The construction of high-efficiency and low-cost non-noble metal bifunctional electrocatalysts for water electrolysis is crucial for commercial large-scale application of hydrogen energy.Here,we report a novel strateg...The construction of high-efficiency and low-cost non-noble metal bifunctional electrocatalysts for water electrolysis is crucial for commercial large-scale application of hydrogen energy.Here,we report a novel strategy with erbiumdoped NiCoP nanowire arrays in situ grown on conductive nickel foam(Er-NiCoP/NF).Significantly,the developed electrode shows exceptional bifunctional catalytic activity,which only requires overpotentials of 46 and 225 mV to afford a current density of 10 mAcm^(−2) for the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER),respectively.Density functional theory calculations reveal that the appropriate Er incorporation into the NiCoP lattice can significantly modulate the electronic structure with the d-band centers of Ni and Co atoms by shifting to lower energies with respect to the Fermi level,and optimize the Gibbs free energies of HER/OER intermediates,thereby accelerating water-splitting kinetics.When assembled as a solar-driven overall water-splitting electrolyzer,the as-prepared electrode shows a high and stable solar-to-hydrogen efficiency of 19.6%,indicating its potential for practical storage of intermittent energy.展开更多
The epitaxial heterostructure can be rationally designed based on the in situ growth of two compatible phases with lattice similarity,in which the modulated electronic states and tuned adsorption behaviors are conduci...The epitaxial heterostructure can be rationally designed based on the in situ growth of two compatible phases with lattice similarity,in which the modulated electronic states and tuned adsorption behaviors are conducive to the enhancement of electrocatalytic activity.Herein,theoretical simulations first disclose the charge transfer trend and reinforced inherent electron conduction around the epitaxial heterointerface between Ru clusters and Ni_(3)N substrate(cRu-Ni_(3)N),thus leading to the optimized adsorption behaviors and reduced activation energy barriers.Subsequently,the defectrich nanosheets with the epitaxially grown cRu-Ni_(3)N heterointerface are successfully constructed.Impressively,by virtue of the superiority of intrinsic activity and reaction kinetics,such unique epitaxial heterostructure exhibits remarkable bifunctional catalytic activity toward electrocatalytic OER(226 mV@20 mA cm^(−2))and HER(32 mV@10 mA cm^(−2))in alkaline media.Furthermore,it also shows great application prospect in alkaline freshwater and seawater splitting,as well as solar-to-hydrogen integrated system.This work could provide beneficial enlightenment for the establishment of advanced electrocatalysts with epitaxial heterointerfaces.展开更多
Developing efficient and durable hydrogen evolution reaction(HER)electrocatalysts is one of the most important issues for the commercialization of seawater electrolysis,but it remains challenging.Here,we report a CeO_...Developing efficient and durable hydrogen evolution reaction(HER)electrocatalysts is one of the most important issues for the commercialization of seawater electrolysis,but it remains challenging.Here,we report a CeO_(2)-CoP nanoneedle array catalyst loaded on Ti mesh(CeO_(2)-CoP/TM)with workfunction-induced directional charge transport properties.The CeO_(2)-CoP/TM catalyst showed superior HER catalytic activity and stability,with over potentials of 41 and 60 mV to attain 10 mA cm^(-2),in 1 M KOH and 1 M KOH+seawater electrolyte,respectively.Experimental results and theoretical calculations reveal that the work function drives the charge transfer from CeO_(2)to CoP,which effectively balances the electronic density of CoP and CeO_(2),optimizes the d-band center,and accelerates the water activation kinetics,thus enhancing the HER activity.The solar-driven water electrolysis device displays a high and stable solar-to-hydrogen conversion efficiency of 19.6%.This study offers a work function-induced directional charge transport strategy to design efficient and durable catalysts for hydrogen production.展开更多
The construction of efficient and durable electrocatalysts with highly dispersed metal clusters and hydrophilic surface for alkaline hydrogen evolution reaction(HER)remains a great challenge.Herein,we prepared hydroph...The construction of efficient and durable electrocatalysts with highly dispersed metal clusters and hydrophilic surface for alkaline hydrogen evolution reaction(HER)remains a great challenge.Herein,we prepared hydrophilic nanocomposites of Ru clusters(~1.30 nm)anchored on Na^(+),K^(+)-decorated porous carbon(Ru/Na^(+),K^(+)-PC)through hydrothermal method and subsequent annealing treatment at 500℃.The Ru/Na^(+),K^(+)-PC exhibits ultralow overpotential of 7 mV at 10 mA·cm^(-2),mass activity of 15.7 A·mgRu^(-1)at 100 mV,and long-term durability of 20,000 cycles potential cycling and 200 h chronopotentiometric measurement with a negligible decrease in activity,much superior to benchmarked commercial Pt/C.Density functional theory based calculations show that the energy barrier of H-OH bond breaking is efficiently reduced due to the presence of Na and K ions,thus favoring the Volmer step.Furthermore,the Ru/Na^(+),K^(+)-PC effectively employs solar energy for obtaining H_(2)in both alkaline water and seawater electrolyzer.This finding provides a new strategy to construct high-performance and cost-effective alkaline HER electrocatalyst.展开更多
