Replicating the Palladium Structure Enables Ni3InN to Surpass Nickel in Selective Hydrogenation

In heterogeneous catalysis, enhancing selectivity and activity simultaneously is crucial for industrial and environmental applications. Herein, we address this challenge by replicating the catalytically relevant structural characteristics of palladium (Pd) using a nickel-indium-nitrogen (Ni3InN) antiperovskite catalyst, which significantly improves the performance of Ni in selective hydrogenation reactions. The coordination of indium and subsurface interstitial nitrogen downshifts the d-band center from −1.42 to −1.59 eV. It expands the Ni-Ni distance from 2.49 to 2.72 Å, approaching the values observed in Pd. The ordered structure of Ni3InN mirrors the surface atomic arrangements of Pd with selective ensembles. Consequently, a significantly increase was observed for both butenes selectivity (from 14% to 93%) and a 3.5- to 6.3-fold enhancement in activity for 1,3-butadiene hydrogenation. This improvement is attributed to weakened adsorption, which alters the rate-determining step to one with a lower barrier, while suppressing side reactions, as revealed by theoretical simulations. These findings highlight the potential of structural mimicry in developing efficient and cost-effective non-precious metal catalysts.