Engineering non-precious metals into nitrogen-doped carbon is employed to improve electrocatalyst activity towards oxygen reduction reaction(ORR). A nickel-doped Co-N/C mesoporous nanopolyhedron is successfully evolut...Engineering non-precious metals into nitrogen-doped carbon is employed to improve electrocatalyst activity towards oxygen reduction reaction(ORR). A nickel-doped Co-N/C mesoporous nanopolyhedron is successfully evoluted from a Ni-doped ZIF-67 precursor. The Ni & Co synergistic N/C catalyst exhibits a half-wave potential of 0.895 V(vs. reversible hydrogen electrode(RHE)) with a diffusion-limiting current density of 6.1 m A cm^(-2)for alkaline ORR at 1600 r min^(-1), which is competitive to commercial Pt/C in terms of cost, methanol tolerance, and long-term stability. In situ surface-enhanced Raman scattering(SERS) study reveals the formation and fast conversion of superoxide ion(O_(2)^(-)) intermediate on the catalyst surface. Density functional theory(DFT) calculations demonstrate the decrease of energy barrier for potential-determining step(O* protonation) by Co-Ni synergy as well as the reduction of adsorption energy on catalyst surface upon nickel doping. The joint results of in situ SERS study and DFT calculations suggest a favourable ORR process on nickel-doped Co-N/C.展开更多
The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this wor...The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this work,we strategi-cally engineer the active site structure of Co-N-C via B substitution,which is accomplished by the pyrolysis of ammonium borate.During this process,the in-situ generated NH_(3)gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure.The well-designed CoB_(1)N_(3)active site endows Co with higher charge density and stronger adsorption energy toward oxygen species,potentially accelerating ORR kinetics.As expected,the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart,with 40 mV,and fivefold en-hancement in half-wave potential and turnover frequency(TOF).More importantly,the excellent ORR performance could be translated into membrane electrode assembly(MEA)in a fuel cell test,delivering an impressive peak power density of 824 mW·cm^(-2),which is currently the best among Co-based catalysts under the same conditions.This work not only demon-strates an effective method for designing advanced catalysts,but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.展开更多
基金supported by the National Natural Science Foundation of China (No. 21874053)the Science and Technology Development Project of Jilin Province, China (No. 20180414022GH)funding from the Advanced Low Carbon Technology Research and Development Program (ALCA), specially promoted research for innovative nextgeneration batteries (SPRING)。
文摘Engineering non-precious metals into nitrogen-doped carbon is employed to improve electrocatalyst activity towards oxygen reduction reaction(ORR). A nickel-doped Co-N/C mesoporous nanopolyhedron is successfully evoluted from a Ni-doped ZIF-67 precursor. The Ni & Co synergistic N/C catalyst exhibits a half-wave potential of 0.895 V(vs. reversible hydrogen electrode(RHE)) with a diffusion-limiting current density of 6.1 m A cm^(-2)for alkaline ORR at 1600 r min^(-1), which is competitive to commercial Pt/C in terms of cost, methanol tolerance, and long-term stability. In situ surface-enhanced Raman scattering(SERS) study reveals the formation and fast conversion of superoxide ion(O_(2)^(-)) intermediate on the catalyst surface. Density functional theory(DFT) calculations demonstrate the decrease of energy barrier for potential-determining step(O* protonation) by Co-Ni synergy as well as the reduction of adsorption energy on catalyst surface upon nickel doping. The joint results of in situ SERS study and DFT calculations suggest a favourable ORR process on nickel-doped Co-N/C.
基金the National Key Research and Development Program of China(2022YFB4004100)National Natural Science Foundation of China(22272161,22179126)+1 种基金the Jilin Province Science and Technology Development Program(YDZJ202202CXJD011,20240101019JC)Jilin Province major science and technology project(222648GX0105103875)for financial supports.
文摘The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this work,we strategi-cally engineer the active site structure of Co-N-C via B substitution,which is accomplished by the pyrolysis of ammonium borate.During this process,the in-situ generated NH_(3)gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure.The well-designed CoB_(1)N_(3)active site endows Co with higher charge density and stronger adsorption energy toward oxygen species,potentially accelerating ORR kinetics.As expected,the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart,with 40 mV,and fivefold en-hancement in half-wave potential and turnover frequency(TOF).More importantly,the excellent ORR performance could be translated into membrane electrode assembly(MEA)in a fuel cell test,delivering an impressive peak power density of 824 mW·cm^(-2),which is currently the best among Co-based catalysts under the same conditions.This work not only demon-strates an effective method for designing advanced catalysts,but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.