Photoelectrochemical(PEC) cells involved with semiconductor electrodes can simultaneously absorb solar energy and perform chemical reactions, which are considered as an attractive strategy to produce renewable and cle...Photoelectrochemical(PEC) cells involved with semiconductor electrodes can simultaneously absorb solar energy and perform chemical reactions, which are considered as an attractive strategy to produce renewable and clean hydrogen energy. Sb_(2)Se_(3) has been widely investigated in constructing PEC photocathodes benefitting of its low toxicity, suitable band gap, superior optoelectronic properties, and outstanding photocorrosion stability. We first present a brief overview of basic concepts and principles of PEC water splitting as well as a comparison between Sb_(2)Se_(3) and other numerous candidates. Then the material characteristics and preparation methods of Sb_(2)Se_(3) are introduced. The development of Sb_(2)Se_(3)-based photocathodes in PEC water splitting with various architectures and engineering efforts(i.e., absorber engineering, interfaces engineering, co-catalyst engineering and tandem engineering) to improve solar-to-hydrogen(STH) efficiency are highlighted. Finally, we debate the possible future directions to further explore the researching fields of Sb_(2)Se_(3)-based photocathodes with a strongly positive outlook in PEC processed solar hydrogen production.展开更多
Two-dimensional(2 D)van der Waals materials have been widely adopted as photocatalysts for water splitting,but the energy conversion efficiency remains low.On the basis of first-principles calculations,we demonstrate ...Two-dimensional(2 D)van der Waals materials have been widely adopted as photocatalysts for water splitting,but the energy conversion efficiency remains low.On the basis of first-principles calculations,we demonstrate that the 2 D Janus group-Ⅲchalcogenide multilayers:In Ga XY,M2XY and In GaX2(M=In/Ga;X,Y=S/Se/Te),are promising photocatalysts for highly-efficient overall water splitting.The intrinsic electric field enhances the spatial separations of photogenerated carriers and alters the band alignment,which is more pronounced compared with the Janus monolayers.High solar-to-hydrogen(STH)efficiency with the upper limit of 38.5%was predicted in the Janus multilayers.More excitingly,the Ga vacancy of In Ga SSe bilayer effectively lowers the overpotentials of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)to the levels provided solely by the photogenerated carriers.Our theoretical results suggest that the 2 D Janus group-III chalcogenide multilayers could be utilized as highly efficient photocatalysts for overall water splitting without the needs of sacrificial reagents.展开更多
Due to the growing demand for clean and renewable hydrogen fuel,there has been a surge of interest in electrocatalytic water-splitting devices driven by renewable energy sources.However,the feasibility of self-driven ...Due to the growing demand for clean and renewable hydrogen fuel,there has been a surge of interest in electrocatalytic water-splitting devices driven by renewable energy sources.However,the feasibility of self-driven water splitting is limited by inefficient connections between functional modules,lack of highly active and stable electrocatalysts,and intermittent and unpredictable renewable energy supply.Herein,we construct a dualmodulated three-dimensional(3D)NiCo_(2)O_(4)@NiCo_(2)S_(4)(denoted as NCONCS)heterostructure deposited on nickel foam as a multifunctional electrode for electrocatalytic water splitting driven by photovoltaic-powered supercapacitors.Due to a stable 3D architecture configuration,abundant active sites,efficient charge transfer,and tuned interface properties,the NCONCS delivers a high specific capacity and rate performance for supercapacitors.A twoelectrode electrolyzer assembled with the NCONCS as both the anode and the cathode only requires a low cell voltage of 1.47 V to achieve a current density of 10 mA cm^(−2) in alkaline electrolyte,which outperforms the state-of-the-art bifunctional electrocatalysts.Theoretical calculations suggest that the generated heterointerfaces in NCONCS improve the surface binding capability of reaction intermediates while regulating the local electronic structures,which thus accelerates the reaction kinetics of water electrolysis.As a proof of concept,an integrated configuration comprising a two-electrode electrolyzer driven by two series-connected supercapacitors charged by a solar cell delivers a high product yield with superior durability.展开更多
