Artificial carbon fixation is a promising pathway for achieving the carbon cycle and environment remediation.However,the sluggish kinetics of oxygen evolution reaction(OER)and poor selectivity of CO_(2) reduction seri...Artificial carbon fixation is a promising pathway for achieving the carbon cycle and environment remediation.However,the sluggish kinetics of oxygen evolution reaction(OER)and poor selectivity of CO_(2) reduction seriously limited the overall conversion efficiencies of solar energy to chemical fuels.Herein,we demonstrated a facile and feasible strategy to rationally regulate the coordination environment and electronic structure of surface-active sites on both photoanode and cathode.More specifically,the defect engineering has been employed to reduce the coordination number of ultrathin FeNi catalysts decorated on BiVO4 photoanodes,resulting in one of the highest OER activities of 6.51 mA cm^(−2)(1.23 VRHE,AM 1.5G).Additionally,single-atom cobalt(II)phthalocyanine anchoring on the N-rich carbon substrates to increase Co–N coordination number remarkably promotes CO_(2) adsorption and activation for high selective CO production.Their integration achieved a record activity of 109.4μmol cm^(−2) h−1 for CO production with a faradaic efficiency of>90%,and an outstanding solar conversion efficiency of 5.41%has been achieved by further integrating a photovoltaic utilizing the sunlight(>500 nm).展开更多
Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silic...Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silicate hydroxide[Co_(2.5)Ni_(0.5)Si_(2)O_(5)(OH)_(4)]is vertically grown on a reduced graphene oxide(rGO)support(CNS@rGO).This is developed as a low-cost and prospective OER catalyst.Compared to cobalt or nickel silicate hydroxide@rGO(CS@rGO and NS@rGO,respectively)nanoarrays,the bimetal CNS@rGO nanoarray exhibits impressive OER performance with an overpotential of 307 mV@10 mA cm^(-2).This value is higher than that of CS@rGO and NS@rGO.The CNS@rGO nanoarray has an overpotential of 446 mV@100 mA cm^(-2),about 1.4 times that of the commercial RuO_(2)electrocatalyst.The achieved OER activity is superior to the state-of-the-art metal oxides/hydroxides and their derivatives.The vertically grown nanostructure and optimized metal-support electronic interactions play an indispensable role for OER performance improvement,including a fast electron transfer pathway,short proton/electron diffusion distance,more active metal centers,as well as optimized dualatomic electron density.Taking advantage of interlay chemical regulation and the in-situ growth method,the advanced-structural CNS@rGO nanoarrays provide a new horizon to the rational and flexible design of efficient and promising OER electrocatalysts.展开更多
Developing non‐noble‐metal electrocatalyst with efficient and durable activity is a urgent task for addressing the sluggish reaction kinetics of electrochemical water oxidation.Structural evolution of the electrocat...Developing non‐noble‐metal electrocatalyst with efficient and durable activity is a urgent task for addressing the sluggish reaction kinetics of electrochemical water oxidation.Structural evolution of the electrocatalyst is an important strategy for achieving enhanced performance.Herein,in situ evolution of surface Co_(2)CrO_(4) to CoOOH/CrOOH(CoOOH/CrOOH‐Co_(2)CrO_(4))by an electrochemical method under alkaline conditions was designed for enhancing the electrocatalytic performance of water oxidation.The experiments demonstrated that the synergy between CoOOH/CrOOH and Co_(2)CrO_(4) resulted in a marked increase in the number of active sites and improved the rate of charge transfer,which enhanced the activity for water oxidation.At a geometrical current density of 20 mA cm^(−2),the overpotential of the oxygen evolution reaction was 244 mV and the turnover frequency was 0.536 s^(−1) in 1.0 M NaOH.展开更多
