Coordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity

To achieve zero-carbon economy, advanced anode catalysts are desirable for hydrogen production and biomass upgrading powered by renewable energy. Ni-based non-precious electrocatalysts are considered as potential candidates because of intrinsic redox attributes, but in-depth understanding and rational design of Ni site coordination still remain challenging. Here, we perform anodic electrochemical oxidation of Ni-metalloids (NiP(x), NiS(x), and NiSe(x)) to in-situ construct different oxyanion-coordinated amorphous nickel oxyhydroxides (NiOOH-TO(x)), among which NiOOH-PO(x) shows optimal local coordination environment and boosts electrocatalytic activity of Ni sites towards selective oxidation of methanol to formate. Experiments and theoretical results demonstrate that NiOOH-PO(x) possesses improved adsorption of OH* and methanol, and favors the formation of CH(3)O* intermediates. The coordinated phosphate oxyanions effectively tailor the d band center of Ni sites and increases Ni-O covalency, promoting the catalytic activity. This study provides additional insights into modulation of active-center coordination environment via oxyanions for organic molecules transformation.