In this study,dual-metal atomic pairs of manganese(Mn)-iron(Fe)binuclear sites(BNSs)with two conjoint MnN4 and FeN4 moieties(MnFeN8)anchored onto a graphite-like structure(GLS)(Mn-Fe BNSs/GLS)were constructed.The binu...In this study,dual-metal atomic pairs of manganese(Mn)-iron(Fe)binuclear sites(BNSs)with two conjoint MnN4 and FeN4 moieties(MnFeN8)anchored onto a graphite-like structure(GLS)(Mn-Fe BNSs/GLS)were constructed.The binuclear MnFeN8 structure was verified experimentally and theoretically.Magnetic measurements and Gaussian calculations reveal that this unique Mn-Fe BNSs exhibit strong short-range electronic interaction between Mn and Fe sites,which decouples two paired d electrons in Fe sites,thereby transforming Fe sites from an intermediate to a high spin state.The optimal electronic configuration of Fe sites and their binuclear structure facilitate an oxygen reduction reaction(ORR)thermodynamically and dynamically,respectively,endowing Mn-Fe BNSs with improved ORR performance.展开更多
基金support of Shenzhen Basic Research Project(Nos.JCYJ20170818092720054,JCYJ20190808145203535,and JCYJ20190808144413257)National Natural Science Foundation of China(No.21671136)+3 种基金Postdoctoral Science Foundation of China(No.2019M663085)Major Programs for Science and Technology Development of Shenzhen(Nos.JSGG20160328151657828 and XCL201110060)Major Industrial Projects of Shenzhen(No.s2017001850011)the Project of Natural Science Foundation of Guangdong Province(Nos.2020A1515010380 and 2014A030311028).
文摘In this study,dual-metal atomic pairs of manganese(Mn)-iron(Fe)binuclear sites(BNSs)with two conjoint MnN4 and FeN4 moieties(MnFeN8)anchored onto a graphite-like structure(GLS)(Mn-Fe BNSs/GLS)were constructed.The binuclear MnFeN8 structure was verified experimentally and theoretically.Magnetic measurements and Gaussian calculations reveal that this unique Mn-Fe BNSs exhibit strong short-range electronic interaction between Mn and Fe sites,which decouples two paired d electrons in Fe sites,thereby transforming Fe sites from an intermediate to a high spin state.The optimal electronic configuration of Fe sites and their binuclear structure facilitate an oxygen reduction reaction(ORR)thermodynamically and dynamically,respectively,endowing Mn-Fe BNSs with improved ORR performance.
