Leveraging Ligand and Composition Effects: Morphology‐Tailorable Pt–Bi Bimetallic Aerogels for Enhanced (Photo‐)Electrocatalysis

Abstract Metal aerogels (MAs) are emerging porous materials displaying unprecedented potential in catalysis, sensing, plasmonic technologies, etc. However, the lack of efficient regulation of their nano‐building blocks (NBBs) remains a big hurdle that hampers the in‐depth investigation and performance enhancement. Here, by harmonizing composition and ligand effects, Pt‐ and Bi‐based single‐ and bimetallic aerogels bearing NBBs of controlled dimensions and shapes are obtained by facilely tuning the metal precursors and the applied ligands. Particularly, by further modulating the electronic and optic properties of the aerogels via adjusting the content of the catalytically active Pt component and the semiconducting Bi component, both the electrocatalytic and photoelectrocatalytic performance of the Pt–Bi aerogels can be manipulated. In this light, an impressive catalytic performance for electro‐oxidation of methanol is acquired, marking a mass activity of 6.4‐fold higher under UV irradiation than that for commercial Pt/C. This study not only sheds light on in situ manipulating NBBs of MAs, but also puts forward guidelines for crafting high‐performance MAs‐based electrocatalysts and photoelectrocatalysts toward energy‐related electrochemical processes.