High entropy alloys(HEAs)have gained significant attention in electrocatalysis research due to their distinctive multi-element composition,intricate electronic structure,and superior properties.By harnessing multi-com...High entropy alloys(HEAs)have gained significant attention in electrocatalysis research due to their distinctive multi-element composition,intricate electronic structure,and superior properties.By harnessing multi-component synergy,precise electron regulation,and the high-entropy effect,HEA electrocatalysts exhibit remarkable catalytic activity,selectivity,and stability.These materials demonstrate outstanding catalytic performance in a variety of electrocatalytic small molecule reduction reactions,including oxygen reduction(ORR),hydrogen evolution(HER),and CO_(2)reduction(CO_(2)RR),making them promising candidates for clean energy conversion and storage applications,including fuel cells,metal-air batteries,water electrolysis,and CO_(2)conversion technologies.This review highlights recent advancements in HEA electrocatalyst research,focusing on their synthesis,characterization,and applications in electrocatalytic small molecule reduction reactions.It also explores the underlying mechanisms of the high-entropy effect,multi-component synergy,and structural design.Finally,it discusses key challenges that remain in the application of HEAs for electrocatalytic small molecule reduction and outlines potential directions for future development in this field.展开更多
Developing cost-effective and highly efficient oxygen evolution reaction(OER)electrocatalysts that operate in both acidic and alkaline media is crucial for indus-trial electrocatalytic water splitting.However,achievin...Developing cost-effective and highly efficient oxygen evolution reaction(OER)electrocatalysts that operate in both acidic and alkaline media is crucial for indus-trial electrocatalytic water splitting.However,achieving high performance under dual pH conditions remains a significant challenge.Herein,we report the synthe-sis of multi-sized RuO_(2)sub-nanoclusters on Co_(3)O_(4)nanoarrays via a facile method,which demonstrates exceptional OER activity in both acidic and alkaline environ-ments.The optimized catalyst exhibits remarkably low overpotentials of 165 mV in 0.5 M H_(2)SO_(4)and 223 mV in 1 M KOH at a current density of 10 mA cm^(-2),respectively.Additionally,it exhibits outstanding stability,maintaining perfor-mance over a 10-h continuous operation,which is attributed to the robust struc-tural stability of the dispersed RuO_(2)sub-nanocluster morphology.Atomic-scale investigations reveal a layer-by-layer growth mechanism of Ru on the Co_(3)O_(4)sub-strate,transitioning from single atoms to monolayer clusters and ultimately to sub-nanoclusters as Ru loading increases.This growth mechanism provides a rational strategy for the precise design and synthesis of advanced cluster-based cat-alysts.Density functional theory(DFT)calculations further elucidate the strong oxide-support interactions between RuO_(2)clusters and the Co_(3)O_(4)matrix,facilitat-ing electron transfer from RuO_(2)to Co_(3)O_(4)and generating an electron-deficient region.This electronic modulation enhances–OH adsorption and accelerates OER kinetics.These findings underscore the potential of metal sub-nanoclusters for designing highly efficient and durable electrocatalysts for water electrolysis.展开更多
CO_(x)(x=1,2)and O_(2) chemistry play key roles in tackling global severe environmental challenges and energy issues.To date,the efficient selective electrocatalytic transformations of COx-carbon chemicals,and O_(2)-h...CO_(x)(x=1,2)and O_(2) chemistry play key roles in tackling global severe environmental challenges and energy issues.To date,the efficient selective electrocatalytic transformations of COx-carbon chemicals,and O_(2)-hydrogenated products are still huge challenges.Single-atom catalysts(SACs)as atomic-scale novel catalysts in which only isolated metal atoms are dispersed on supports shed new insights in overcome these obstacles in CO_(x) and O_(2) chemistry,including CO oxidation,CO_(2) reduction reaction(CO_(2)RR),oxygen reduction reaction(ORR),and oxygen evolution reaction(OER).In this review,the unique features and advanced synthesis strategies of SACs from a viewpoint of fundamental synthesis design are first highlighted to guide future strategy design for controllable SAC synthesis.Then,the to-date reported CO_(2)RR,CO oxidation,OER,and ORR mechanism are included and summarized.More importantly,the design principles and design strategies of improving the intrinsic activity,selectivity,and stability are extensively discussed and the engineering strategy is classified as neighbor coordination engineering,metal-atom engineering,and substrate engineering.Via the comprehensive review and summary of state-of-the-art SACs,the synthesis–structure–property–mechanism–design principle relation can be revealed to shed lights into the structural construction of SACs.Finally,we present an outlook on current challenges and future directions for SACs in CO_(x) and O_(2) chemistry.展开更多