The development of conjugated polymer photocatalysts for efficient solar-to-hydrogen energy conversion is highly desirable for the sustainability of our society.Although the construction of donor-acceptor(D-A)structur...The development of conjugated polymer photocatalysts for efficient solar-to-hydrogen energy conversion is highly desirable for the sustainability of our society.Although the construction of donor-acceptor(D-A)structure in conjugated polymer photocatalysts for solar-to-hydrogen energy conversion has been well documented,less attention has been paid on how large D and how large A units combined together could achieve the best performance.Herein,a series of D-A copolymers P(BDT-DBTSOx)(x=7,19,39,and 79)composed of a benzodithiophene(BDT)donor unit and an oligomeric dibenzo[b,d]thiophene sulfone(DBTSO)acceptor segment were synthesized and studied.It was found that the polymer photocatalytic stabilities under full-arc irradiation improved upon shortening the length of the acceptor segment.Under visible light irradiation and in the presence of 3 wt%Pt cocatalyst,P(BDT-DBTSO79)displayed the best performance with an optimal hydrogen evolution rate of 119.3±5.8 mmol·g^(-1)·h^(-1).This is 1.4-fold as that of DBTSO homopolymer and 22.5-fold as that of BDT/DBTSO alternative copolymer,highlighting the importance of acceptor length in D-A structure for achieving high photocatalytic performance.展开更多
The efficiency of photo-electrocatalytic（PECa） devices for the production of solar fuels depends on several limiting factors such as light harvesting, charge recombination and mass transport diffusion. We analyse he...The efficiency of photo-electrocatalytic（PECa） devices for the production of solar fuels depends on several limiting factors such as light harvesting, charge recombination and mass transport diffusion. We analyse here how they influence the performances in PECa cells having a photo-anode based on Au-modified TiOnanotube（TNT） arrays, with the aim of developing design criteria to optimize the photo-anode and the PECa cell configuration for water photo-electrolysis（splitting） and ethanol photo-reforming processes.The TNT samples were prepared by controlled anodic oxidation of Ti foils and then decorated with gold nanoparticles using different techniques to enhance the visible light response through heterojunction and plasmonic effects. The activity tests were made in a gas-phase reactor, as well as in a PECa cell without applied bias. Results were analysed in terms of photo-generated current, Hproduction rate and photoconversion efficiency. Particularly, a solar-to-hydrogen efficiency of 0.83% and a Faradaic efficiency of 91%were obtained without adding sacrificial reagents.展开更多
The generation of green hydrogen(H_2) energy is of great significance to solve worldwide energy and environmental issues. Reduced Ti based photocatalyst has recently attracted intensive attention due to its excellent ...The generation of green hydrogen(H_2) energy is of great significance to solve worldwide energy and environmental issues. Reduced Ti based photocatalyst has recently attracted intensive attention due to its excellent photocatalytic activity, while the synthesis of reduced Ti based photocatalysts with high stability is still a great challenge. Here, we report a facile method for synthesis of reduced Ti metal organic frameworks(small amounts of Pt incorporated) encapsulated BP(BP/R-Ti-MOFs/Pt) hybrid nanomaterial with enhanced photocatalytic activity. The strong interaction between Ti and P reduces the valence state of the binding Ti^(4+)on the BP surface, forming abundant reduced Ti^(4+)within R-Ti-MOFs/BP. Such reduced Ti^(4+)render R-Ti-MOFs/BP efficient charge transfer and excellent light absorption capability, thus promote the photocatalytic H_2 production efficiency. Furthermore, the Ti-P interaction stabilizes both reduced Ti^(4+)and BP during the photocatalytic reaction, which greatly enhanced the stability of the obtained BP/R-TiMOFs/Pt photocatalyst.展开更多
