In the end,current challenges and future research directions are proposed.It is expected that this review will not only deepen the understanding of environmentally friendly catalytic systems for alcohol conversion as well as H_(2) production,but also enlighten significance and inspirations for the follow-up study of selective oxidation of various types of organic molecules to value-added chemicals.展开更多
A controllable approach that combines surface plasmon resonance and twodimensional(2D)graphene/MoS2 heterojunction has not been implemented despite its potential for efficient photoelectrochemical(PEC)water splitting....A controllable approach that combines surface plasmon resonance and twodimensional(2D)graphene/MoS2 heterojunction has not been implemented despite its potential for efficient photoelectrochemical(PEC)water splitting.In this study,plasmonic Ag-decorated 2D MoS2 nanosheets were vertically grown on graphene substrates in a practical large-scale manner through metalorganic chemical vapor deposition of MoS2 and thermal evaporation of Ag.The plasmonic Ag-decorated MoS2 nanosheets on graphene yielded up to 10 times higher photo-to-dark current ratio than MoS2 nanosheets on indium tin oxide.The significantly enhanced PEC activity could be attributed to the synergetic effects of SPR and favorable graphene/2D MoS2 heterojunction.Plasmonic Ag nanoparticles not only increased visible-light and near-infrared absorption of 2D MoS2,but also induced highly amplified local electric field intensity in 2D MoS2.In addition,the vertically aligned 2D MoS2 on graphene acted as a desirable heterostructure for efficient separation and transportation of photo-generated carriers.This study provides a promising path for exploiting the full potential of 2D MoS2 for practical large-scale and efficient PEC water-splitting applications.展开更多
ZnO/graphene/polyaniline(PANI) composite is synthesized and used for photoelectrocatalytic oxidation of methane under simulated sun light illumination with ambient conditions. The photoelectrochemical(PEC) performance...ZnO/graphene/polyaniline(PANI) composite is synthesized and used for photoelectrocatalytic oxidation of methane under simulated sun light illumination with ambient conditions. The photoelectrochemical(PEC) performance of pure ZnO, ZnO/graphene, ZnO/PANI, and ZnO/graphene/PANI photoanodes is investigated by cyclic voltammetry(CV),chronoamerometry(J–t) and electrochemical impedance spectroscopy(EIS). The yields of methane oxidation products,mainly methanol(CH_3OH) and formic acid(HCOOH), catalysed by the synthesized ZnO/graphene/PANI composite are 2.76 and 3.20 times those of pure ZnO, respectively. The mechanism of the photoelectrocatalytic process converting methane into methanol and formic acid is proposed on the basis of the experimental results. The enhanced photoelectrocatalytic activity of the ZnO/graphene/PANI composite can be attributed to the fact that graphene can efficiently transfer photo-generated electrons from the inner region to the surface reaction to form free radicals due to its superior electrical conductivity as an inter-media layer. Meanwhile, the introduction of PANI promotes solar energy harvesting by extending the visible light absorption and enhances charge separation efficiency due to its conducting polymer characteristics.In addition, the PANI can create a favorable π-conjunction structure together with graphene layers, which can achieve a more effective charge separation. This research demonstrates that the fabricated ZnO/graphene/PANI composite promises to implement the visible-light photoelectrocatalytic methane oxidation.展开更多
Hydrogen generation via artificial photosynthesis paves a promising way to remit the ever-increasing energy crisis and deteriorative environmental issues.Among all the materials utilized for solar hydrogen production,...Hydrogen generation via artificial photosynthesis paves a promising way to remit the ever-increasing energy crisis and deteriorative environmental issues.Among all the materials utilized for solar hydrogen production,perovskite has emerged as a rising star due to its superior optoelectronic properties.This manuscript aims to provide a comprehensive review summarizing the recent inspiring advancements on perovskite-based solar hydrogen production systems,including the particulate photocatalysis,photoelectrochemical cells,and photovoltaic-electrocatalytic cells.We start with a brief introduction of the advantages of perovskites for solar hydrogen production and the basic principles of the three most prominent solar hydrogen production systems.The representative progresses in this field are then detailed with a special emphasis on the strategies to improve the efficiency and the stability of the systems.Finally,challenges and opportunities for the further development of the PVK-based solar hydrogen production systems are presented with perspective given on outlook,performance,cost and stability.展开更多
