Canonic‐Like HER Activity of Cr_1–xMo_xB₂ Solid Solution: Overpowering Pt/C at High Current Density

Abstract 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 Cr_1–xMo_xB₂ (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, Cr_0.4Mo_0.6B₂ outperforms Pt/C, as it needs 180 mV less overpotential to drive an 800 mA cm⁻² current density. Cr_0.4Mo_0.6B₂ 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.