Calcium sulfate(CaSO_(4))has been verified as a promising oxygen carrier(OC)in the chemical looping combustion(CLC)for its high oxygen capacity,abundant reserve and low cost,but its low reactivity and deleterious sulf...Calcium sulfate(CaSO_(4))has been verified as a promising oxygen carrier(OC)in the chemical looping combustion(CLC)for its high oxygen capacity,abundant reserve and low cost,but its low reactivity and deleterious sulfur species emission from the side reactions of CaSO_(4) should be well considered for its wide application in CLC.In order to promote the reactivity of CaSO_(4) and increase its potential to inhibit the gaseous sulfur emission,a CeO_(2)-enhanced CaSO_(4) OC mixed OC of core–shell structure was prepared using the combined template synthesis method.Reaction characteristics of the prepared CaSO_(4)-CeO_(2) mixed OC with a typical lignite was first conducted and systematically investigated,and an improved reactivity of the prepared CaSO_(4)-CeO_(2) mixed OC was demonstrated than its single component CaSO_(4) or CeO_(2) due to the fast transfer and exchange of oxygen from the CaSO_(4) substrate to coal via the doped CeO_(2).Furthermore,the solid products formed from the mixed CaSO_(4)-CeO_(2) OC with the selected coal were collected and analyzed.Especially,evolution and redistribution of the sulfur species of different forms were focused.At the latter reaction stage of YN reaction with the CaSO_(4)-CeO_(2) mixed OC,the SO_(2) emitted from the side reactions of CaSO_(4) was greatly diminished and the doped CeO_(2) was proven effective to directionally fix the SO_(2) released to turn into different solid sulfur compounds,which were determined as Ce_(2)O_(2)S,Ce_(2)S_(3) and Ce_(2)(SO_(4))_(3)·5H_(2)O and formed through the different pathways.In addition,good regeneration of the reduced CaSO_(4)-CeO_(2) mixed OC could be reached in spite of the unavoidable interaction between the included minerals in coal and the reduced mixed OC.Overall,the combined template method-made CaSO_(4)-CeO_(2) mixed OC reported herein was not only endowed with enhanced reactivity for coal conversion,but also owned the potential to directionally fix the gaseous sulfur emission,which is quite applicable as OC for simultaneous decarbonatization and desulfurization in the real CLC process.展开更多
Stable and high‐efficiency bifunctional catalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desired for the practical application of Li‐O_(2)batteries with excellent rate performanc...Stable and high‐efficiency bifunctional catalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desired for the practical application of Li‐O_(2)batteries with excellent rate performance and cycle stability.Herein,a novel hybrid bifunctional catalyst with carbon nanofibers inlaid with hollow Co_(3)O_(4)nanoparticles and separate active sites for ORR and OER were prepared and applied in Li‐O_(2)batteries.Benefiting from the synergistic effect of unique porous structural features and high electrocatalytic activity of hollow Co3O4 intimately bound to N‐doped carbon nanofibers,the assembled Li‐O_(2)batteries with novel catalyst exhibited high specific capacity,excellent rate capability,and cycle stability up to 150 cycles under a capacity limitation of 500 mAh g^(–1)at a current density of 100 mA g^(–1).The facile synthesis and preliminary results in this work show the as‐prepared catalyst as a promising bifunctional electrocatalyst for applications in metal‐air batteries,fuel cells,and electrocatalysis.展开更多
