Anion-modulated nickel-based nanoheterostructures as high performance electrocatalysts for hydrogen evolution reaction

The two-phase interface of hybrid catalysts plays an important role in improving their electrocatalytic activity due to the strong electronic interactions at the interface region. Therefore, we aim to elaborately design and exploit the architectures and interactions at the interface of binary nanoheterostructures, thus offering great potential to significantly boost the electrocatalytic performance of the hydrogen evolution reaction (HER) and gain deep insight into the HER mechanisms. Herein, we present a new strategy for the fabrication of a library of Ni-based anion-modulated nanoheterostructures (Ni-a-m-NHs), including nickel foam (NF)-supported ultrathin Ni(3)Se(4)nanosheets decorated with uniform Ni2P nanoparticles, Ni(3)S(4)nanorods, and NiSe(2)nanowires, as highly active electrocatalysts for the HER. All the Ni-a-m-NH catalysts exhibited superior electrocatalytic HER performances compared to that of their corresponding single-component catalysts and previously reported hybrid electrocatalysts. Unlike multi-metal hybrid electrocatalysts, Ni-a-m-NHs uniquely modulate the electronic interactions at the interface region due to the large difference in the electronegativity and magnitude of the electron-attracting effects between their different nonmetallic elements, which is supported by the experimental and DFT analyses.