GaP has been shown to be a promising photoelectrocatalyst for selective CO_(2)reduction to methanol.Due to the relevance of the interface structure to important processes such as electron/proton transfer,a detailed un...GaP has been shown to be a promising photoelectrocatalyst for selective CO_(2)reduction to methanol.Due to the relevance of the interface structure to important processes such as electron/proton transfer,a detailed understanding of the GaP(110)-water interfacial structure is of great importance.Ab initio molecular dynamics(AIMD)can be used for obtaining the microscopic information of the interfacial structure.However,the GaP(110)-water interface cannot converge to an equilibrated structure at the time scale of the AIMD simulation.In this work,we perform the machine learning accelerated molecular dynamics(MLMD)to overcome the difficulty of insufficient sampling by AIMD.With the help of MLMD,we unravel the microscopic information of the structure of the GaP(110)-water interface,and obtain a deeper understanding of the mechanisms of proton transfer at the GaP(110)-water interface,which will pave the way for gaining valuable insights into photoelectrocatalytic mechanisms and improving the performance of photoelectrochemical cells.展开更多
Energy storage is pivotal for the continuous utilization of solar energy suffering from the intermittency issue. Herein, we demonstrate a solar rechargeable flow cell（SRFC） based on photoelectrochemical regeneration...Energy storage is pivotal for the continuous utilization of solar energy suffering from the intermittency issue. Herein, we demonstrate a solar rechargeable flow cell（SRFC） based on photoelectrochemical regeneration of vanadium redox species for in-situ solar energy harvest and storage. In this device, TiO_2 and MWCNT/acetylene black（MWCNT/AB） composite are served as the photoanode and the counter electrode,respectively, with all vanadium redox couples, VO_2~＋/VO^（2＋）and VO^（2＋）/V^（3＋）, as solar energy storage media.Benefitting from solar energy, the cell can be photocharged under a bias as low as 0.1 V, which is much lower than the discharge voltage of ~0.5 V. Photocharged under the optimized condition, the cell delivers a discharge energy of 23.0 mWh/L with 67.4% input electric energy savings. This prototype work may inspire the rational design for cost-effective solar energy storage devices.展开更多
Converting CO_(2)and water into valuable chemicals like plant do is considered a promising approach to address both environmental and energy issues.Taking inspiration from the structures of natural leaves,we designed ...Converting CO_(2)and water into valuable chemicals like plant do is considered a promising approach to address both environmental and energy issues.Taking inspiration from the structures of natural leaves,we designed and synthesized a novel copper-coordinated covalent triazine framework(CuCTF)supported by silicon nanowire arrays on wafer chip.This marks the first-ever application of such a hybrid material in the photoelectrocatalytic reduction of CO_(2)under mild conditions.The Si@CuCTF6 heterojunction has exhibited exceptional selectivity of 95.6%towards multicarbon products(C_(2+))and apparent quantum efficiency(AQE)of 0.89%for carbon-based products.The active sites of the catalysts are derived from the nitrogen atoms of unique triazine ring structure in the ordered porous framework and the abundant Cu-N coordination sites with bipyridine units.Furthermore,through DFT calculations and operando FTIR spectra analysis,we proposed a comprehensive mechanism for the photoelectrocatalytic CO_(2)reduction,confirming the existence of key intermediate species such as*CO_(2)-,*=C=O,*CHO and*CO-CHO etc.This work not only provides a new way to mimic photosynthesis of plant leaves but also gives a new opportunity to enter this research field in the future.展开更多
基金FAPESP,Brazil(#2023/10027-5,#2014/50945-4,#2020/15230-5,and#2021/000675-4)CNPq,Brazil(#465571/2014-0,#303269/2021-9,and#307837/2014-9)+6 种基金Instituto Serrapilheira(grant number Serra-2211-41925)FAPEMIG,Brazil(#PPM-00831-15)for support of this workCNPq,Brazil(#105944/2022-0)and PROPEUNESP(13/2022)FAPESP(#2019/00463-7,#2018/22845-6,and#2021/08007-0,respectively)for scholarshipsthe National Institute for Alternative Technologies of Detection,Toxicological Evaluation and Removal of Micropollutants and Radioactives(INCT-DATREM)the support of the Research Centre for Greenhouse Gas Innovation(RCGI),hosted by the University of Sao Paulo(USP)and sponsored by FAPESP and Shell Brasilthe strategic support given by ANP,Brazil(Brazilian National Oil,Natural Gas,and Biofuels Agency)through the R&D levy regulation。
