Methane plasma-mediated phase engineering of Ni nanosheets for alkaline hydrogen evolution

Engineering of the crystal structures of metallic nanomaterials is an alternative avenue to control the size and shape of nanocatalysts. However, the phase-controlled synthesis of Ni nanocatalysts is challenging because of its low reduction potential under mild conditions. We developed a room-temperature CH4 plasma conversion of Ni(OH)(2) nanosheets to hexagonal close packed (hcp) Ni while maintaining a pristine shape. Increasing the temperature resulted in the formation of face-centered cubic (fcc) Ni. The hcp Ni nanosheets exhibited an overpotential of 85 mV at 10 mA cm(-2) for an electrocatalytic hydrogen evolution reaction (HER) in alkaline solution, which was superior to that of the fcc (122 mV) counterpart. Density-functional-theory calculations demonstrated that during the HER, the d-band center of hcp Ni was closer to the Fermi level, which aided the formation of H-2 molecules. This work could facilitate the synthesis of other metastable metals and metallic alloys with high efficiency for various applications.