With the increased energy demand,developing renewable and clean energy technologies becomes more and more significant to mitigate climate warming and alleviate the environmental pollution.The key point is design and s...With the increased energy demand,developing renewable and clean energy technologies becomes more and more significant to mitigate climate warming and alleviate the environmental pollution.The key point is design and synthesis of low cost and efficient materials for a wide variety of electrochemical reactions.Over the past ten years,two-dimensional(2D)nanomaterials that graphene represents have been paid much attention as a class of the most promising candidates for heterogeneous electrocatalysts in electrochemical storage and conversion.Their unique properties,such as good chemical stability,good flexibility,and good electronic properties,along with their nanosized thickness and large specific area,make them exhibit comprehensively good performances for energy storage and conversion.Here,we present an overview on the recent advances in electrochemical applications of graphene,graphdiyne,transition metal dichalcogenides(TMDs),and MXenes for supercapacitors(SCs),oxygen reduction reaction(ORR),and hydrogen evolution reaction(HER).展开更多
The demand for efficient and environmentally-benign electrocatalysts that help availably harness the renewable energy resources is growing rapidly. In recent years, increasing insights into the design of water electro...The demand for efficient and environmentally-benign electrocatalysts that help availably harness the renewable energy resources is growing rapidly. In recent years, increasing insights into the design of water electrolysers, fuel cells, and metal–air batteries emerge in response to the need for developing sustainable energy carriers, in which the oxygen evolution reaction and the oxygen reduction reaction play key roles. However, both reactions suffer from sluggish kinetics that restricts the reactivity. Therefore, it is vital to probe into the structure of the catalysts to exploit high-performance bifunctional oxygen electrocatalysts. Spinel-type catalysts are a class of materials with advantages of versatility, low toxicity, low expense, high abundance, flexible ion arrangement, and multivalence structure. In this review, we afford a basic overview of spinel-type materials and then introduce the relevant theoretical principles for electrocatalytic activity, following that we shed light on the structure–property relationship strategies for spinel-type catalysts including electronic structure, microstructure, phase and composition regulation,and coupling with electrically conductive supports. We elaborate the relationship between structure and property, in order to provide some insights into the design of spinel-type bifunctional oxygen electrocatalysts.展开更多
To satisfy the rapid development of gas-involving electrocatalysis(O2, CO2, N2, etc.), nanostructured electrocatalysts with favorably regulated electronic structure and surface nanostructures are urgently required. He...To satisfy the rapid development of gas-involving electrocatalysis(O2, CO2, N2, etc.), nanostructured electrocatalysts with favorably regulated electronic structure and surface nanostructures are urgently required. Herein, we highlighted a core-branch hydroxysulfide as a significantly enhanced oxygen evolution reaction electrocatalyst. This hydroxysulfide was facilely fabricated via a versatile interfacial reaction in S2- inorganic solution at room temperature for a designed period. The moderative growth kinetics contributed to the growth of interconnected hydroxysulfide nanosheets with high-sulfur contents on the hydroxide precursor substrates, resulting in a hierarchical nanostructure with multifunctional modifications, including regulated electronic structure, rapid electron highway, excellent accessibility, and facilitated mass transfer. Such synthetic methodology can be generalized and facilely governed by regulating the temperature, concentration, duration, and solvent for targeted nanostructures. Contributed to the favorably regulated electronic structure and surface nanostructure, the as-obtained core-branch Co2NiS2.4(OH)1.2 sample exhibits superior OER performance, with a remarkably low overpotential(279 m V required for 10.0 m A c^m-2), a low Tafel slope(52 m V dec^-1), and a favorable long-term stability. This work not only presents a promising nanostructured hydroxysulfide for excellent OER electrocatalysis, but also shed fresh lights on the further rational development of efficient electrocatalysts.展开更多
Electrocatalytic oxygen reduction reaction (ORR) via two-electron pathway is a promising approach to decentralized and on-site hydrogen peroxide (H_(2)O_(2)) production beyond the traditional anthraquinone process.In ...Electrocatalytic oxygen reduction reaction (ORR) via two-electron pathway is a promising approach to decentralized and on-site hydrogen peroxide (H_(2)O_(2)) production beyond the traditional anthraquinone process.In recent years,electrochemical H_(2)O_(2) production in acidic media has attracted increasing attention owing to its stronger oxidizing capacity,superior stability,and higher compatibility with various applications.Here,recent advances of H_(2)O_(2) electrosynthesis in acidic media are summarized.Specifically,fundamental aspects of two-electron ORR mechanism are firstly presented with an emphasis on the pH effect on catalytic performance.Major categories of promising electrocatalysts are then reviewed,including noble-metal-based materials,non-noble-metal single-atom catalysts,non-noblemetal compounds,and metal-free carbon-based materials.The innovative development of electrochemical devices and in situ/on-site application of electrogenerated H_(2)O_(2) are also highlighted to bridge the gap between laboratory-scale fundamental research and practically relevant H_(2)O_(2) electrosynthesis.Finally,critical perspectives on present challenges and promising opportunities for future research are provided.展开更多
