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 CH₃O* 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.

为了实现零碳经济，先进的阳极催化剂对于以可再生能源为动力的制氢和生物质升级是可取的。Ni基非贵重电催化剂由于其固有的氧化还原特性而被认为是潜在的候选者，但对Ni位点配位的深入理解和合理设计仍然具有挑战性。_{在这里，我们对镍类金属（NiP x}、NiS _x和NiSe _x ）进行阳极电化学氧化，以原位构建不同的氧阴离子配位无定形羟基氧化镍（NiOOH-TO _x），其中NiOOH-PO _x显示了最佳的局部配位环境，并提高了 Ni 位点对甲醇选择性氧化为甲酸盐的电催化活性。实验和理论结果表明，NiOOH-PO _x对 OH* 和甲醇的吸附能力有所提高，有利于 CH ₃ O* 中间体的形成。配位的磷酸盐氧阴离子有效地调整了Ni位点的d带中心并增加了Ni-O的共价键，从而提高了催化活性。该研究为通过氧阴离子调节活性中心配位环境以进行有机分子转化提供了额外的见解。