Photocatalytic water splitting is a promising strategy to produce hydrogen as a sustainable and clean energy carrier,based on abundant solar energy and semiconductor photocatalysts,and it has received extensive resear...Photocatalytic water splitting is a promising strategy to produce hydrogen as a sustainable and clean energy carrier,based on abundant solar energy and semiconductor photocatalysts,and it has received extensive research and discussion over the past several decades.It is challenging,however,to achieve an efficient solar-to-hydrogen evolution process with a single particulate photocatalyst due to the weak solar spectrum harvest and the rapid recombination of photogenerated electron-hole pairs during the photocatalysis reaction.Combining semiconductors to create different co-catalysts presents a viable solution to the above issues.Recently,semiconductor photocatalysts modified by different transition metal sulfidebased co-catalysts with designed functions,especially in light absorption enhancement and chargecarrier-separation efficiency promotion,have attracted much attention.As continued breakthroughs have been made in the preparation,modification,and solar-to-hydrogen evolution application of the 1T phase MS_(2)(M=W,Mo)co-catalyst-based photocatalysis system in recent years,we believe that a comprehensive review of this kind of co-catalyst would further promote its research and development to address the energy and environmental challenges that we are currently facing.Herein,recent studies and progress are summarized on the fabrication of 1T phase MS_(2)(M=W,Mo)-based co-catalyst materials,as well as their roles and functional mechanisms for photocatalytic H;evolution.Finally,concluding perspectives on the opportunities in and challenges for the further exploration of the 1T-MS_(2)(M=W,Mo)-based solar-tohydrogen evolution system are presented.展开更多
Designing and developing the highly efficient photocatalysts is full of significance to achieve spontaneous photolysis water.In this work,using the first-principles calculations,we have performed a systematic theoreti...Designing and developing the highly efficient photocatalysts is full of significance to achieve spontaneous photolysis water.In this work,using the first-principles calculations,we have performed a systematic theoretical study of water splitting photocatalytic activity of the InS e/g-CN heterojunction.It is concluded that the In Se/g-CN heterojunction is a typical type-II semiconductor,whose electrons and holes can be effectively separated.And the potential of the conduction band minimum(CBM)and valence band maximum(VBM)satisfy the requirements for photolysis water.Moreover,the changes of Gibbs free energy(ΔG)of the oxygen evolution reaction(OER)and the hydrogen evolution reaction(HER)are calculated to investigate thermodynamic sustainability of photolysis water.The results show that when pH=7,the potential driving force provided by the InSe/g-CN heterojunction can ensure the spontaneous progress of HER and OER.In addition,it is found that the solar conversion efficiency(η;)of the In Se/g-CN heterojunction is up to 13.7%,which indicates it has broad commercial application prospects.Hence,the In Se/g-CN heterojunction is expected to be an excellent candidate for photolysis water.展开更多
Solar-hydrogen system has great potential for contributing to sustainable and clean energy supply. The aim of this study is to clarify the impact of heat transfer media in solar collector such as methane, ammonium, hy...Solar-hydrogen system has great potential for contributing to sustainable and clean energy supply. The aim of this study is to clarify the impact of heat transfer media in solar collector such as methane, ammonium, hydrogen, air and water on the performance of solar-hydrogen system. After estimating the highest temperature attainable by each heat transfer media, the amount of thermal energy that could be saved in the production of hydrogen or preheat for power generation by fuel cell was calculated. The power generation performance of fuel cell using each heat transfer media was also investigated. As a result, it has been revealed that the temperature changes of methane, ammonium and air follow the horizontal solar radiation intensity irrespective of seasons, and their highest temperatures are almost the same among them. The temperature response of hydrogen is slower than methane, ammonium and air. This study defines the ratio of saving thermal energy which indicates the effect of solar thermal utilization for production of hydrogen or preheat for power generation by fuel cell without using utility gas. It has been found that the biggest thermal energy saving is obtained when hydrogen and air are used as the heat transfer media. The power generated by PEFC system per effective area of evacuated tube collector in the case of using methane or ammonium is 3.309×10-2 kWh/m2 and 2.076×10-2 kWh/m2, respectively, while it is 2.466×10-2 kWh in the case of using hydrogen and air.展开更多
基金supported by the Double Tops Joint Fund of the Yunnan Science and Technology Bureau and Yunnan University(2019FY003025)the National Natural Science Foundation of China(U2002213 and 51621001)+2 种基金the East-Land Middle-aged and Young Backbone Teacher of Yunnan University(No.C176220200)Yunnan Applied Basic Research Projects(202001BB050006,202001BB050007)the Double-First Class University Plan(C176220100042).
