Efficient descriptors for the design of high-performance Ni-based catalysts modified with electronic inducers for the hydrogenation of 1,4-butynediol†

Manipulating the electronic structure and coordination configuration of heterogeneous catalysts presents a promising strategy for enhancing their intrinsic catalytic efficiency; however, it remains a complex challenge. In this study, guided by the theoretical principles of the d-band center and density functional theory, we systematically developed a unique class of heterogeneous nickel (Ni) (111) framework systems that utilize zirconium (Zr) species as electronic inducers (EIs) for the hydrogenation of 1,4-butynediol (BYD), involving the catalytic reaction over typical oxygen-containing unsaturated alkynes. The electronic inducer interaction significantly enhances electronic separation around Zr, and the d-band center gap (Δd) of Ni decreases linearly with the increase of incorporated Zr concentration, reaching a minimum of −0.67 eV at 36 at% Zr. Additionally, a strong linear correlation was observed between Δd and the adsorption energy of the key intermediate cis-1,4-butenediol (cis-BED), with the most favorable adsorption energy of −3.49 eV occurring at this minimum Δd. Furthermore, the energy barrier for the reaction cis-BED + H → cis-BEDH exhibits a perfect linear relationship with Δd, achieving its lowest activation barrier of 0.45 eV when Δd is minimized. These findings provide valuable insights for the design and optimization of efficient Ni-based catalysts for hydrogenation of oxygen-containing unsaturated compounds.