Regulating the orbital spin-electron filling of metal centers via interatomic electron transfer in transition metal oxides is one promising approach to enhancing their electrocatalytic oxygen evolution reaction(OER)pe...Regulating the orbital spin-electron filling of metal centers via interatomic electron transfer in transition metal oxides is one promising approach to enhancing their electrocatalytic oxygen evolution reaction(OER)performances,while it is still a challenge due to lacking of efficient strategy and deep understanding.In this work,a facile strategy containing electrochemical deposition and annealing in air atmosphere has been proposed to introduce monodispersed neodymium(Nd)atoms into spinel Co_(3)O_(4)nanosheets to trigger the electron transfer.Accordingly,the as-prepared Nd doped Co_(3)O_(4)nanosheets(Nd/Co_(3)O_(4))on nickel foam or carbon cloth showed greatly enhanced OER performances,with low overpotential of 284 and 396 mV at 10 m A cm^(-2),small Tafel slope of 95 and 119 mV dec^(-1)in 1.0 M KOH and 0.5 M H_(2)SO_(4),respectively.The experimental and density function theory results coherently indicate that the charge transfer in the Nd-O-Co asymmetric configuration not only enhances the conductivity of Co_(3)O_(4),but also regulates the filling degree of egorbitals of Co,leading to higher spin states,optimized adsorption ability,and accelerated H_(2)O dissociation process,thus achieving boosted OER activity.展开更多
Cubic perovskite oxides usually suffer from delamination and Sr^(2+) segregation for catalyzing oxygen evolution reaction (OER) at the anodes of solid oxide electrolysis cells (SOECs). It is crucial to develop alterna...Cubic perovskite oxides usually suffer from delamination and Sr^(2+) segregation for catalyzing oxygen evolution reaction (OER) at the anodes of solid oxide electrolysis cells (SOECs). It is crucial to develop alternative and efficient anode materials for SOECs. Herein, a series of novel Y_(0.95-x)Sr_(x)Co_(0.3)Fe_(0.7)O_(3-δ) (YSCF-x) orthorhombic perovskite oxides in the Pnma (62) space group are synthesized as anode materials of SOECs. Physicochemical characterizations and density functional theory calculations reveal that the partial substitution of Y^(3+) by Sr^(2+) increases the oxygen vacancy concentration and mobility as well as improves the electrical conductivity, which contributes to the excellent OER activity of YSCF-x. At 800 °C, the current density of SOEC with YSCF-0.05-Ce0.8Sm0.2O2-δ anode can reach 1.32 A cm^(−2) at 1.6 V, about twice that of SOEC with Y_(0.95-x)Sr_(x)Co_(0.3)Fe_(0.7)O_(3-δ)-Ce_(0.8)Sm_(0.2)O_(2-δ) anode. This work paves a new avenue for the design of advanced anode materials of SOECs.展开更多
Self-reconstruction of catalysts during oxygen evolution reaction(OER)is crucial for the development of energy conversion technologies.However,the relationship between the specific atomic structure of pre-catalysts an...Self-reconstruction of catalysts during oxygen evolution reaction(OER)is crucial for the development of energy conversion technologies.However,the relationship between the specific atomic structure of pre-catalysts and their electrocatalytic behavior after reconstruction via dual-ion leaching has not been extensively researched.In this work,we design a highly effective non-noble metal OER catalyst with heterointerface through continuous self-reconstruction of Co_(2)(OH)_(3)Cl@NiMoO_(4)as pre-catalyst by a straightforward dual-ion(i.e.MoO_(4)^(2-)and Cl^(-))leaching.In-situ Raman and in-situ Fourier transform infrared(FT-IR)spectroscopy have precisely identified the progressive phase transformation of the pre-catalyst during self-reconstruction,which results in a stable heterojunction of CoOOH and NiOOH(CoOOH@NiOOH).Further calculations based on density functional theory(DFT)of CoOOH@NiOOH evident that more electrons will be aggregated in the Fermi level of Co.Notably,Gibbs free energy(ΔG)for different OER steps of CoOOH@NiOOH exhibit lower energy costs of all intermediates,implying the well catalytic properties.Ultimately,the catalyst derived from dual-ion leaching displays outstanding OER performance,characterized by an overpotential of 275 mV at a current density of 10 mA·cm^(-2)and exceptional stability over 12 h reaction.This work successfully paves a way of finding high-performance OER catalysts based on non-noble metal through dual-ion leaching during self-reconstruction.展开更多
基金supported by the National Natural Science Foundation of China(21832005,22072168,22002175)Major Program of the Lanzhou Institute of Chemical Physics,CAS(No.ZYFZFX-3)+1 种基金Major Science and Technology Projects in Gansu Province(22ZD6GA003)West Light Foundation of The Chinese Academy of Sciences(xbzg-zdsys-202209).
