Atomic-Scale Platinum Catalysts via Electron-Beam Irradiation: A Strategy for Robust Hydrogen Evolution Reaction

Achieving atomically dispersed and robust Pt electrocatalysts through mild, efficient synthesis remains an urgent and challenging objective for the hydrogen evolution reaction (HER). Here, atomic-scale Pt clusters supported on carbon nanotubes (CNTs) were fabricated via room-temperature electron-beam irradiation under an ambient atmosphere. The resulting Pt/CNT catalyst with a Pt loading of 6 wt % exhibits superior HER activity and stability compared to commercial 20% Pt/C. Notably, after 6000 cyclic voltammetry cycles, the Pt/CNT-300 kGy sample shows a continuous improvement in HER performance, with the overpotential at 10 mA cm^-2 decreasing from 30.5 to 27.5 mV and the mass activity at an overpotential of 40 mV increasing from 3.0 to 3.3 A mg_Pt^-1. Density functional theory calculations and experiments reveal that the Pt active sites and electronic structure could be effectively regulated by irradiation of the adsorbed dose from 100 to 400 kGy and Pt₄-Cl-C active sites could transform into more robust Pt₄-C structures after durability measurement. This work develops an effective strategy for fabricating high-performance HER catalysts via atomic-scale Pt modification.