Switch Volmer‐Heyrovsky to Volmer‐Tafel Pathway for Efficient Acidic Electrocatalytic Hydrogen Evolution by Correlating Pt Single Atoms with Clusters

As cost‐effective catalysts, platinum (Pt) single‐atom catalysts (SACs) have attracted substantial attention. However, most studies indicate that Pt SACs in acidic hydrogen evolution reaction (HER) follow the slow Volmer‐Heyrovsky (VH) mechanism instead of the fast kinetic Volmer‐Tafel (VT) pathway. Here, this work propose that the VH mechanism in Pt SACs can be switched to the faster VT pathway for efficient HER by correlating Pt single atoms (SAs) with Pt clusters (Cs). Our calculations reveal that the correlation between Pt SAs and Cs significantly impacts the electronic structure of exposed Pt atoms, lowering the adsorption barrier for atomic hydrogen and enabling a faster VT mechanism. To validate these findings, this work purposely synthesize three catalysts: l ‐Pt@MoS 2 , m ‐Pt@MoS 2 and h ‐Pt@MoS 2 with low, moderate, and high Pt‐loading, having different distributions of Pt SAs and Cs. The m‐Pt@MoS 2 catalyst with properly correlating Pt SAs and Cs exhibits outstanding performance with an overpotential of 47 mV and Tafel slope of 32 mV dec −1 . Further analysis of the Tafel values confirms that the m ‐Pt@MoS 2 sample indeed follows the VT reaction mechanism, aligning with the theoretical findings. This study offers a deep understanding of the synergistic mechanism, paving a way for designing novel‐advanced catalysts.