文摘The construction of high-efficiency and low-cost non-noble metal bifunctional electrocatalysts for water electrolysis is crucial for commercial large-scale application of hydrogen energy.Here,we report a novel strategy with erbiumdoped NiCoP nanowire arrays in situ grown on conductive nickel foam(Er-NiCoP/NF).Significantly,the developed electrode shows exceptional bifunctional catalytic activity,which only requires overpotentials of 46 and 225 mV to afford a current density of 10 mAcm^(−2) for the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER),respectively.Density functional theory calculations reveal that the appropriate Er incorporation into the NiCoP lattice can significantly modulate the electronic structure with the d-band centers of Ni and Co atoms by shifting to lower energies with respect to the Fermi level,and optimize the Gibbs free energies of HER/OER intermediates,thereby accelerating water-splitting kinetics.When assembled as a solar-driven overall water-splitting electrolyzer,the as-prepared electrode shows a high and stable solar-to-hydrogen efficiency of 19.6%,indicating its potential for practical storage of intermittent energy.
基金financially sponsored by the National Natural Science Foundation of China(Grant No.22075223,22179104)the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology)(2021-ZD-4)the Fundamental Research Funds for the Central Universities(No.2020-YB-012)。
文摘The epitaxial heterostructure can be rationally designed based on the in situ growth of two compatible phases with lattice similarity,in which the modulated electronic states and tuned adsorption behaviors are conducive to the enhancement of electrocatalytic activity.Herein,theoretical simulations first disclose the charge transfer trend and reinforced inherent electron conduction around the epitaxial heterointerface between Ru clusters and Ni_(3)N substrate(cRu-Ni_(3)N),thus leading to the optimized adsorption behaviors and reduced activation energy barriers.Subsequently,the defectrich nanosheets with the epitaxially grown cRu-Ni_(3)N heterointerface are successfully constructed.Impressively,by virtue of the superiority of intrinsic activity and reaction kinetics,such unique epitaxial heterostructure exhibits remarkable bifunctional catalytic activity toward electrocatalytic OER(226 mV@20 mA cm^(−2))and HER(32 mV@10 mA cm^(−2))in alkaline media.Furthermore,it also shows great application prospect in alkaline freshwater and seawater splitting,as well as solar-to-hydrogen integrated system.This work could provide beneficial enlightenment for the establishment of advanced electrocatalysts with epitaxial heterointerfaces.
基金financially supported by the National Natural Science Foundation of China(22369025)the Yunnan Applied Basic Research Projects(202201AT070095,202301AT070098)+2 种基金the Scientific Research Fund Project of Yunnan Provincial Department of Education(2023Y0262)the Education Reform Research Project of Yunnan University(2021Z06)the Yunnan Revitalization Talent Support Program。
文摘Developing efficient and durable hydrogen evolution reaction(HER)electrocatalysts is one of the most important issues for the commercialization of seawater electrolysis,but it remains challenging.Here,we report a CeO_(2)-CoP nanoneedle array catalyst loaded on Ti mesh(CeO_(2)-CoP/TM)with workfunction-induced directional charge transport properties.The CeO_(2)-CoP/TM catalyst showed superior HER catalytic activity and stability,with over potentials of 41 and 60 mV to attain 10 mA cm^(-2),in 1 M KOH and 1 M KOH+seawater electrolyte,respectively.Experimental results and theoretical calculations reveal that the work function drives the charge transfer from CeO_(2)to CoP,which effectively balances the electronic density of CoP and CeO_(2),optimizes the d-band center,and accelerates the water activation kinetics,thus enhancing the HER activity.The solar-driven water electrolysis device displays a high and stable solar-to-hydrogen conversion efficiency of 19.6%.This study offers a work function-induced directional charge transport strategy to design efficient and durable catalysts for hydrogen production.
基金This work was supported by the National Natural Science Foundation of China(No.21571038)Education Department of Guizhou Province(No.2021312)+4 种基金Foundation of Guizhou Province(No.2019-5666)State Key Laboratory of Coal Mine Disaster Dynamics and Control(Chongqing University,No.2011DA105287-ZR202101)Science Foundation for After graduated Students of Guizhou Province(No.YJSKYJJ2021023)State Key Laboratory of Physical Chemistry of Solid Surfaces(Xiamen University,No.202009)the Open Fund of the Key Lab of Organic Optoelectronics and Molecular Engineering(Tsinghua University).
