Oxygen‐Vacancy‐Induced Formation of Pt‐Based Intermetallics on MXene with Strong Metal‐Support Interactions for Efficient Oxygen Reduction Reaction

Abstract The Pt‐based alloys can moderate the binding energies of oxygenated species on the catalytic surface, endowing the superior catalytic performance towards oxygen reduction reaction (ORR). Nevertheless, it is still challenging to explore general methods to synthesize structurally ordered intermetallics with uniform distributions. Herein, the strong metal‐support interaction is employed to facilitate the interdiffusion of Pt/M atoms by establishing a tunnel of oxygen vacancy on ultrathin Ti₃C₂T_x (MXene) sheets, synthesizing the ordered PtFe, PtCo, PtZn, PdFe, PdZn intermetallics loaded onto Ti₃C₂T_x. Furthermore, the in‐situ generation of Ti–O from Ti₃C₂T_x could be bonded with Pt and forming Pt–O–Ti, resulting in charge redistribution through Pt–O–Ti structure. Theoretical calculations demonstrate that the valuable charge redistribution can be observed at the interface and extended even to at the distance of two nanometers from the interface, which can modulate the Pt–Pt distance, optimize Pt–O binding energy and enhance intrinsic activity towards ORR. The strong coupling interaction between PtFe and Ti₃C₂T_x containing the titanium oxide layer endows the high stability of the composites. This work not only presents a general synthesis strategy for intermetallics but also provides a new insight that metal‐support interaction is essential for the structural evolution of intermetallics on materials with oxygen vacancies.