Rationally Designed L12‐Pt2RhFe Intermetallic Catalyst with High CO‐Tolerance for Alkaline Methanol Electrooxidation

Abstract It is a grand challenge to deep understanding of and precise control over functional sites for the rational design of highly efficient catalysts for methanol electrooxidation. Here, an L1 2 ‐Pt 2 RhFe intermetallic catalyst with integrated functional components is demonstrated, which exhibits exceptional CO tolerance. The Pt 2 RhFe/C achieves a superior mass activity of 6.43 A mg Pt −1 , which is 2.23‐fold and 3.53‐fold higher than those of PtRu/C and Pt/C. Impressively, the Pt 2 RhFe/C exhibits a significant enhancement in durability owing to its high CO‐tolerance and stability. Density functional theory calculations reveal that high performance of Pt 2 RhFe intermetallic catalyst arises from the synergistic effect: the strong OH binding energy (OHBE) at Fe sites induce stably adsorbed OH species and thus facilitate the dehydrogenation step of methanol via rapid hydrogen transfer, while moderate OHBE at Rh sites promote the formation of the transition state (Pt‐CO···OH‐Rh) with a low activation barrier for CO removal. This work provides new insights into the role of OH binding strength in the removal of CO species, which is beneficial for the rational design of highly efficient catalysts.