文摘Artificial carbon fixation is a promising pathway for achieving the carbon cycle and environment remediation.However,the sluggish kinetics of oxygen evolution reaction(OER)and poor selectivity of CO_(2) reduction seriously limited the overall conversion efficiencies of solar energy to chemical fuels.Herein,we demonstrated a facile and feasible strategy to rationally regulate the coordination environment and electronic structure of surface-active sites on both photoanode and cathode.More specifically,the defect engineering has been employed to reduce the coordination number of ultrathin FeNi catalysts decorated on BiVO4 photoanodes,resulting in one of the highest OER activities of 6.51 mA cm^(−2)(1.23 VRHE,AM 1.5G).Additionally,single-atom cobalt(II)phthalocyanine anchoring on the N-rich carbon substrates to increase Co–N coordination number remarkably promotes CO_(2) adsorption and activation for high selective CO production.Their integration achieved a record activity of 109.4μmol cm^(−2) h−1 for CO production with a faradaic efficiency of>90%,and an outstanding solar conversion efficiency of 5.41%has been achieved by further integrating a photovoltaic utilizing the sunlight(>500 nm).
基金supported by the Fundamental Research Funds for the Central Universities(DUT21LK34)Natural Science Foundation of Liaoning Province(2020-MS-113).
文摘Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silicate hydroxide[Co_(2.5)Ni_(0.5)Si_(2)O_(5)(OH)_(4)]is vertically grown on a reduced graphene oxide(rGO)support(CNS@rGO).This is developed as a low-cost and prospective OER catalyst.Compared to cobalt or nickel silicate hydroxide@rGO(CS@rGO and NS@rGO,respectively)nanoarrays,the bimetal CNS@rGO nanoarray exhibits impressive OER performance with an overpotential of 307 mV@10 mA cm^(-2).This value is higher than that of CS@rGO and NS@rGO.The CNS@rGO nanoarray has an overpotential of 446 mV@100 mA cm^(-2),about 1.4 times that of the commercial RuO_(2)electrocatalyst.The achieved OER activity is superior to the state-of-the-art metal oxides/hydroxides and their derivatives.The vertically grown nanostructure and optimized metal-support electronic interactions play an indispensable role for OER performance improvement,including a fast electron transfer pathway,short proton/electron diffusion distance,more active metal centers,as well as optimized dualatomic electron density.Taking advantage of interlay chemical regulation and the in-situ growth method,the advanced-structural CNS@rGO nanoarrays provide a new horizon to the rational and flexible design of efficient and promising OER electrocatalysts.
文摘Developing non‐noble‐metal electrocatalyst with efficient and durable activity is a urgent task for addressing the sluggish reaction kinetics of electrochemical water oxidation.Structural evolution of the electrocatalyst is an important strategy for achieving enhanced performance.Herein,in situ evolution of surface Co_(2)CrO_(4) to CoOOH/CrOOH(CoOOH/CrOOH‐Co_(2)CrO_(4))by an electrochemical method under alkaline conditions was designed for enhancing the electrocatalytic performance of water oxidation.The experiments demonstrated that the synergy between CoOOH/CrOOH and Co_(2)CrO_(4) resulted in a marked increase in the number of active sites and improved the rate of charge transfer,which enhanced the activity for water oxidation.At a geometrical current density of 20 mA cm^(−2),the overpotential of the oxygen evolution reaction was 244 mV and the turnover frequency was 0.536 s^(−1) in 1.0 M NaOH.
基金supported by the National Natural Science Foundation of China(Grant No.22302042)the Pilot Group Program of the Research Fund for International Senior Scientists(Grant No.22250710676).