文摘The construction of efficient and durable electrocatalysts with highly dispersed metal clusters and hydrophilic surface for alkaline hydrogen evolution reaction(HER)remains a great challenge.Herein,we prepared hydrophilic nanocomposites of Ru clusters(~1.30 nm)anchored on Na^(+),K^(+)-decorated porous carbon(Ru/Na^(+),K^(+)-PC)through hydrothermal method and subsequent annealing treatment at 500℃.The Ru/Na^(+),K^(+)-PC exhibits ultralow overpotential of 7 mV at 10 mA·cm^(-2),mass activity of 15.7 A·mgRu^(-1)at 100 mV,and long-term durability of 20,000 cycles potential cycling and 200 h chronopotentiometric measurement with a negligible decrease in activity,much superior to benchmarked commercial Pt/C.Density functional theory based calculations show that the energy barrier of H-OH bond breaking is efficiently reduced due to the presence of Na and K ions,thus favoring the Volmer step.Furthermore,the Ru/Na^(+),K^(+)-PC effectively employs solar energy for obtaining H_(2)in both alkaline water and seawater electrolyzer.This finding provides a new strategy to construct high-performance and cost-effective alkaline HER electrocatalyst.
基金supported by the National Natural Science Foundation of China(No.62074102)Natural Science Foundation of Guangdong Province(2020A1515010805)China+1 种基金the Key Project of Department of Education of Guangdong Province(No.2018KZDXM059)Chinathe Science and Technology plan project of Shenzhen(20200812000347001,JCYJ20190808153409238)China。
文摘Photoelectrochemical(PEC) cells involved with semiconductor electrodes can simultaneously absorb solar energy and perform chemical reactions, which are considered as an attractive strategy to produce renewable and clean hydrogen energy. Sb_(2)Se_(3) has been widely investigated in constructing PEC photocathodes benefitting of its low toxicity, suitable band gap, superior optoelectronic properties, and outstanding photocorrosion stability. We first present a brief overview of basic concepts and principles of PEC water splitting as well as a comparison between Sb_(2)Se_(3) and other numerous candidates. Then the material characteristics and preparation methods of Sb_(2)Se_(3) are introduced. The development of Sb_(2)Se_(3)-based photocathodes in PEC water splitting with various architectures and engineering efforts(i.e., absorber engineering, interfaces engineering, co-catalyst engineering and tandem engineering) to improve solar-to-hydrogen(STH) efficiency are highlighted. Finally, we debate the possible future directions to further explore the researching fields of Sb_(2)Se_(3)-based photocathodes with a strongly positive outlook in PEC processed solar hydrogen production.
基金supported by the National Natural Science Foundation of China (21433006 and 11774201)
文摘Two-dimensional(2 D)van der Waals materials have been widely adopted as photocatalysts for water splitting,but the energy conversion efficiency remains low.On the basis of first-principles calculations,we demonstrate that the 2 D Janus group-Ⅲchalcogenide multilayers:In Ga XY,M2XY and In GaX2(M=In/Ga;X,Y=S/Se/Te),are promising photocatalysts for highly-efficient overall water splitting.The intrinsic electric field enhances the spatial separations of photogenerated carriers and alters the band alignment,which is more pronounced compared with the Janus monolayers.High solar-to-hydrogen(STH)efficiency with the upper limit of 38.5%was predicted in the Janus multilayers.More excitingly,the Ga vacancy of In Ga SSe bilayer effectively lowers the overpotentials of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)to the levels provided solely by the photogenerated carriers.Our theoretical results suggest that the 2 D Janus group-III chalcogenide multilayers could be utilized as highly efficient photocatalysts for overall water splitting without the needs of sacrificial reagents.
文摘Due to the growing demand for clean and renewable hydrogen fuel,there has been a surge of interest in electrocatalytic water-splitting devices driven by renewable energy sources.However,the feasibility of self-driven water splitting is limited by inefficient connections between functional modules,lack of highly active and stable electrocatalysts,and intermittent and unpredictable renewable energy supply.Herein,we construct a dualmodulated three-dimensional(3D)NiCo_(2)O_(4)@NiCo_(2)S_(4)(denoted as NCONCS)heterostructure deposited on nickel foam as a multifunctional electrode for electrocatalytic water splitting driven by photovoltaic-powered supercapacitors.Due to a stable 3D architecture configuration,abundant active sites,efficient charge transfer,and tuned interface properties,the NCONCS delivers a high specific capacity and rate performance for supercapacitors.A twoelectrode electrolyzer assembled with the NCONCS as both the anode and the cathode only requires a low cell voltage of 1.47 V to achieve a current density of 10 mA cm^(−2) in alkaline electrolyte,which outperforms the state-of-the-art bifunctional electrocatalysts.Theoretical calculations suggest that the generated heterointerfaces in NCONCS improve the surface binding capability of reaction intermediates while regulating the local electronic structures,which thus accelerates the reaction kinetics of water electrolysis.As a proof of concept,an integrated configuration comprising a two-electrode electrolyzer driven by two series-connected supercapacitors charged by a solar cell delivers a high product yield with superior durability.
