Surface Confinement of Atomically Thin Pt Nanoclusters on 2D δ‐Mon for Durable pH‐Universal Hydrogen Evolution

Abstract Engineering precious metals’ sub‐nanometer cluster on 2D earth‐abundant supports provides a promising approach for the development of high‐efficient electrocatalysts in pursuit of green hydrogen. Herein, a novel solid phase deposition approach is demonstrated for the homogenous confinement of atomically thin Pt nanoclusters on 2D delta‐MoN as a viable catalyst for pH‐universal hydrogen evolution reaction. Notably, the optimized material (MoN‐5% Pt) exhibits excellent catalytic performance as evidenced by low overpotentials required, excellent mass activity exceeding 20 A mg_Pt⁻¹ at 100 mV overpotential, and outstanding stability with negligible activity degradation. The enhanced performance is attributed to (1) novel nanostructure, constituting atomically thin Pt nanoclusters confined on 2D δ‐MoN substrate, thus rendering high atomic utilization and seamless surface mass transfer, and (2) influence of strong metal‐support interaction that effectively limits structural deformation and performance degradation. Theoretical simulations reveal that the strong metal‐support interaction induces substantial charge redistribution across the heterointerface, initiating an energy‐favorable multi‐active site microkinetics in which Pt atoms with an optimal hydrogen adsorption energy making way for enhanced H2 evolution, while Mo atoms situated at the heterointerface enhance water absorption/dissociation steps, enriching the catalytic surface with adsorbed hydrogen atoms.