文摘This work describes the use of TiO_(2)nanotubes-based electrodes(TNT)modified with Cu_(2)O nanostructures and gold nanoparticles for the photoelectroreduction of CO_(2)to produce value-added compounds.A thin layer of polydopamine was used as both an adherent agent and an electron transfer mediator,due to itsπ-conjugated electron system.The highest production yield was achieved using a TNT@PDA/Nc/Au40%electrode,with Faradaic efficiencies of 47.4%(110.5μM cm^(-2))and 27.8%(50.4μM cm^(-2))for methanol and methane,respectively.The performance of the photoelectrodes was shown to be Cu_(2)O facet-dependent,with cubic structures leading to greater conversion of CO_(2)to methanol(43%)and methane(27%),compared to the octahedral morphology,while a higher percentage of metallic gold on the nanostructured Cu_(2)O surface was mainly important for CH4production.Density functional theory(DFT)calculations supported these findings,attributing the superior photoelectrocatalytic performance of the TNT@PDA/Nc/Au40%electrode for CH4generation to the formation of an OCH3intermediate bonded to Au atoms.Studies using isotope-labeling and analysis by gas chromatograph-mass(GC-MS)demonstrated that13CO_(2)was the source for photoelectrocatalytic generation of13CH3OH and13CH313CH2OH.
基金financially supported by the Natural Science Foundation of China(52172106)the Anhui Provincial Natural Science Foundation(2108085QB60 and 2108085QB61)+2 种基金the China Postdoctoral Science Foundation(2020M682057)the Special Research Assistant Program,Chinese Academy of SciencesJiangsu Provincial Double-Innovation Doctor Program(JSSCBS20210996)。
文摘Photocatalysis is critically important for environmental remediation and renewable energy technologies.The ability to objectively characterize photocatalyst properties and photocatalysis processes is paramount for meaningful performance evaluation and fundamental studies to guide the design and development of high-performance photocatalysts and photocatalysis systems.Photocatalysis is essentially an electron transfer process,and photoelectrocatalysis(PEC)principles can be used to directly quantify transferred electrons to determine the intrinsic properties of photocatalysts and photocatalysis processes in isolation,without interference from counter reactions due to physically separated oxidation and reduction half-reactions.In this review,we discuss emphatically the PEC-based principles for characterizing intrinsic properties of photocatalysts and important processes of photocatalysis,with a particular focus on their environmental applications in the degradation of pollutants,disinfection,and detection of chemical oxygen demand(COD).An outlook towards the potential applications of PEC technique is given.
基金financially supported by the National Natural Science Foundation of China(21802089)Natural Science Foundation of Shandong Province(ZR2019BB015)+5 种基金The Science and Technology Plan of Shandong Province Colleges and Universities under Grant(No.J14LC16)the Natural Science Foundation of Shandong Province under Grant(No.ZR2017MB018)funding support from the Shandong Province Double Hundred Talents Program for Foreign Expertsthe Energy Education Trust of New Zealandthe Dodd Walls Centre for Photonic and Quantum Technologiesthe Mac Diarmid Institute for Advanced Materials and Nanotechnology
文摘Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a novel photoelectrocatalytic catalyst for the selective reduction of CO2 to methanol,comprising a copper catalyst modified with flower-like cerium oxide nanoparticles(CeO2 NPs)(a n-type semiconductor)and copper oxide nanoparticles(CuO NPs)(a p-type semiconductor).At an applied potential of−1.0 V(vs SCE)under visible light irradiation,the CeO2 NPs/CuO NPs/Cu catalyst yielded methanol at a rate of 3.44μmol cm^−2 h^−1,which was approximately five times higher than that of a CuO NPs/Cu catalyst(0.67μmol cm^−2 h^−1).The carrier concentration increased by^108 times when the flower-like CeO2 NPs were deposited on the CuO NPs/Cu catalyst,due to synergistic transfer of photoexcited electrons from the conduction band of CuO to that of CeO2,which enhanced both photocatalytic and photoelectrocatalytic CO2 reduction on the CeO2 NPs.The facile migration of photoexcited electrons and holes across the p–n heterojunction that formed between the CeO2 and CuO components was thus critical to excellent light-induced CO2 reduction properties of the CeO2 NPs/CuO NPs/Cu catalyst.Results encourage the wider application of composite semiconductor electrodes in carbon dioxide reduction.