基金support from the National Natural Science Foundation of China(Nos.21674125,21672251,21975279,and 51761145043)the Strategic Priority Research Program of Ghines Asademy of Scienses(No,XDB20020000)+1 种基金Shanghai Institute of Organic Chemistry(No.sioczz202123)Zhengzhou University of Technology.
文摘The development of conjugated polymer photocatalysts for efficient solar-to-hydrogen energy conversion is highly desirable for the sustainability of our society.Although the construction of donor-acceptor(D-A)structure in conjugated polymer photocatalysts for solar-to-hydrogen energy conversion has been well documented,less attention has been paid on how large D and how large A units combined together could achieve the best performance.Herein,a series of D-A copolymers P(BDT-DBTSOx)(x=7,19,39,and 79)composed of a benzodithiophene(BDT)donor unit and an oligomeric dibenzo[b,d]thiophene sulfone(DBTSO)acceptor segment were synthesized and studied.It was found that the polymer photocatalytic stabilities under full-arc irradiation improved upon shortening the length of the acceptor segment.Under visible light irradiation and in the presence of 3 wt%Pt cocatalyst,P(BDT-DBTSO79)displayed the best performance with an optimal hydrogen evolution rate of 119.3±5.8 mmol·g^(-1)·h^(-1).This is 1.4-fold as that of DBTSO homopolymer and 22.5-fold as that of BDT/DBTSO alternative copolymer,highlighting the importance of acceptor length in D-A structure for achieving high photocatalytic performance.
基金The TERRA(Tandem Electrocatalytic Reactor for energy/Resource efficiency and process intensification,H2020 project 677471)Eco~2CO_2(Eco-friendly biorefinery fine chemicals from CO_2 photo-catalytic reduction,FP7 project 309701)
文摘The efficiency of photo-electrocatalytic（PECa） devices for the production of solar fuels depends on several limiting factors such as light harvesting, charge recombination and mass transport diffusion. We analyse here how they influence the performances in PECa cells having a photo-anode based on Au-modified TiOnanotube（TNT） arrays, with the aim of developing design criteria to optimize the photo-anode and the PECa cell configuration for water photo-electrolysis（splitting） and ethanol photo-reforming processes.The TNT samples were prepared by controlled anodic oxidation of Ti foils and then decorated with gold nanoparticles using different techniques to enhance the visible light response through heterojunction and plasmonic effects. The activity tests were made in a gas-phase reactor, as well as in a PECa cell without applied bias. Results were analysed in terms of photo-generated current, Hproduction rate and photoconversion efficiency. Particularly, a solar-to-hydrogen efficiency of 0.83% and a Faradaic efficiency of 91%were obtained without adding sacrificial reagents.
基金financially supported by the National Natural Science Foundation of China (21771154, 31371005)the Shenzhen Fundamental Research Programs (JCYJ20190809161013453)+1 种基金the Natural Science Foundation of Fujian Province of China (Nos. 2018J01019, 2018J05025)the Fundamental Research Funds for the Central Universities (20720180019, 20720180016)。
文摘The generation of green hydrogen(H_2) energy is of great significance to solve worldwide energy and environmental issues. Reduced Ti based photocatalyst has recently attracted intensive attention due to its excellent photocatalytic activity, while the synthesis of reduced Ti based photocatalysts with high stability is still a great challenge. Here, we report a facile method for synthesis of reduced Ti metal organic frameworks(small amounts of Pt incorporated) encapsulated BP(BP/R-Ti-MOFs/Pt) hybrid nanomaterial with enhanced photocatalytic activity. The strong interaction between Ti and P reduces the valence state of the binding Ti^(4+)on the BP surface, forming abundant reduced Ti^(4+)within R-Ti-MOFs/BP. Such reduced Ti^(4+)render R-Ti-MOFs/BP efficient charge transfer and excellent light absorption capability, thus promote the photocatalytic H_2 production efficiency. Furthermore, the Ti-P interaction stabilizes both reduced Ti^(4+)and BP during the photocatalytic reaction, which greatly enhanced the stability of the obtained BP/R-TiMOFs/Pt photocatalyst.
