Multi-site coupling is a promising strategy for developing highly efficient and CO-resistant hydrogen oxidation reaction(HOR)catalysts for proton exchange membrane fuel cells(PEMFCs).However,designing multifunctional ...Multi-site coupling is a promising strategy for developing highly efficient and CO-resistant hydrogen oxidation reaction(HOR)catalysts for proton exchange membrane fuel cells(PEMFCs).However,designing multifunctional synergistic schemes for single-atom sites remains a significant challenge.Herein,we propose a dual-template-confined oxophilic engineering strategy to construct well-dispersed iridium-nickel(IrNi)atomic dimers adjacent to IrNi nanoclusters on porous nitrogen-doped carbon(IrNi_(Dimer/NC1.8)-PNC).The paired IrNi dimer features an asymmetric Ir-N_(3)configuration coordinated with heteroatomic Ni-N_(3)O via an N-bridge.Remarkably,IrNi_(Dimer/NC1.8)-PNC exhibits a~23-fold enhancement in mass activity(4.36 A mg-1Ir at 20 mV)and 5-fold longer stability compared to benchmarking Pt/C toward HOR,while achieving a high rated power density of 1.18 W cm^(-2)in PEMFC anode applications.Furthermore,IrNi_(Dimer/NC1.8)-PNC demonstrates superior CO tolerance over monometallic Ir and Pt/C in both half-cell and full-cell devices.Combined experimental and density functional theory studies reveal that oxophilic Ni modulates the electronic environment of Ir through alloying and dimer interactions,thereby enhancing HOR activity.Importantly,the asymmetric IrNi dimer enables efficient CO^(*)and OH^(*)co-adsorption while facilitating CO_(2)^(*)desorption,synergistically mitigating CO poisoning and improving atom utilization efficiency.This work provides a design strategy and fundamental insights for multi-site synergistic catalysts in PEMFC anodes.展开更多
基金supported by the National Natural Science Foundation of China(22279079 and 22472101)Guangdong Science and Technology Department Program(2021QN02L252,2023A1515010021,and 2024A1515011543)Research Team Cultivation Program of Shenzhen University(2023QNT007)。
文摘Multi-site coupling is a promising strategy for developing highly efficient and CO-resistant hydrogen oxidation reaction(HOR)catalysts for proton exchange membrane fuel cells(PEMFCs).However,designing multifunctional synergistic schemes for single-atom sites remains a significant challenge.Herein,we propose a dual-template-confined oxophilic engineering strategy to construct well-dispersed iridium-nickel(IrNi)atomic dimers adjacent to IrNi nanoclusters on porous nitrogen-doped carbon(IrNi_(Dimer/NC1.8)-PNC).The paired IrNi dimer features an asymmetric Ir-N_(3)configuration coordinated with heteroatomic Ni-N_(3)O via an N-bridge.Remarkably,IrNi_(Dimer/NC1.8)-PNC exhibits a~23-fold enhancement in mass activity(4.36 A mg-1Ir at 20 mV)and 5-fold longer stability compared to benchmarking Pt/C toward HOR,while achieving a high rated power density of 1.18 W cm^(-2)in PEMFC anode applications.Furthermore,IrNi_(Dimer/NC1.8)-PNC demonstrates superior CO tolerance over monometallic Ir and Pt/C in both half-cell and full-cell devices.Combined experimental and density functional theory studies reveal that oxophilic Ni modulates the electronic environment of Ir through alloying and dimer interactions,thereby enhancing HOR activity.Importantly,the asymmetric IrNi dimer enables efficient CO^(*)and OH^(*)co-adsorption while facilitating CO_(2)^(*)desorption,synergistically mitigating CO poisoning and improving atom utilization efficiency.This work provides a design strategy and fundamental insights for multi-site synergistic catalysts in PEMFC anodes.
