Local Hydrogen Field Engineering in Ni-Based Catalysts for Low-Temperature Aromatic Hydrogenation

Abstract Efficient low-temperature hydrogenation of both heteroaromatic and benzenoid compounds using nonprecious metals remains challenging. Here, we report a nitrogen-doped carbon interfacial modification that creates a local hydrogen field (LHF) at the Ni/NC/HAP interface. In situ spectroscopy, kinetic isotope measurements, and molecular dynamics simulations elucidate the origin and kinetic basis of this interfacial microenvironment. Initially, H2 dissociates at Ni sites, and H atoms rapidly migrate across the NC layer via N-functional groups to the HAP surface, where they bind to surface phosphate oxygens to form hydroxyls. As hydrogen supply outruns the slow furan ring saturation, these terminal hydroxyls accumulate to form the LHF. Electronic feedback from this localized field shifts the d-band center and lowers the work function of adjacent Ni sites. This electronic modulation drives substrate molecules into a parallel adsorption geometry at the interfacial active sites, strengthening reactant binding and facilitating activation. The optimized Ni/NC/HAP-0.25 catalyst achieves 99.9% furfural conversion at 40 °C with an apparent tetrahydrofurfuryl alcohol formation rate of 1936.3 mmol molmetal–1 h–1, outperforming Raney Ni by 21.3-fold, and works for diverse aromatic substrates. This study demonstrates that coupling rapid hydrogen supply to interfacial electronic modulation advances low-temperature hydrogenation on nonprecious metals.