基金the National High Technology Research and Development Program of China (Grant No.2009AA063003)the National Nature Science Foundation of China (No.20677039) for financial support
文摘The inhibition effect of tert-butyl alcohol(TBA), identified as the·OH radical inhibitor, on the TiO_2 nano assays(TNA) photoelectrocatalytic oxidation of different organics such as glucose and phthalate was reported. The adsorption performance of these organics on the TNA photoelectrode was investigated by using the instantaneous photocurrent value, and the degradation property was examined by using the exhausted reaction. The results showed that glucose exhibited the poor adsorption and easy degradation performance, phthalate showed the strong adsorption and harddegradation, but TBA showed the weak adsorption and was the most difficult to be degraded. The degradation of both glucose and phthalate could be inhibited evidently by TBA. But the effect on glucose was more obvious. The different inhibition effects of TBA on different organics could be attributed to the differences in the adsorption and the degradation property. For instance, phthalate of the strong adsorption property could avoid from the capture of·OH radicals by TBA in TNA photoelectrocatalytic process.
基金supported by the National Natural Science Foundation of China(Nos.21972115,91945301,21690082 and 21503176)the China Postdoctoral Science Foundation(Nos.2015M570555,2016T90597)。
文摘Developing an efficient artificial photosynthetic system for transforming carbon dioxide and storing solar energy in the form of chemical bonds is one of the greatest challenges in modern chemistry.However,the limited choice of catalysts with wide light absorption range,long-term stability and excellent selectivity for CO_(2) reduction makes the process sluggish.Here,a core-shell-structured nonnoble-metal Ni@In co-catalyst loaded p-type silicon nanowire arrays(SiNWs)for efficient CO_(2) reduction to formate is demonstrated.The formation rate and Faradaic efficiency of formate over the Ni@In/SiNWs catalyst reach 58μmol h^(-1) cm^(-2) and 87% under the irradiation of one simulated sunlight(AM 1.5 G,100 mW cm^(-2)),respectively,which are about 24 and 12 times those over the pristine SiNWs.The enhanced photoelectrocatalytic performance for CO_(2) reduction is attributed to the rational combination of Ni capable of effectively extracting the photogenerated electrons and In responsible for the selective activation of CO_(2).
基金support from the National Natural Science Foundation of China(21976054,22176054)the Fundamental Research Funds for the Central Universities(2020MS036,FRF-TP-20-005A3)+1 种基金the Fundamental Research Funds for the Central Universities and the Youth Teacher International Exchange&Growth Program(QNXM20220026)MOE Key Laboratory of Resources and Environmental System Optimization,College of Environmental Science and Engineering,North China Electric Power University(KLRE-KF202201)。
文摘Traditional conversion of alcohols into carbonyl compounds exists a few drawbacks such as harsh reaction conditions,production of large amounts of hazardous wastes,and poor selectivity.The newly emerging conversion approaches via photo-,electro-,and photoelectro-catalysis to oxidize alcohols into high value-added corresponding carbonyl compounds as well as the possible simultaneous production of clean fuel hydrogen(H_(2))under mild conditions are promising to substitute the traditional approach to form greener and sustainable reaction systems and thus have aroused tremendous investigations.In this review,the state-of-the-art photocatalytic,electrocatalytic,and photoelectrocatalytic strategies for selective oxidation of different types of alcohols(aromatic and aliphatic alcohols,single alcohol,and polyols,etc.)as well as the simultaneous production of H_(2) in certain systems are discussed.The design of photocatalysts,electrocatalysts,and photoelectrocatalysts as well as reaction mechanism is summarized and discussed in detail.In the end,current challenges and future research directions are proposed.It is expected that this review will not only deepen the understanding of environmentally friendly catalytic systems for alcohol conversion as well as H_(2) production,but also enlighten significance and inspirations for the follow-up study of selective oxidation of various types of organic molecules to value-added chemicals.
