Nitrogen-Regulated Nickel d Band Sites in Fullerene-Derived Electrocatalysts Boost the Alkaline Hydrogen Evolution Reaction

Design and construction of efficient and robust electrocatalysts for the hydrogen evolution reaction (HER) are of great importance for renewable energy technologies, but challenge remains for the large-scale commercial application. The good stability and large electrochemical active area of nanomaterials have been widely studied in the field of energy storage and conversion. Regulating the d band electronic structure has been considered as a powerful approach to boost the HER activity. Herein, an efficient electrocatalyst comprising Ni nanoparticles anchored on the N-doped carbon matrix derived from a fullerene/nickel tetraphenylporphyrin (C 60 /NiTPP) nanoflower assembly was fabricated successfully. The as-synthesized Ni(TPP)/NC exhibited promising HER activity under alkaline condition. To deliver a current density of 10 mA cm –2, it required an overpotential of 114 mV along with a nearly 100% Faradaic efficiency. Both experimental and density functional theory calculation results revealed that the pyrrolic N could modulate the 3d band center of Ni sites in Ni(TPP)/NC, which facilitate the adsorption of water molecules and desorption of hydrogen intermediates, leading to the reduced kinetic energy barrier and enhanced electrocatalytic HER activity. This work would provide useful guidance for designing and developing efficient electrocatalysts for hydrogen production.