Sub-2 nm Microstrained High-Entropy-Alloy Nanoparticles Boost Hydrogen Electrocatalysis.

High-entropy alloys (HEAs) confine multifarious elements into the same lattice, leading to intense lattice distortion effect. The lattice distortion tends to induce local microstrain at atomic level and thus affect surface adsorptions toward different adsorbates in various electrocatalytic reactions, yet remains unexplored. Herein, this work reports a class of sub-2 nm IrRuRhMoW HEA nanoparticles (NPs) with distinct local microstrain induced by lattice distortion for boosting alkaline hydrogen oxidation (HOR) and evolution reactions (HER). This work demonstrates that the distortion-rich HEA catalysts with optimized electronic structure can downshift the d-band center and generate uncoordinated oxygen sites to enhance the surface oxophilicity. As a result, the IrRuRhMoW HEA NPs show a remarkable HOR kinetic current density of 8.09 mA µg at 50 mV versus RHE, 8.89, 22.47 times higher than those of IrRuRh NPs without internal strain and commercial Pt/C, respectively, which is the best value among all the reported non-Pt based catalysts. IrRuRhMoW HEA NPs also display great HER performances with a turnover frequency (TOF) value of 5.93 H s at 70 mV versus RHE, 4.6-fold higher than that of Pt/C catalyst, exceeding most noble metal-based catalysts. Experimental characterizations and theoretical studies collectively confirm that weakened hydrogen (H) and enhanced hydroxyl (OH) adsorption are achieved by simultaneously modulating the hydrogen adsorption binding energy and surface oxophilicity originated from intensified ligand effect and microstrain effect over IrRuRhMoW HEA NPs, which guarantees the remarkable performances toward HOR/HER.