基金This work was supported by the National Research Foundation of Korea(NRF)grants funded by the Ministry of Education(2020R1I1A3A04037241 and 2019R1A6A3A13095792)and the Korea Government(MSIT)(2020R1A4A4079397).
文摘A controllable approach that combines surface plasmon resonance and twodimensional(2D)graphene/MoS2 heterojunction has not been implemented despite its potential for efficient photoelectrochemical(PEC)water splitting.In this study,plasmonic Ag-decorated 2D MoS2 nanosheets were vertically grown on graphene substrates in a practical large-scale manner through metalorganic chemical vapor deposition of MoS2 and thermal evaporation of Ag.The plasmonic Ag-decorated MoS2 nanosheets on graphene yielded up to 10 times higher photo-to-dark current ratio than MoS2 nanosheets on indium tin oxide.The significantly enhanced PEC activity could be attributed to the synergetic effects of SPR and favorable graphene/2D MoS2 heterojunction.Plasmonic Ag nanoparticles not only increased visible-light and near-infrared absorption of 2D MoS2,but also induced highly amplified local electric field intensity in 2D MoS2.In addition,the vertically aligned 2D MoS2 on graphene acted as a desirable heterostructure for efficient separation and transportation of photo-generated carriers.This study provides a promising path for exploiting the full potential of 2D MoS2 for practical large-scale and efficient PEC water-splitting applications.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51602021 and 51474017)the Fundamental Research Funds for the Central Universities(Grant No.FRF-TP-15-107A1)
文摘ZnO/graphene/polyaniline(PANI) composite is synthesized and used for photoelectrocatalytic oxidation of methane under simulated sun light illumination with ambient conditions. The photoelectrochemical(PEC) performance of pure ZnO, ZnO/graphene, ZnO/PANI, and ZnO/graphene/PANI photoanodes is investigated by cyclic voltammetry(CV),chronoamerometry(J–t) and electrochemical impedance spectroscopy(EIS). The yields of methane oxidation products,mainly methanol(CH_3OH) and formic acid(HCOOH), catalysed by the synthesized ZnO/graphene/PANI composite are 2.76 and 3.20 times those of pure ZnO, respectively. The mechanism of the photoelectrocatalytic process converting methane into methanol and formic acid is proposed on the basis of the experimental results. The enhanced photoelectrocatalytic activity of the ZnO/graphene/PANI composite can be attributed to the fact that graphene can efficiently transfer photo-generated electrons from the inner region to the surface reaction to form free radicals due to its superior electrical conductivity as an inter-media layer. Meanwhile, the introduction of PANI promotes solar energy harvesting by extending the visible light absorption and enhances charge separation efficiency due to its conducting polymer characteristics.In addition, the PANI can create a favorable π-conjunction structure together with graphene layers, which can achieve a more effective charge separation. This research demonstrates that the fabricated ZnO/graphene/PANI composite promises to implement the visible-light photoelectrocatalytic methane oxidation.
基金National Key Research Program of China(2017YFA0204800)National Natural Science Foundation of China(No.21603136)+1 种基金the National Science Basic Research Plan in Shaanxi Province of China(2017JM2007)the Fundamental Research Funds for the Central Universities(2019TS005)。
文摘Hydrogen generation via artificial photosynthesis paves a promising way to remit the ever-increasing energy crisis and deteriorative environmental issues.Among all the materials utilized for solar hydrogen production,perovskite has emerged as a rising star due to its superior optoelectronic properties.This manuscript aims to provide a comprehensive review summarizing the recent inspiring advancements on perovskite-based solar hydrogen production systems,including the particulate photocatalysis,photoelectrochemical cells,and photovoltaic-electrocatalytic cells.We start with a brief introduction of the advantages of perovskites for solar hydrogen production and the basic principles of the three most prominent solar hydrogen production systems.The representative progresses in this field are then detailed with a special emphasis on the strategies to improve the efficiency and the stability of the systems.Finally,challenges and opportunities for the further development of the PVK-based solar hydrogen production systems are presented with perspective given on outlook,performance,cost and stability.
