Synergistically Coupled Ni/CeO_x@C Electrocatalysts for the Hydrogen Evolution Reaction: Remarkable Performance to Pt/C at High Current Density

Incredibly active electrocatalysts comprising earth-abundant materials that operate as effectively as noble metal catalysts are essential for the sustainable generation of hydrogen through water splitting. However, the vast majority of active catalysts are produced via complicated synthetic processes, making scale-up considerably tricky. In this work, a facile strategy is developed to synthesize superhydrophilic Ni/CeO_x nanoparticles (NPs) integrated into porous carbon (Ni/CeO_x@C) by a simple two-step synthesis strategy as efficient hydrogen evolution reaction (HER) electrocatalysts in 1.0 M KOH. Benefiting from the electron transport induced by the heterogeneous interface between Ni and CeO_x NPs and the superhydrophilic structure of the catalyst, the resultant Ni₂Ce₁@C/500 catalysts exhibit a low overpotential of 26 and 184 mV at a current density of 10 and 300 mA cm^–2, respectively, for HER with a small Tafel slope of 62.03 mV dec^–1 and robust durability over 300 h, and its overpotential at a high current density is much better than the benchmark commercial Pt/C. Results revealed that the electronic rearrangement between Ni and CeO_x integrated into porous carbon could effectively regulate the local conductivity and charge density. In addition, the oxygen vacancies and Ni/CeO_x heterointerface promote water adsorption and hydrogen intermediate dissociation into H₂ molecules, which ultimately accelerate the HER reaction kinetics. Notably, the electrochemical results demonstrate that structural optimization by regulating synthesis temperature and metal concentration could improve the surface features contributing to high electrical conductivity and increase the number of electrochemically active sites on the Ni/CeO_x@C heterointerface, high crystal purity, and better electrical conductivity, resulting in its exceptional electrocatalytic performance toward the HER. These results indicated that the Ni/CeO_x@C electrocatalyst has the potential for practical water-splitting applications because of its controlled production strategy and outstanding Pt-like HER performance.