Seeded Synthesis of Hollow PdSn Intermetallic Nanomaterials for Highly Efficient Electrocatalytic Glycerol Oxidation

Abstract Intermetallic nanomaterials have shown promising potential as high‐performance catalysts in various catalytic reactions due to their unconventional crystal phases with ordered atomic arrangements. However, controlled synthesis of intermetallic nanomaterials with tunable crystal phases and unique hollow morphologies remains a challenge. Here, a seeded method is developed to synthesize hollow PdSn intermetallic nanoparticles (NPs) with two different intermetallic phases, that is, orthorhombic Pd 2 Sn and monoclinic Pd 3 Sn 2 . Benefiting from the rational regulation of the crystal phase and morphology, the obtained hollow orthorhombic Pd 2 Sn NPs deliver excellent electrocatalytic performance toward glycerol oxidation reaction (GOR), outperforming solid orthorhombic Pd 2 Sn NPs, hollow monoclinic Pd 3 Sn 2 NPs, and commercial Pd/C, which places it among the best reported Pd‐based GOR electrocatalysts. The reaction mechanism of GOR using the hollow orthorhombic Pd 2 Sn as the catalyst is investigated by operando infrared reflection absorption spectroscopy, which reveals that the hollow orthorhombic Pd 2 Sn catalyst cleaves the CC bond more easily compared to the commercial Pd/C. This work can pave an appealing route to the controlled synthesis of diverse novel intermetallic nanomaterials with hollow morphology for various promising applications.