Heteroatom-doped carbon-based transition-metal single-atom catalysts(SACs) are promising electrocatalysts for oxygen reduction reaction(ORR). Herein, with the aid of hierarchically porous silica as hard template, a fa...Heteroatom-doped carbon-based transition-metal single-atom catalysts(SACs) are promising electrocatalysts for oxygen reduction reaction(ORR). Herein, with the aid of hierarchically porous silica as hard template, a facile and general melting perfusion and mesopore-confined pyrolysis method was reported to prepare single-atomic Fe/N–S-doped carbon catalyst(FeNx/NC-S) with hierarchically porous structure and well-defined morphology. The FeNx/NC-S exhibited excellent ORR activity with a half-wave potential(E_(1/2)) of 0.92 V, and a lower overpotential of 320 mV at a current density of 10 mA cm^(-2)for OER under alkaline condition. The remarkable electrocatalysis performance can be attributed to the hierarchically porous carbon nanospheres with S doping and high content of Fe-Nx sites(up to 3.7 wt% of Fe), resulting from the nano-confinement effect of the hierarchically porous silica spheres(NKM-5) during the pyrolysis process. The rechargeable Zn-air battery with FeNx/NC-S as a cathode catalyst demonstrated a superior power density of 194.5 mW cm-2charge–discharge stability. This work highlights a new avenue to design advanced SACs for efficient sustainable energy storage and conversion.展开更多
Fe-NX/C electrocatalysts have aroused extensive interest in accelerating sluggish oxygen reduction reaction (ORR) kinetics as potential alternatives to platinum catalysts in rechargeable Zn-air batteries (ZABs).Howeve...Fe-NX/C electrocatalysts have aroused extensive interest in accelerating sluggish oxygen reduction reaction (ORR) kinetics as potential alternatives to platinum catalysts in rechargeable Zn-air batteries (ZABs).However,the low density and poor accessibility of Fe-NXsites have severely restricted the electrocatalytic performance of Fe-NX/C.Herein,Fe,N co-doped ordered mesoporous carbon fiber bundles are prepared through a ligand-assisted strategy with nitrogen-rich 1,10-phenanthroline as space isolation agent.1,10-Phenanthroline reveals a six-membered heterocyclic structure containing abundant nitrogen species to tightly coordinate with Fe ions,which is conducive to achieving high-density Fe-NXsites.Meanwhile,the adoption of SBA-15 as hard-templates enables the catalysts with highly ordered channels and large specific surface areas,improving the accessibility of Fe-NXsites.The optimal catalyst (PDA-Fe-900) demonstrates a positive half-wave potential of 0.84 V (vs.RHE) in alkaline solution,outperforming the commercial Pt/C (0.83 V).In addition,PDA-Fe-900 delivers comparable ORR performance to commercial Pt/C in acidic electrolyte.Impressively,when PDA-Fe-900 is employed as an air cathode,it achieves large power densities of 163.0 m W/cm^(2) in liquid-state ZAB and 116.6 m W/cm^(2) in the flexible solid-state ZAB.This work provides an efficient ligand-assisted pathway for fabricating catalysts with dense and accessible FeNXsites as high-performance ORR electrocatalysts for ZABs.展开更多
The design and development of low-cost,efficient,and stable bifunctional electrocatalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desirable for rechargeable metal-air batteries.In t...The design and development of low-cost,efficient,and stable bifunctional electrocatalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desirable for rechargeable metal-air batteries.In this work,N-doped porous hollow carbon spheres encapsulated with ultrafine Fe/Fe3O4 nanoparticles(FeOx@N-PHCS)were fabricated by impregnation and subsequent pyrolysis,using melamine-formaldehyde resin spheres as self-sacrifice templates