Through partial deligandation of metal-organic frameworks(MOFs),quasi-MOFs with a transition structure between MOFs and metal compounds(such as metal oxides,nitrides,sulfides,and phosphides)can be fabricated.Quasi-MOF...Through partial deligandation of metal-organic frameworks(MOFs),quasi-MOFs with a transition structure between MOFs and metal compounds(such as metal oxides,nitrides,sulfides,and phosphides)can be fabricated.Quasi-MOFs can not only retain the porous structure of MOFs to a certain extent,but also expose the inorganic nodes to the guest species(e.g.,metal nanoparticles)to show enhanced metal-support interaction for synergistic catalysis.This concept was first demonstrated by our group through calcining Au/MIL-101 at different temperatures under Ar flow to adjust the interface between Au nanoparticles and the inorganic Cr–O nodes.The obtained Au/quasi-MIL-101 showed superior enhanced catalytic activity in the oxidation of carbon monoxide.This study has inspired further research interest to fabricate other quasi-MOFs through controlled deligandation of mono-and bimetallic MOFs and their composites for the design of efficient catalysts.展开更多
Carb on nanospheres(XC-72R)were functionalized by boron-oxygen(B-O)through coannealing with boric acid,to which highly dispersed palladium nanoparticles(Pd NPs)(-1.7 nm)were immobilized by a wet chemical reduction for...Carb on nanospheres(XC-72R)were functionalized by boron-oxygen(B-O)through coannealing with boric acid,to which highly dispersed palladium nanoparticles(Pd NPs)(-1.7 nm)were immobilized by a wet chemical reduction for the first time.The resultant Pd/OB-C catalystexhibits significantly improved activity for the dehydrogenation from formic acid(FA)compared to pristine XC-72R supported Pd NPs(Pd/C).Impressively,by adding melamine precursor,the B-0 and nitrogen(N)-functionalized product OB-C-N displays an extremely high B content,ca.34 times higher than OB-C.The Pd/OB-C-N catalyst with an ultrafine Pd particle size of-1.4 nm shows a superb activity,with a turnoverfrequency(TOF)as high as 5,354 h^-1 at 323 K,owing to the uniform ultrafine Pd NPs and the effect from B-0 and N functionalities.展开更多
Porous metal phosphide cubes with exposed vertices and edges containing abundant catalytically active sites are promising electrocatalysts. Herein, by integrating the advantages of the phosphorus-rich cobalt phosphide...Porous metal phosphide cubes with exposed vertices and edges containing abundant catalytically active sites are promising electrocatalysts. Herein, by integrating the advantages of the phosphorus-rich cobalt phosphides and bimetallic oxides to form hybrid architectures, we prepared CoP3/CoSnO2 via phosphating CoSn(OH)6 nanocubes, which has unique porous nanocubic structure. The optimized CoP3/CoSnO2 porous nanaocubes showed excellent electrocatalytic activity for OER/ORR. What’s more, the electrochemical performances of CoP3/CoSnO2 porous nanaocubes as air cathode catalyst for zinc air batteries were better than that of commercial RuO2 and 20 wt% Pt/C with a mass ratio of 1:1 as the air cathode catalyst. This work offers a new strategy to fabricate metal phosphide with porous nanocubic structures.展开更多
Two-dimensional(2D)carbon nanostructures play a critical role in energy-related applications,but developing facile and efficient strategies to synthesize these kinds of nanostructures is extremely rare.Herein,ultrathi...Two-dimensional(2D)carbon nanostructures play a critical role in energy-related applications,but developing facile and efficient strategies to synthesize these kinds of nanostructures is extremely rare.Herein,ultrathin carbon nanoribbons(CNRibs),with a thickness of 2–6 nm and length over 100 nm,have been strategically fabricated via a one-step pyrolysis of one-dimensional(1D)metal–organic framework nanorods(MOF NRods).Manipulating the diameters of MOF NRods will result in the formation of porous carbon nanostructures in 1D or 2D morphologies.Functional CNRibs with N doping or metal active site immobilization have also been studied.The CNRibs decorated with iron nanoclusters and single atoms have been used as excellent catalysts for the oxygen reduction reaction under both alkaline and acidic conditions,as well as zinc–air batteries.This work gives deep insights into the structural evolution from 1D to 2D morphology,providing an efficient approach to fabricate low-dimensional nanomaterials with controllable morphologies and functionalities for electrochemical applications.展开更多
