Graphene Oxide-Assisted Synthesis of Pt-Co Alloy Nanocrystals with High-Index Facets and Enhanced Electrocatalytic Properties

Metal nanocrystals (NCs) are grown directly on the surface of reduced graphene oxide (rGO), which can maximize the rGO‐NCs contact/interaction to achieve the enhanced catalytic activity. However, it is difficult to control the size and morphology of metal NCs by in situ method due to the effects of functional groups on the surface of GO, and as a result, the metal NCs/rGO hybrids are conventionally synthesized by two‐step method. Herein, one‐pot synthesis of Pt–Co alloy NCs is demonstrated with concave‐polyhedrons and concave‐nanocubes bounded by {hkl} and {hk0} high‐index facets (HIFs) distributed on rGO. GO can affect the geometry and electronic structure of Pt–Co NCs. Thanks to the synergy of the HIFs and the electronic effect of the intimate contact/interaction between Pt–Co alloy and rGO, these as‐prepared Pt–Co NCs/rGO hybrids presents enhanced catalytic properties for the electrooxidation of formic acid, as well as for the oxygen reduction reaction. The morphology of Pt–Co alloy nano­crystals can be tuned from ladder‐like nanocubes to concave nanocubes (CNCs) and concave polyhedrons (CPHs) by varying the amount of graphene oxide (GO). GO is used to manipulate the nucleation and growth rates of Pt–Co alloy nanocrystals more than as a support. Pt–Co CPHs/rGO and Pt–Co CNCs/rGO show excellent electrocatalytic properties.