Abstract
P-rich transition metal phosphides (TMPs) with abundant P sites have been predicted to be more favorable for hydrogen evolution reaction (HER) catalysis. However, the actual activities of P-rich TMPs do not behave as expected, and the underlying essence especially at the atomic level is also ambiguous. Our structural analysis reveals the inferior activity could stem from the reduced overlap of atomic wave functions between metal and P with the increase in P contents, which consequently results in too strong P-H interaction. To this end, we used N-induced lattice contraction to generally boost the HER catalysis of P-rich TMPs including CoP(2), FeP(2), NiP(2), and MoP(2). Refined structural characterization and theoretical analysis indicate the N-P strong interaction could increase the atomic wave function overlap and eventually modulate the H adsorption strength. The concept of lattice engineering offers a new vision for tuning the catalytic activities of P-rich TMPs and beyond.