and polydopamine as N and C sources.The sufficient adsorption of Fe3+on the polydopamine endowed the formation of Fe-Nx species upon high-temperature carbonization.The prepared FeOx@N-PHCS has advanced features of large specific surface area,porous hollow structure,high content of N dopants,sufficient Fe-Nx species and ultrafine FeOx nanoparticles.These features endow FeOx@N-PHCS with enhanced mass transfer and considerable active sites,leading to high activity and stability in catalyzing ORR and OER in alkaline electrolyte.Furthermore,the rechargeable Zn-air battery with FeOx@N-PHCS as air cathode catalyst exhibits a large peak power density,narrow charge-discharge potential gap and robust cycling stability,demonstrating the potential of the fabricated FeOx@N-PHCS as a promising electrode material for metal-air batteries.This new finding may open an avenue for rational design of bifunctional catalysts by integrating different active components within all-in-one catalyst for different electrochemical reactions.展开更多
Air cathodes with high electrocatalytic activity are vital for developing H2/O_(2) proton exchange membrane fuel cells(PEMFC)and Zn-air batteries.However,the state-of-the-art air cathodes suffer from either limited ca...Air cathodes with high electrocatalytic activity are vital for developing H2/O_(2) proton exchange membrane fuel cells(PEMFC)and Zn-air batteries.However,the state-of-the-art air cathodes suffer from either limited catalytic activity or high cost,which thus hinder their applications.Herein,we designed ZIF-8 derived nitrogen and atomic iron dual-doped porous carbon nanocubes as high-quality catalysts for ORR,through a novel gas-doping approach.The porous carbon nanocubic architecture and abundant Fe-Nxactive species endow ZIF-8 derived single atomic iron catalyst(PCN-A@Fe SA)with superior catalytic activity,and surpass Pt/C and a majority of the reported catalysts.Both XAS and DFT calculations suggest that Fe2+N4 moieties are the main active centers that are favorable for oxygen affinity and OH*intermediate desorption,which can result in promising catalytic performance.Most importantly,PCNA@Fe SA can achieve power density of 514 m W cm^(-2) as cathodic catalyst in a PEMFC and discharge peak power density of 185 m W cm^(-2) in an alkaline Zn-air battery.The outstanding performance is derived from both the high specific surface area and high-density of iron single atom in nitrogen doped nanocubic carbon matrix.展开更多
基金supported by National Natural Science Foundation of China (21773128)。
文摘Heteroatom-doped carbon-based transition-metal single-atom catalysts(SACs) are promising electrocatalysts for oxygen reduction reaction(ORR). Herein, with the aid of hierarchically porous silica as hard template, a facile and general melting perfusion and mesopore-confined pyrolysis method was reported to prepare single-atomic Fe/N–S-doped carbon catalyst(FeNx/NC-S) with hierarchically porous structure and well-defined morphology. The FeNx/NC-S exhibited excellent ORR activity with a half-wave potential(E_(1/2)) of 0.92 V, and a lower overpotential of 320 mV at a current density of 10 mA cm^(-2)for OER under alkaline condition. The remarkable electrocatalysis performance can be attributed to the hierarchically porous carbon nanospheres with S doping and high content of Fe-Nx sites(up to 3.7 wt% of Fe), resulting from the nano-confinement effect of the hierarchically porous silica spheres(NKM-5) during the pyrolysis process. The rechargeable Zn-air battery with FeNx/NC-S as a cathode catalyst demonstrated a superior power density of 194.5 mW cm-2charge–discharge stability. This work highlights a new avenue to design advanced SACs for efficient sustainable energy storage and conversion.
