Abstract

We report here an electrocatalyst that exhibits superior performance in the electrooxidation of ethanol. The reactive centers of the catalyst have a nest‐type configuration with outer Zn‐NxC nest covering inner PtZn intermetallic compound nanoparticle loaded on carbon support (ZnNC⊂PtZn/C). The high‐energy stepped facets of the inner PtZn nanoparticle confined and shaped by the outer Zn‐NxC nest is highly active for the critical C‐C bond cleavage of ethanol in oxidation, confirmed by experimental characterizations and density functional theory calculations. The catalyst shows a rare high‐performance and demonstrates a mass activity of 3.7 A mgPt‐1 and a Faradaic efficiency of 78.2%, following the C1 pathway of reaction and the retention of initial activity remains 97% after 5,000 cycles. The unique configuration, also mitigating the concentration polarization, endows the catalyst with innate ethanol electrooxidation property by inner‐outer synergic interactions, leading to unexpected power output of an acidic direct ethanol fuel cell.