Functionalizing ligands on surface metal atoms has been implemented to tune the adsorption behaviors of intermediates in electrochemical CO_(2) reduction reaction(CO_(2)RR).However,it is always bound within an unfavor...Functionalizing ligands on surface metal atoms has been implemented to tune the adsorption behaviors of intermediates in electrochemical CO_(2) reduction reaction(CO_(2)RR).However,it is always bound within an unfavorable linear scaling relationship of the synchronously changed adsorption energies of intermediates.To break it,a win-win diethylamine(DEA)-mediated strategy was proposed to functionalize surface Pd atoms by exchanging the residual oleylamine(OAm) on ultrafine Pd nanoparticles(Pd NPs) with DEA.The molecular dynamics simulations,coupled with in situ Fourier transform infrared spectroscopy results,revealed that DEA hindered less toward CO_(2) than H_(2)O on Pd NPs surface,and induced more CO linear configuration intermediate(^(*)CO_L),indicative of ease CO_(2) transport and CO desorption.Additionally,computational calculations implied that-NH-in DEA delocalized more electrons to surface Pd atoms and formed H-bond with ^(*)COOH,asynchronously changing the adsorption energies of ^(*)COOH and ^(*)CO,which enabled a CO Faraday efficiency(FE_(CO)) close to 100% in an ultrawide potential window and a stability of over 50 h with a FE_(CO) over 90%.This study dexterously addresses the residual issue of end-blocking agents on metal nanostructures from synthesis,and synchronously realizes the surface molecular functionalization,paving a smart avenue to design high-performance electrocatalysts.展开更多
基金supported by the Pilot Group Program of the Research Fund for International Senior Scientists (No.22350710789)the Start-up Funding of Central South University (No.206030104)。
文摘Functionalizing ligands on surface metal atoms has been implemented to tune the adsorption behaviors of intermediates in electrochemical CO_(2) reduction reaction(CO_(2)RR).However,it is always bound within an unfavorable linear scaling relationship of the synchronously changed adsorption energies of intermediates.To break it,a win-win diethylamine(DEA)-mediated strategy was proposed to functionalize surface Pd atoms by exchanging the residual oleylamine(OAm) on ultrafine Pd nanoparticles(Pd NPs) with DEA.The molecular dynamics simulations,coupled with in situ Fourier transform infrared spectroscopy results,revealed that DEA hindered less toward CO_(2) than H_(2)O on Pd NPs surface,and induced more CO linear configuration intermediate(^(*)CO_L),indicative of ease CO_(2) transport and CO desorption.Additionally,computational calculations implied that-NH-in DEA delocalized more electrons to surface Pd atoms and formed H-bond with ^(*)COOH,asynchronously changing the adsorption energies of ^(*)COOH and ^(*)CO,which enabled a CO Faraday efficiency(FE_(CO)) close to 100% in an ultrawide potential window and a stability of over 50 h with a FE_(CO) over 90%.This study dexterously addresses the residual issue of end-blocking agents on metal nanostructures from synthesis,and synchronously realizes the surface molecular functionalization,paving a smart avenue to design high-performance electrocatalysts.
