Canonic‐Like HER Activity of Cr1–xMoxB2 Solid Solution: Overpowering Pt/C at High Current Density

Abundant transition metal borides are emerging as substitute electrochemical hydrogen evolution reaction (HER) catalysts for noble metals. Herein, an unusual canonic‐like behavior of the c lattice parameter in the AlB2‐type solid solution Cr1–xMoxB2 (x = 0, 0.25, 0.4, 0.5, 0.6, 0.75, 1) and its direct correlation to the HER activity in 0.5 M H2SO4 solution are reported. The activity increases with increasing x, reaching its maximum at x = 0.6 before decreasing again. At high current densities, Cr0.4Mo0.6B2 outperforms Pt/C, as it needs 180 mV less overpotential to drive an 800 mA cm−2 current density. Cr0.4Mo0.6B2 has excellent long‐term stability and durability showing no significant activity loss after 5000 cycles and 25 h of operation in acid. First‐principles calculations have correctly reproduced the nonlinear dependence of the c lattice parameter and have shown that the mixed metal/B layers, such as (110), promote hydrogen evolution more efficiently for x = 0.6, supporting the experimental results. An unusual canonic‐like behavior of the c lattice parameter in the AlB2‐type solid solution Cr1–xMoxB2 is found to directly correlate to its hydrogen evolution reaction activity in 0.5 m H2SO4 solution. The best catalyst, Cr0.4Mo0.6B2, outperforms Pt/C at high current density. Density functional theory calculations demonstrate that the (110) mixed metal/B layer promotes hydrogen evolution more efficiently for x = 0.6, supporting the experimental results.