CONSPECTUS:Energy electrocatalysis is an essential part for the modern energy network serving as the core technique in many electrochemical energy devices such as batteries,fuel cells,electrolyzers,etc.Developing high...CONSPECTUS:Energy electrocatalysis is an essential part for the modern energy network serving as the core technique in many electrochemical energy devices such as batteries,fuel cells,electrolyzers,etc.Developing high-performance electrocatalysts,especially the pursuit for higher intrinsic electrocatalytic activity,is the eternal theme for high-efficiency energy electrocatalysis.Transition metal compounds are highly considered as promising highperformance electrocatalysts due to their facile fabrication,well-defined structure,and encouraging intrinsic activity.However,further promotion on intrinsic electrocatalytic activity of conventional transition metal compounds encounters an unavoidable bottleneck originated from the rigid homoanion structure with limited choice of anions.Facing the above issue,heteroanion substitution on pristine transition metal compounds has been proposed in some recent research.Their unique structure and properties that distinguish them from routine transition metal compounds have attracted wide attention to reveal distinct electronic structures,synthesis methodologies,and functions in energy electrocatalysis for future application.展开更多
文摘With the increased energy demand,developing renewable and clean energy technologies becomes more and more significant to mitigate climate warming and alleviate the environmental pollution.The key point is design and synthesis of low cost and efficient materials for a wide variety of electrochemical reactions.Over the past ten years,two-dimensional(2D)nanomaterials that graphene represents have been paid much attention as a class of the most promising candidates for heterogeneous electrocatalysts in electrochemical storage and conversion.Their unique properties,such as good chemical stability,good flexibility,and good electronic properties,along with their nanosized thickness and large specific area,make them exhibit comprehensively good performances for energy storage and conversion.Here,we present an overview on the recent advances in electrochemical applications of graphene,graphdiyne,transition metal dichalcogenides(TMDs),and MXenes for supercapacitors(SCs),oxygen reduction reaction(ORR),and hydrogen evolution reaction(HER).
基金supported by the Natural Scientific Foundation of China (21825501)National Key Research and Development Program (2016YFA0202500 and 2016YFA0200102)+1 种基金Australian Research Council (DP160103107, FT170100224)Tsinghua University Initiative Scientific Research Program。
文摘The demand for efficient and environmentally-benign electrocatalysts that help availably harness the renewable energy resources is growing rapidly. In recent years, increasing insights into the design of water electrolysers, fuel cells, and metal–air batteries emerge in response to the need for developing sustainable energy carriers, in which the oxygen evolution reaction and the oxygen reduction reaction play key roles. However, both reactions suffer from sluggish kinetics that restricts the reactivity. Therefore, it is vital to probe into the structure of the catalysts to exploit high-performance bifunctional oxygen electrocatalysts. Spinel-type catalysts are a class of materials with advantages of versatility, low toxicity, low expense, high abundance, flexible ion arrangement, and multivalence structure. In this review, we afford a basic overview of spinel-type materials and then introduce the relevant theoretical principles for electrocatalytic activity, following that we shed light on the structure–property relationship strategies for spinel-type catalysts including electronic structure, microstructure, phase and composition regulation,and coupling with electrically conductive supports. We elaborate the relationship between structure and property, in order to provide some insights into the design of spinel-type bifunctional oxygen electrocatalysts.
基金supported by the National Key Research and Development Program(2016YFA0202500 and 2016YFA0200101)the Natural Scientific Foundation of China(21825501)
文摘To satisfy the rapid development of gas-involving electrocatalysis(O2, CO2, N2, etc.), nanostructured electrocatalysts with favorably regulated electronic structure and surface nanostructures are urgently required. Herein, we highlighted a core-branch hydroxysulfide as a significantly enhanced oxygen evolution reaction electrocatalyst. This hydroxysulfide was facilely fabricated via a versatile interfacial reaction in S2- inorganic solution at room temperature for a designed period. The moderative growth kinetics contributed to the growth of interconnected hydroxysulfide nanosheets with high-sulfur contents on the hydroxide precursor substrates, resulting in a hierarchical nanostructure with multifunctional modifications, including regulated electronic structure, rapid electron highway, excellent accessibility, and facilitated mass transfer. Such synthetic methodology can be generalized and facilely governed by regulating the temperature, concentration, duration, and solvent for targeted nanostructures. Contributed to the favorably regulated electronic structure and surface nanostructure, the as-obtained core-branch Co2NiS2.4(OH)1.2 sample exhibits superior OER performance, with a remarkably low overpotential(279 m V required for 10.0 m A c^m-2), a low Tafel slope(52 m V dec^-1), and a favorable long-term stability. This work not only presents a promising nanostructured hydroxysulfide for excellent OER electrocatalysis, but also shed fresh lights on the further rational development of efficient electrocatalysts.