文摘High entropy alloys(HEAs)have gained significant attention in electrocatalysis research due to their distinctive multi-element composition,intricate electronic structure,and superior properties.By harnessing multi-component synergy,precise electron regulation,and the high-entropy effect,HEA electrocatalysts exhibit remarkable catalytic activity,selectivity,and stability.These materials demonstrate outstanding catalytic performance in a variety of electrocatalytic small molecule reduction reactions,including oxygen reduction(ORR),hydrogen evolution(HER),and CO_(2)reduction(CO_(2)RR),making them promising candidates for clean energy conversion and storage applications,including fuel cells,metal-air batteries,water electrolysis,and CO_(2)conversion technologies.This review highlights recent advancements in HEA electrocatalyst research,focusing on their synthesis,characterization,and applications in electrocatalytic small molecule reduction reactions.It also explores the underlying mechanisms of the high-entropy effect,multi-component synergy,and structural design.Finally,it discusses key challenges that remain in the application of HEAs for electrocatalytic small molecule reduction and outlines potential directions for future development in this field.
基金NSFC,Grant/Award Number:52203304Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory,Grant/Award Numbers:XHD2022-001,XHD2021-001,XHQN2022-005,XHRD2023-005Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2022A1515110627。
文摘Developing cost-effective and highly efficient oxygen evolution reaction(OER)electrocatalysts that operate in both acidic and alkaline media is crucial for indus-trial electrocatalytic water splitting.However,achieving high performance under dual pH conditions remains a significant challenge.Herein,we report the synthe-sis of multi-sized RuO_(2)sub-nanoclusters on Co_(3)O_(4)nanoarrays via a facile method,which demonstrates exceptional OER activity in both acidic and alkaline environ-ments.The optimized catalyst exhibits remarkably low overpotentials of 165 mV in 0.5 M H_(2)SO_(4)and 223 mV in 1 M KOH at a current density of 10 mA cm^(-2),respectively.Additionally,it exhibits outstanding stability,maintaining perfor-mance over a 10-h continuous operation,which is attributed to the robust struc-tural stability of the dispersed RuO_(2)sub-nanocluster morphology.Atomic-scale investigations reveal a layer-by-layer growth mechanism of Ru on the Co_(3)O_(4)sub-strate,transitioning from single atoms to monolayer clusters and ultimately to sub-nanoclusters as Ru loading increases.This growth mechanism provides a rational strategy for the precise design and synthesis of advanced cluster-based cat-alysts.Density functional theory(DFT)calculations further elucidate the strong oxide-support interactions between RuO_(2)clusters and the Co_(3)O_(4)matrix,facilitat-ing electron transfer from RuO_(2)to Co_(3)O_(4)and generating an electron-deficient region.This electronic modulation enhances–OH adsorption and accelerates OER kinetics.These findings underscore the potential of metal sub-nanoclusters for designing highly efficient and durable electrocatalysts for water electrolysis.
基金supported by the National Natural Science Foundation of China(No.51632007)the National Science and Technology Major Project(2017-VI-0007-0077)。
文摘CO_(x)(x=1,2)and O_(2) chemistry play key roles in tackling global severe environmental challenges and energy issues.To date,the efficient selective electrocatalytic transformations of COx-carbon chemicals,and O_(2)-hydrogenated products are still huge challenges.Single-atom catalysts(SACs)as atomic-scale novel catalysts in which only isolated metal atoms are dispersed on supports shed new insights in overcome these obstacles in CO_(x) and O_(2) chemistry,including CO oxidation,CO_(2) reduction reaction(CO_(2)RR),oxygen reduction reaction(ORR),and oxygen evolution reaction(OER).In this review,the unique features and advanced synthesis strategies of SACs from a viewpoint of fundamental synthesis design are first highlighted to guide future strategy design for controllable SAC synthesis.Then,the to-date reported CO_(2)RR,CO oxidation,OER,and ORR mechanism are included and summarized.More importantly,the design principles and design strategies of improving the intrinsic activity,selectivity,and stability are extensively discussed and the engineering strategy is classified as neighbor coordination engineering,metal-atom engineering,and substrate engineering.Via the comprehensive review and summary of state-of-the-art SACs,the synthesis–structure–property–mechanism–design principle relation can be revealed to shed lights into the structural construction of SACs.Finally,we present an outlook on current challenges and future directions for SACs in CO_(x) and O_(2) chemistry.
