Self‐Templating‐Oriented Manipulation of Ultrafine Pt₃Cu Alloyed Nanoparticles into Asymmetric Porous Bowl‐Shaped Configuration for High‐Efficiency Methanol Electrooxidation

Abstract The precise and comprehensive manipulation of the component, size, and geometric nano‐architecture of platinum‐based electrocatalysts into porous and hollow structure can effectively impart the catalysts with substantially improved electrochemical performance, yet remain formidably challenging. Herein, a straightforward fabrication of porous platinum‐copper alloyed nanobowls (abbreviated as Pt₃Cu NBs hereafter) assembled by ultrafine nanoparticles (≈2.9 nm) via a one‐pot hydrothermal approach with the assistance of a structure‐directing agent of N,N′‐methylenebisacrylamide (MBAA) is reported. The involvement of MBAA plays a decisive role in the formation of Pt‐MBAA complex solid nanospheres, which serve as the self‐sacrificial reactive template for the deposition/growth of Pt₃Cu nanoparticles and the eventual formation of the asymmetric open‐shelled nanobowls. Benefitting from the 3D sufficient accessibility of exterior/interior surfaces, high atom‐utilization efficiency, and PtCu bimetallic alloy synergy, the self‐supported Pt₃Cu NBs demonstrate remarkably enhanced activity, better anti‐poisoning capability, and reinforced robustness for the methanol oxidation reaction (MOR) as compared with the commercial Pt black benchmark, exhibiting great application promises in practical fuel cell systems. It is envisaged that the innovative self‐templated synthetic strategy outlined here may provide a perspective to design a range of porous bowl‐shaped high‐performance nanocatalysts.