基金The University of Adelaide for Early Career Researcher Seed Funding(15128587)the University of Electronic Science and Technology of China(UESTC)for Startup funding(A1098531023601264)the National Natural Science Foundation of China(NSFC 22102018 and 52171201)。
文摘Electrocatalytic oxygen reduction reaction (ORR) via two-electron pathway is a promising approach to decentralized and on-site hydrogen peroxide (H_(2)O_(2)) production beyond the traditional anthraquinone process.In recent years,electrochemical H_(2)O_(2) production in acidic media has attracted increasing attention owing to its stronger oxidizing capacity,superior stability,and higher compatibility with various applications.Here,recent advances of H_(2)O_(2) electrosynthesis in acidic media are summarized.Specifically,fundamental aspects of two-electron ORR mechanism are firstly presented with an emphasis on the pH effect on catalytic performance.Major categories of promising electrocatalysts are then reviewed,including noble-metal-based materials,non-noble-metal single-atom catalysts,non-noblemetal compounds,and metal-free carbon-based materials.The innovative development of electrochemical devices and in situ/on-site application of electrogenerated H_(2)O_(2) are also highlighted to bridge the gap between laboratory-scale fundamental research and practically relevant H_(2)O_(2) electrosynthesis.Finally,critical perspectives on present challenges and promising opportunities for future research are provided.
基金This work was financially supported by the National Institute of Advanced Industrial Science and Technology(AIST),Jiangsu University(4023000046)Shenzhen Key Laboratory of Micro/Nano-Porous Functional Materials(SKLPM)(ZDSYS20210709112802010)+2 种基金China Postdoctoral Science Foundation(2022TQ0126 and 2022M721375)Guangdong Grants(2021ZT09C064)the National Key Research and Development Project(2022YFA1503900).
基金supported by the National Natural Science Foundation of China(U1904215,21671170 and 21875207)the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP)+4 种基金the Program for New Century Excellent Talents of the University in China(NCET-13-0645)the Six Talent Plan(2015XCL-030)Qinglan Projectthe Priority Academic Program Development of Jiangsu Higher Education Institutionsthe support from the postdoctoral fund of Yangzhou University。
文摘二维金属有机骨架(2D MOF)具有较大的比表面积和较高的活性位点密度,是改善电催化性能的理想载体.通过简单的制备方法获得2D纳米结构受到了广泛的关注.本文提出了一种吡啶调节溶剂热合成方法,用于合成镍/钴双金属MOF纳米片.得到的MOF材料具有矩形2D形貌,厚度约20纳米.这些纳米片作为电催化剂在碱性条件下表现出析氧反应(OER)活性.其中,Ni0.5Co1.5-bpy(PyM)在1.0 mol L-1KOH溶液中、电流密度10 mA cm-2时过电位低至256 mV,Tafel斜率为81.8 mV dec-1,且具有良好的电化学稳定性.对催化反应后的电极材料研究表明,Ni0.5Co1.5-bpy(PyM)的高催化活性来源于原位形成的活性氢氧化物和羟基氧化物.该研究为2D MOF材料的可控合成及其与电催化性能构效关系的研究提供了理论基础.
基金This work was supported by the National Institute of Advanced Industrial Science and Technology,and the National Natural Science Foundation of China(NSFC-21875207).
文摘Through partial deligandation of metal-organic frameworks(MOFs),quasi-MOFs with a transition structure between MOFs and metal compounds(such as metal oxides,nitrides,sulfides,and phosphides)can be fabricated.Quasi-MOFs can not only retain the porous structure of MOFs to a certain extent,but also expose the inorganic nodes to the guest species(e.g.,metal nanoparticles)to show enhanced metal-support interaction for synergistic catalysis.This concept was first demonstrated by our group through calcining Au/MIL-101 at different temperatures under Ar flow to adjust the interface between Au nanoparticles and the inorganic Cr–O nodes.The obtained Au/quasi-MIL-101 showed superior enhanced catalytic activity in the oxidation of carbon monoxide.This study has inspired further research interest to fabricate other quasi-MOFs through controlled deligandation of mono-and bimetallic MOFs and their composites for the design of efficient catalysts.