基金supported by the National Natural Science Foundation of China(21501137)Graduate Education Innovation Fund of Wuhan Institute of Technology(CX2020257)the Australian Research Council for funding through Discovery Early Career Researcher Award(DECRA,No.DE180101478)。
文摘Photocatalytic water splitting is a promising strategy to produce hydrogen as a sustainable and clean energy carrier,based on abundant solar energy and semiconductor photocatalysts,and it has received extensive research and discussion over the past several decades.It is challenging,however,to achieve an efficient solar-to-hydrogen evolution process with a single particulate photocatalyst due to the weak solar spectrum harvest and the rapid recombination of photogenerated electron-hole pairs during the photocatalysis reaction.Combining semiconductors to create different co-catalysts presents a viable solution to the above issues.Recently,semiconductor photocatalysts modified by different transition metal sulfidebased co-catalysts with designed functions,especially in light absorption enhancement and chargecarrier-separation efficiency promotion,have attracted much attention.As continued breakthroughs have been made in the preparation,modification,and solar-to-hydrogen evolution application of the 1T phase MS_(2)(M=W,Mo)co-catalyst-based photocatalysis system in recent years,we believe that a comprehensive review of this kind of co-catalyst would further promote its research and development to address the energy and environmental challenges that we are currently facing.Herein,recent studies and progress are summarized on the fabrication of 1T phase MS_(2)(M=W,Mo)-based co-catalyst materials,as well as their roles and functional mechanisms for photocatalytic H;evolution.Finally,concluding perspectives on the opportunities in and challenges for the further exploration of the 1T-MS_(2)(M=W,Mo)-based solar-tohydrogen evolution system are presented.
基金supports by National Natural Science Foundation of China(NSFC,Nos.51471124,U1766216)National Key R&D Program of China(No.2018YFB0905600)+1 种基金Natural Science Foundation of Shaanxi province,China(Nos.2019JM-189,2020JM218)supported by HPC Platform,Xi’an Jiaotong University。
文摘Designing and developing the highly efficient photocatalysts is full of significance to achieve spontaneous photolysis water.In this work,using the first-principles calculations,we have performed a systematic theoretical study of water splitting photocatalytic activity of the InS e/g-CN heterojunction.It is concluded that the In Se/g-CN heterojunction is a typical type-II semiconductor,whose electrons and holes can be effectively separated.And the potential of the conduction band minimum(CBM)and valence band maximum(VBM)satisfy the requirements for photolysis water.Moreover,the changes of Gibbs free energy(ΔG)of the oxygen evolution reaction(OER)and the hydrogen evolution reaction(HER)are calculated to investigate thermodynamic sustainability of photolysis water.The results show that when pH=7,the potential driving force provided by the InSe/g-CN heterojunction can ensure the spontaneous progress of HER and OER.In addition,it is found that the solar conversion efficiency(η;)of the In Se/g-CN heterojunction is up to 13.7%,which indicates it has broad commercial application prospects.Hence,the In Se/g-CN heterojunction is expected to be an excellent candidate for photolysis water.
文摘Solar-hydrogen system has great potential for contributing to sustainable and clean energy supply. The aim of this study is to clarify the impact of heat transfer media in solar collector such as methane, ammonium, hydrogen, air and water on the performance of solar-hydrogen system. After estimating the highest temperature attainable by each heat transfer media, the amount of thermal energy that could be saved in the production of hydrogen or preheat for power generation by fuel cell was calculated. The power generation performance of fuel cell using each heat transfer media was also investigated. As a result, it has been revealed that the temperature changes of methane, ammonium and air follow the horizontal solar radiation intensity irrespective of seasons, and their highest temperatures are almost the same among them. The temperature response of hydrogen is slower than methane, ammonium and air. This study defines the ratio of saving thermal energy which indicates the effect of solar thermal utilization for production of hydrogen or preheat for power generation by fuel cell without using utility gas. It has been found that the biggest thermal energy saving is obtained when hydrogen and air are used as the heat transfer media. The power generated by PEFC system per effective area of evacuated tube collector in the case of using methane or ammonium is 3.309×10-2 kWh/m2 and 2.076×10-2 kWh/m2, respectively, while it is 2.466×10-2 kWh in the case of using hydrogen and air.