基金the National Natural Science Foundation of China(22225302,21991151,21991150,22021001,92161113,91945301)the Fundamental Research Funds for the Central Universities(20720220009)+1 种基金the China Postdoctoral Science Foundation(2020 M682079)the Guangdong Basic and Applied Basic Research Foundation(2020A1515110539)。
文摘GaP has been shown to be a promising photoelectrocatalyst for selective CO_(2)reduction to methanol.Due to the relevance of the interface structure to important processes such as electron/proton transfer,a detailed understanding of the GaP(110)-water interfacial structure is of great importance.Ab initio molecular dynamics(AIMD)can be used for obtaining the microscopic information of the interfacial structure.However,the GaP(110)-water interface cannot converge to an equilibrated structure at the time scale of the AIMD simulation.In this work,we perform the machine learning accelerated molecular dynamics(MLMD)to overcome the difficulty of insufficient sampling by AIMD.With the help of MLMD,we unravel the microscopic information of the structure of the GaP(110)-water interface,and obtain a deeper understanding of the mechanisms of proton transfer at the GaP(110)-water interface,which will pave the way for gaining valuable insights into photoelectrocatalytic mechanisms and improving the performance of photoelectrochemical cells.
基金financially supported by the National Natural Science Foundation of China(grant no.21573230)973 National Basic Research Program of the Ministry of Science and Technology(grant no.2014CB239400)
文摘Energy storage is pivotal for the continuous utilization of solar energy suffering from the intermittency issue. Herein, we demonstrate a solar rechargeable flow cell（SRFC） based on photoelectrochemical regeneration of vanadium redox species for in-situ solar energy harvest and storage. In this device, TiO_2 and MWCNT/acetylene black（MWCNT/AB） composite are served as the photoanode and the counter electrode,respectively, with all vanadium redox couples, VO_2~＋/VO^（2＋）and VO^（2＋）/V^（3＋）, as solar energy storage media.Benefitting from solar energy, the cell can be photocharged under a bias as low as 0.1 V, which is much lower than the discharge voltage of ~0.5 V. Photocharged under the optimized condition, the cell delivers a discharge energy of 23.0 mWh/L with 67.4% input electric energy savings. This prototype work may inspire the rational design for cost-effective solar energy storage devices.
基金supported by Natural Science Foundation of Gansu Province(23JRRA745)the Fundamental Research Funds for the Central Universities(lzujbky2021-sp55).
文摘Converting CO_(2)and water into valuable chemicals like plant do is considered a promising approach to address both environmental and energy issues.Taking inspiration from the structures of natural leaves,we designed and synthesized a novel copper-coordinated covalent triazine framework(CuCTF)supported by silicon nanowire arrays on wafer chip.This marks the first-ever application of such a hybrid material in the photoelectrocatalytic reduction of CO_(2)under mild conditions.The Si@CuCTF6 heterojunction has exhibited exceptional selectivity of 95.6%towards multicarbon products(C_(2+))and apparent quantum efficiency(AQE)of 0.89%for carbon-based products.The active sites of the catalysts are derived from the nitrogen atoms of unique triazine ring structure in the ordered porous framework and the abundant Cu-N coordination sites with bipyridine units.Furthermore,through DFT calculations and operando FTIR spectra analysis,we proposed a comprehensive mechanism for the photoelectrocatalytic CO_(2)reduction,confirming the existence of key intermediate species such as*CO_(2)-,*=C=O,*CHO and*CO-CHO etc.This work not only provides a new way to mimic photosynthesis of plant leaves but also gives a new opportunity to enter this research field in the future.