基金supported by the National Natural Science Foundation of China(No.U1804255)the Key Research&Development and Promotion Projects in Henan Province(Nos.222102520038 and 212102210651)。
文摘Fe-NX/C electrocatalysts have aroused extensive interest in accelerating sluggish oxygen reduction reaction (ORR) kinetics as potential alternatives to platinum catalysts in rechargeable Zn-air batteries (ZABs).However,the low density and poor accessibility of Fe-NXsites have severely restricted the electrocatalytic performance of Fe-NX/C.Herein,Fe,N co-doped ordered mesoporous carbon fiber bundles are prepared through a ligand-assisted strategy with nitrogen-rich 1,10-phenanthroline as space isolation agent.1,10-Phenanthroline reveals a six-membered heterocyclic structure containing abundant nitrogen species to tightly coordinate with Fe ions,which is conducive to achieving high-density Fe-NXsites.Meanwhile,the adoption of SBA-15 as hard-templates enables the catalysts with highly ordered channels and large specific surface areas,improving the accessibility of Fe-NXsites.The optimal catalyst (PDA-Fe-900) demonstrates a positive half-wave potential of 0.84 V (vs.RHE) in alkaline solution,outperforming the commercial Pt/C (0.83 V).In addition,PDA-Fe-900 delivers comparable ORR performance to commercial Pt/C in acidic electrolyte.Impressively,when PDA-Fe-900 is employed as an air cathode,it achieves large power densities of 163.0 m W/cm^(2) in liquid-state ZAB and 116.6 m W/cm^(2) in the flexible solid-state ZAB.This work provides an efficient ligand-assisted pathway for fabricating catalysts with dense and accessible FeNXsites as high-performance ORR electrocatalysts for ZABs.
基金supported by the National Natural Science Foundation of China(21421001,21573115,21875118)Tianjin Science and Technology Commission(18JCTPJC55900)+1 种基金the Natural Science Foundation of Tianjin(17JCYBJC17100,19JCZDJC37700)the 111 Project(B12015).
文摘The design and development of low-cost,efficient,and stable bifunctional electrocatalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desirable for rechargeable metal-air batteries.In this work,N-doped porous hollow carbon spheres encapsulated with ultrafine Fe/Fe3O4 nanoparticles(FeOx@N-PHCS)were fabricated by impregnation and subsequent pyrolysis,using melamine-formaldehyde resin spheres as self-sacrifice templates and polydopamine as N and C sources.The sufficient adsorption of Fe3+on the polydopamine endowed the formation of Fe-Nx species upon high-temperature carbonization.The prepared FeOx@N-PHCS has advanced features of large specific surface area,porous hollow structure,high content of N dopants,sufficient Fe-Nx species and ultrafine FeOx nanoparticles.These features endow FeOx@N-PHCS with enhanced mass transfer and considerable active sites,leading to high activity and stability in catalyzing ORR and OER in alkaline electrolyte.Furthermore,the rechargeable Zn-air battery with FeOx@N-PHCS as air cathode catalyst exhibits a large peak power density,narrow charge-discharge potential gap and robust cycling stability,demonstrating the potential of the fabricated FeOx@N-PHCS as a promising electrode material for metal-air batteries.This new finding may open an avenue for rational design of bifunctional catalysts by integrating different active components within all-in-one catalyst for different electrochemical reactions.
基金supported by the National Natural Science Foundation of China(NSFC Project Nos.21776104,21476088)the National Key Research and Development Program of China(Project Nos.2016YFB0101201,2017YFB0102900)+1 种基金the Guangdong Provincial Department of Science and Technology(Project No.2015B010106012)the Guangzhou Science,Technology and Innovation Committee(Project Nos.201504281614372,2016GJ006)。
文摘Air cathodes with high electrocatalytic activity are vital for developing H2/O_(2) proton exchange membrane fuel cells(PEMFC)and Zn-air batteries.However,the state-of-the-art air cathodes suffer from either limited catalytic activity or high cost,which thus hinder their applications.Herein,we designed ZIF-8 derived nitrogen and atomic iron dual-doped porous carbon nanocubes as high-quality catalysts for ORR,through a novel gas-doping approach.The porous carbon nanocubic architecture and abundant Fe-Nxactive species endow ZIF-8 derived single atomic iron catalyst(PCN-A@Fe SA)with superior catalytic activity,and surpass Pt/C and a majority of the reported catalysts.Both XAS and DFT calculations suggest that Fe2+N4 moieties are the main active centers that are favorable for oxygen affinity and OH*intermediate desorption,which can result in promising catalytic performance.Most importantly,PCNA@Fe SA can achieve power density of 514 m W cm^(-2) as cathodic catalyst in a PEMFC and discharge peak power density of 185 m W cm^(-2) in an alkaline Zn-air battery.The outstanding performance is derived from both the high specific surface area and high-density of iron single atom in nitrogen doped nanocubic carbon matrix.