基金supported by the National Natural Science Founda-tion of China(Nos.51776073,51906083)Key Research&Develop-ment program of Henan Province(No.162102210233)+1 种基金North China University of Water Resources and Electric Power Innovative Project(Nos.2019XA014,2019XB058)Scientific Research&Development Project of Ji-Yan Energy Science and Technology Research Institute(NKY2020-05).
文摘Calcium sulfate(CaSO_(4))has been verified as a promising oxygen carrier(OC)in the chemical looping combustion(CLC)for its high oxygen capacity,abundant reserve and low cost,but its low reactivity and deleterious sulfur species emission from the side reactions of CaSO_(4) should be well considered for its wide application in CLC.In order to promote the reactivity of CaSO_(4) and increase its potential to inhibit the gaseous sulfur emission,a CeO_(2)-enhanced CaSO_(4) OC mixed OC of core–shell structure was prepared using the combined template synthesis method.Reaction characteristics of the prepared CaSO_(4)-CeO_(2) mixed OC with a typical lignite was first conducted and systematically investigated,and an improved reactivity of the prepared CaSO_(4)-CeO_(2) mixed OC was demonstrated than its single component CaSO_(4) or CeO_(2) due to the fast transfer and exchange of oxygen from the CaSO_(4) substrate to coal via the doped CeO_(2).Furthermore,the solid products formed from the mixed CaSO_(4)-CeO_(2) OC with the selected coal were collected and analyzed.Especially,evolution and redistribution of the sulfur species of different forms were focused.At the latter reaction stage of YN reaction with the CaSO_(4)-CeO_(2) mixed OC,the SO_(2) emitted from the side reactions of CaSO_(4) was greatly diminished and the doped CeO_(2) was proven effective to directionally fix the SO_(2) released to turn into different solid sulfur compounds,which were determined as Ce_(2)O_(2)S,Ce_(2)S_(3) and Ce_(2)(SO_(4))_(3)·5H_(2)O and formed through the different pathways.In addition,good regeneration of the reduced CaSO_(4)-CeO_(2) mixed OC could be reached in spite of the unavoidable interaction between the included minerals in coal and the reduced mixed OC.Overall,the combined template method-made CaSO_(4)-CeO_(2) mixed OC reported herein was not only endowed with enhanced reactivity for coal conversion,but also owned the potential to directionally fix the gaseous sulfur emission,which is quite applicable as OC for simultaneous decarbonatization and desulfurization in the real CLC process.
文摘Stable and high‐efficiency bifunctional catalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desired for the practical application of Li‐O_(2)batteries with excellent rate performance and cycle stability.Herein,a novel hybrid bifunctional catalyst with carbon nanofibers inlaid with hollow Co_(3)O_(4)nanoparticles and separate active sites for ORR and OER were prepared and applied in Li‐O_(2)batteries.Benefiting from the synergistic effect of unique porous structural features and high electrocatalytic activity of hollow Co3O4 intimately bound to N‐doped carbon nanofibers,the assembled Li‐O_(2)batteries with novel catalyst exhibited high specific capacity,excellent rate capability,and cycle stability up to 150 cycles under a capacity limitation of 500 mAh g^(–1)at a current density of 100 mA g^(–1).The facile synthesis and preliminary results in this work show the as‐prepared catalyst as a promising bifunctional electrocatalyst for applications in metal‐air batteries,fuel cells,and electrocatalysis.
