The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these c...The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.展开更多
The photothermal conversion capacity of pristine organic phase change materials(PCMs)is inherently insufficient in solar energy utilization.To upgrade their photothermal conversion capacity,we developed bimetallic zeo...The photothermal conversion capacity of pristine organic phase change materials(PCMs)is inherently insufficient in solar energy utilization.To upgrade their photothermal conversion capacity,we developed bimetallic zeolitic imidazolate framework(ZIF)derived Co/N co-doped flower-like carbon(Co/N-FLC)-based composite PCMs toward solar energy harvesting.3D interconnected carbon framework with low interfacial thermal resistance,abundant carbon defects and high content of nitrogen doping,excellent localized surface plasmon resonance(LSPR)effect of Co nanoparticles,and light absorber Co_(3)ZnC in Co/N-FLC synergistically upgrade the photothermal capacity of(polyethylene glycol)PEG@Co/N-FLC composite PCMs with an ultrahigh photothermal conversion efficiency of 94.8%under 0.16 W/cm^(2).Uniformly anchored Co and Co_(3)ZnC nanoparticles in carbon framework guarantee excellent photon capture ability.Bridging carbon nanotubes(CNTs)in 2D carbon nanosheets further accelerate the rapid transport of phonons by constructing cross-connected heat transfer paths.Additionally,PEG@Co/N-FLC exhibits a thermal energy storage density of 100.69 J/g and excellent thermal stability and durable reliability.Therefore,PEG@Co/N-FLC composite PCMs are promising candidates to accelerate the efficient utilization of solar energy.展开更多
The sluggish kinetics of the oxygen reduction reaction(ORR)and high over potential of oxygen evolution reaction(OER)are big challenges in the development of high-performance zinc-air batteries(ZABs)and fuel cells.In t...The sluggish kinetics of the oxygen reduction reaction(ORR)and high over potential of oxygen evolution reaction(OER)are big challenges in the development of high-performance zinc-air batteries(ZABs)and fuel cells.In this work,we report a rational design and a simple fabrication strategy of a photo-enhanced Co single-atom catalyst(SAC)comprising g-C3N4 coupled with cobalt-nitrogen-doped hierarchical mesoporous carbon(Co-N/MPC),forming a staggered p-n heterojunction that effectively improves charge separation and enhances electrocatalytic activity.The incorporation of Co SACs and g-C3N4 synergistically optimizes the photogenerated electron-hole pair separation,significantly boosting the intrinsic ORR-OER duplex activity.Under illumination,g-C_(3)N_(4)@Co-N/MPC exhibits an outstanding ORR half-wave potential(E1/2)of 0.841 V(vs.RHE)in 0.1 mol L^(–1)KOH and a low OER overpotential of 497.4 mV(vs.RHE)at 10 mA cm^(–2)in 1 mol L^(–1)KOH.Notably,the catalyst achieves an exceptional peak power density of 850.7 mW cm^(–2)in ZABs and of 411 mW cm^(–2)even in H_(2)-air fuel cell.In addition,g-C_(3)N_(4)@Co-N/MPC-based ZABs also show remarkable cycling stability exceeding 250 h.The advanced photo-induced charge separation at the p-n heterojunction facilitates faster electron transfer kinetics,and the mass transport owing to hierarchical mesoporous structure of Co-N-C,thereby reducing the overpotential and enhancing the overall energy conversion efficiency.This work provides a new perspective on designing next-generation of single-atom dispersed oxygen reaction catalysts,paving the way for high-performance photo-enhanced energy storage and conversion systems.展开更多
基金supported by Shanxi Province Science Foundation for Youths(202203021212300)Taiyuan University of Science and Technology Scientific Research Initial Funding(20212064)Outstanding Doctoral Award Fund in Shanxi Province(20222060).
文摘The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.
基金Beijing Natural Science Foundation,Grant/Award Number:2232053National Natural Science Foundation of China,Grant/Award Number:51902025。
文摘The photothermal conversion capacity of pristine organic phase change materials(PCMs)is inherently insufficient in solar energy utilization.To upgrade their photothermal conversion capacity,we developed bimetallic zeolitic imidazolate framework(ZIF)derived Co/N co-doped flower-like carbon(Co/N-FLC)-based composite PCMs toward solar energy harvesting.3D interconnected carbon framework with low interfacial thermal resistance,abundant carbon defects and high content of nitrogen doping,excellent localized surface plasmon resonance(LSPR)effect of Co nanoparticles,and light absorber Co_(3)ZnC in Co/N-FLC synergistically upgrade the photothermal capacity of(polyethylene glycol)PEG@Co/N-FLC composite PCMs with an ultrahigh photothermal conversion efficiency of 94.8%under 0.16 W/cm^(2).Uniformly anchored Co and Co_(3)ZnC nanoparticles in carbon framework guarantee excellent photon capture ability.Bridging carbon nanotubes(CNTs)in 2D carbon nanosheets further accelerate the rapid transport of phonons by constructing cross-connected heat transfer paths.Additionally,PEG@Co/N-FLC exhibits a thermal energy storage density of 100.69 J/g and excellent thermal stability and durable reliability.Therefore,PEG@Co/N-FLC composite PCMs are promising candidates to accelerate the efficient utilization of solar energy.
文摘The sluggish kinetics of the oxygen reduction reaction(ORR)and high over potential of oxygen evolution reaction(OER)are big challenges in the development of high-performance zinc-air batteries(ZABs)and fuel cells.In this work,we report a rational design and a simple fabrication strategy of a photo-enhanced Co single-atom catalyst(SAC)comprising g-C3N4 coupled with cobalt-nitrogen-doped hierarchical mesoporous carbon(Co-N/MPC),forming a staggered p-n heterojunction that effectively improves charge separation and enhances electrocatalytic activity.The incorporation of Co SACs and g-C3N4 synergistically optimizes the photogenerated electron-hole pair separation,significantly boosting the intrinsic ORR-OER duplex activity.Under illumination,g-C_(3)N_(4)@Co-N/MPC exhibits an outstanding ORR half-wave potential(E1/2)of 0.841 V(vs.RHE)in 0.1 mol L^(–1)KOH and a low OER overpotential of 497.4 mV(vs.RHE)at 10 mA cm^(–2)in 1 mol L^(–1)KOH.Notably,the catalyst achieves an exceptional peak power density of 850.7 mW cm^(–2)in ZABs and of 411 mW cm^(–2)even in H_(2)-air fuel cell.In addition,g-C_(3)N_(4)@Co-N/MPC-based ZABs also show remarkable cycling stability exceeding 250 h.The advanced photo-induced charge separation at the p-n heterojunction facilitates faster electron transfer kinetics,and the mass transport owing to hierarchical mesoporous structure of Co-N-C,thereby reducing the overpotential and enhancing the overall energy conversion efficiency.This work provides a new perspective on designing next-generation of single-atom dispersed oxygen reaction catalysts,paving the way for high-performance photo-enhanced energy storage and conversion systems.
