Coordination Effect-Promoted Durable Ni(OH)(2) for Energy-Saving Hydrogen Evolution from Water/Methanol Co-Electrocatalysis

Electrocatalytic water splitting is a viable technique for generating hydrogen but is precluded from the sluggish kinetics of oxygen evolution reactions (OER). Small molecule oxidation reactions with lower working potentials, such as methanol oxidation reactions, are good alternatives to OER with faster kinetics. However, the typically employed Ni-based electrocatalysts have poor activity and stability. Herein, a novel three-dimensional (3D)-networking Mo-doped Ni(OH)(2) with ultralow Ni–Ni coordination is synthesized, which exhibits a high MOR activity of 100 mA cm(−2) at 1.39 V, delivering 28 mV dec(−1) for the Tafel slope. Meanwhile, hydrogen evolution with value-added formate co-generation is boosted with a current density of more than 500 mA cm(−2) at a cell voltage of 2.00 V for 50 h, showing excellent stability in an industrial alkaline concentration (6 M KOH). Mechanistic studies based on density functional theory and X-ray absorption spectroscopy showed that the improved performance is mainly attributed to the ultralow Ni–Ni coordination, 3D-networking structures and Mo dopants, which improve the catalytic activity, increase the active site density and strengthen the Ni(OH)(2) 3D-networking structures, respectively. This study paves a new way for designing electrocatalysts with enhanced activity and durability for industrial energy-saving hydrogen production. [Image: see text] SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40820-022-00940-3.