Tremella-Like Ni–NiO with O-Vacancy Heterostructure Nanosheets Grown In Situ on MXenes for Highly Efficient Hydrogen and Oxygen Evolution

Electronic modulation via heterostructures or vacancies has been recently regarded as an effective strategy to improve electrocatalytic activity by optimizing the adsorption free energies of hydrogen evolution reaction (HER) or oxygen evolution reaction (OER) active intermediates during the reaction. Herein, tremella-like Ni-NiO with O-vacancy heterostructure nanosheets grown in situ on Ti₃C₂T_x MXenes (Ni-NiO/Ti₃C₂T_x MXene) are fabricated via a facile strategy. Benefitting from the heterointerfaces between Ni and NiO, the synergetic coupling effects of MXenes and Ni-NiO heterostructures, the O-vacancies, and the unique architecture, the as-prepared Ni-NiO/Ti₃C₂T_x MXene showed superior activity toward the HER and OER in alkaline electrolyte, only requiring overpotentials of 72 mV for the HER and 248 mV for the OER to offer 10 mA cm^-2. Density functional theory (DFT) calculations revealed that Ni-NiO with O-vacancies can effectively increase the electron density around the Fermi level and modulate the Gibbs free energies of the intermediates during catalytic reactions, thus accelerating the reaction kinetics.