文摘Carb on nanospheres(XC-72R)were functionalized by boron-oxygen(B-O)through coannealing with boric acid,to which highly dispersed palladium nanoparticles(Pd NPs)(-1.7 nm)were immobilized by a wet chemical reduction for the first time.The resultant Pd/OB-C catalystexhibits significantly improved activity for the dehydrogenation from formic acid(FA)compared to pristine XC-72R supported Pd NPs(Pd/C).Impressively,by adding melamine precursor,the B-0 and nitrogen(N)-functionalized product OB-C-N displays an extremely high B content,ca.34 times higher than OB-C.The Pd/OB-C-N catalyst with an ultrafine Pd particle size of-1.4 nm shows a superb activity,with a turnoverfrequency(TOF)as high as 5,354 h^-1 at 323 K,owing to the uniform ultrafine Pd NPs and the effect from B-0 and N functionalities.
基金supported by the National Natural Science Foundation of China (NSFC-21671170, 21673203, 21875207, 21201010)the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions (TAPP)+4 种基金Program for New Century Excellent Talents of the University in China (NCET-13-0645)Postgraduate Research & Practice Innovation Program of Jiangsu Province (XSJCX17-015)the Priority Academic Program Development of Jiangsu Higher Education InstitutionsYangzhou University Graduate Student International Academic Exchange Special Fund Projectthe Technical Support we received at the Testing Center of Yangzhou University.
文摘Porous metal phosphide cubes with exposed vertices and edges containing abundant catalytically active sites are promising electrocatalysts. Herein, by integrating the advantages of the phosphorus-rich cobalt phosphides and bimetallic oxides to form hybrid architectures, we prepared CoP3/CoSnO2 via phosphating CoSn(OH)6 nanocubes, which has unique porous nanocubic structure. The optimized CoP3/CoSnO2 porous nanaocubes showed excellent electrocatalytic activity for OER/ORR. What’s more, the electrochemical performances of CoP3/CoSnO2 porous nanaocubes as air cathode catalyst for zinc air batteries were better than that of commercial RuO2 and 20 wt% Pt/C with a mass ratio of 1:1 as the air cathode catalyst. This work offers a new strategy to fabricate metal phosphide with porous nanocubic structures.
基金The authors are thankful to Dr.Takeyuki Uchida for microscopic measurements,and AIST and Guangdong-Hong Kong-Macao Joint Laboratory(grant no.2019B121205001)for financial support.
文摘Two-dimensional(2D)carbon nanostructures play a critical role in energy-related applications,but developing facile and efficient strategies to synthesize these kinds of nanostructures is extremely rare.Herein,ultrathin carbon nanoribbons(CNRibs),with a thickness of 2–6 nm and length over 100 nm,have been strategically fabricated via a one-step pyrolysis of one-dimensional(1D)metal–organic framework nanorods(MOF NRods).Manipulating the diameters of MOF NRods will result in the formation of porous carbon nanostructures in 1D or 2D morphologies.Functional CNRibs with N doping or metal active site immobilization have also been studied.The CNRibs decorated with iron nanoclusters and single atoms have been used as excellent catalysts for the oxygen reduction reaction under both alkaline and acidic conditions,as well as zinc–air batteries.This work gives deep insights into the structural evolution from 1D to 2D morphology,providing an efficient approach to fabricate low-dimensional nanomaterials with controllable morphologies and functionalities for electrochemical applications.
基金This work was supported by National Natural Science Foundation of China(21825501)the Tsinghua University Initiative Scientific Research Program.
文摘CONSPECTUS:Energy electrocatalysis is an essential part for the modern energy network serving as the core technique in many electrochemical energy devices such as batteries,fuel cells,electrolyzers,etc.Developing high-performance electrocatalysts,especially the pursuit for higher intrinsic electrocatalytic activity,is the eternal theme for high-efficiency energy electrocatalysis.Transition metal compounds are highly considered as promising highperformance electrocatalysts due to their facile fabrication,well-defined structure,and encouraging intrinsic activity.However,further promotion on intrinsic electrocatalytic activity of conventional transition metal compounds encounters an unavoidable bottleneck originated from the rigid homoanion structure with limited choice of anions.Facing the above issue,heteroanion substitution on pristine transition metal compounds has been proposed in some recent research.Their unique structure and properties that distinguish them from routine transition metal compounds have attracted wide attention to reveal distinct electronic structures,synthesis methodologies,and functions in energy electrocatalysis for future application.