基金support from the Natural Science Foundation and Overseas Talent Projects of Jiangxi Province(20242BAB25217,20232BAB214025,20232BCJ25044)the Jiangxi Provincial Natural Science Foundation(20232BAB204088)the National Natural Science Foundation of China(52402132)。
文摘Regulating the orbital spin-electron filling of metal centers via interatomic electron transfer in transition metal oxides is one promising approach to enhancing their electrocatalytic oxygen evolution reaction(OER)performances,while it is still a challenge due to lacking of efficient strategy and deep understanding.In this work,a facile strategy containing electrochemical deposition and annealing in air atmosphere has been proposed to introduce monodispersed neodymium(Nd)atoms into spinel Co_(3)O_(4)nanosheets to trigger the electron transfer.Accordingly,the as-prepared Nd doped Co_(3)O_(4)nanosheets(Nd/Co_(3)O_(4))on nickel foam or carbon cloth showed greatly enhanced OER performances,with low overpotential of 284 and 396 mV at 10 m A cm^(-2),small Tafel slope of 95 and 119 mV dec^(-1)in 1.0 M KOH and 0.5 M H_(2)SO_(4),respectively.The experimental and density function theory results coherently indicate that the charge transfer in the Nd-O-Co asymmetric configuration not only enhances the conductivity of Co_(3)O_(4),but also regulates the filling degree of egorbitals of Co,leading to higher spin states,optimized adsorption ability,and accelerated H_(2)O dissociation process,thus achieving boosted OER activity.
基金We gratefully acknowledge financial support from the National Key R&D Program of China(Grant 2017YFA0700102)the National Natural Science Foundation of China(Grants 92045302,22072146,22002166 and 22002158)+1 种基金the DNL Cooperation Fund,CAS(DNL201923)G.X.Wang thanks the financial support from the CAS Youth Innovation Promotion(Grant Y201938).
文摘Cubic perovskite oxides usually suffer from delamination and Sr^(2+) segregation for catalyzing oxygen evolution reaction (OER) at the anodes of solid oxide electrolysis cells (SOECs). It is crucial to develop alternative and efficient anode materials for SOECs. Herein, a series of novel Y_(0.95-x)Sr_(x)Co_(0.3)Fe_(0.7)O_(3-δ) (YSCF-x) orthorhombic perovskite oxides in the Pnma (62) space group are synthesized as anode materials of SOECs. Physicochemical characterizations and density functional theory calculations reveal that the partial substitution of Y^(3+) by Sr^(2+) increases the oxygen vacancy concentration and mobility as well as improves the electrical conductivity, which contributes to the excellent OER activity of YSCF-x. At 800 °C, the current density of SOEC with YSCF-0.05-Ce0.8Sm0.2O2-δ anode can reach 1.32 A cm^(−2) at 1.6 V, about twice that of SOEC with Y_(0.95-x)Sr_(x)Co_(0.3)Fe_(0.7)O_(3-δ)-Ce_(0.8)Sm_(0.2)O_(2-δ) anode. This work paves a new avenue for the design of advanced anode materials of SOECs.
基金supported by the National Key Research and Development Program of China(No.2023YFB3809301)the National Natural Science Foundation of China(Nos.61905183,52127816 and 51832004).
文摘Self-reconstruction of catalysts during oxygen evolution reaction(OER)is crucial for the development of energy conversion technologies.However,the relationship between the specific atomic structure of pre-catalysts and their electrocatalytic behavior after reconstruction via dual-ion leaching has not been extensively researched.In this work,we design a highly effective non-noble metal OER catalyst with heterointerface through continuous self-reconstruction of Co_(2)(OH)_(3)Cl@NiMoO_(4)as pre-catalyst by a straightforward dual-ion(i.e.MoO_(4)^(2-)and Cl^(-))leaching.In-situ Raman and in-situ Fourier transform infrared(FT-IR)spectroscopy have precisely identified the progressive phase transformation of the pre-catalyst during self-reconstruction,which results in a stable heterojunction of CoOOH and NiOOH(CoOOH@NiOOH).Further calculations based on density functional theory(DFT)of CoOOH@NiOOH evident that more electrons will be aggregated in the Fermi level of Co.Notably,Gibbs free energy(ΔG)for different OER steps of CoOOH@NiOOH exhibit lower energy costs of all intermediates,implying the well catalytic properties.Ultimately,the catalyst derived from dual-ion leaching displays outstanding OER performance,characterized by an overpotential of 275 mV at a current density of 10 mA·cm^(-2)and exceptional stability over 12 h reaction.This work successfully paves a way of finding high-performance OER catalysts based on non-noble metal through dual-ion leaching during self-reconstruction.
