The effective non‐precious metal catalysts toward the oxygen evolution reaction (OER) are highly desirable for electrochemical water splitting. Herein, we prepare a novel glass‐ceramic (Ni1.5Sn@triMPO4) by embedding crystalline Ni1.5Sn nanoparticles into amorphous trimetallic phosphate (triMPO4) matrix. This unique crystalline‐amorphous nanostructure synergistically accelerates the surface reconstruction to active Ni(Fe)OOH, due to the low vacancy formation energy of Sn in glass‐ceramic and high adsorption energy of PO43− at the VO sites. Compared to the control samples, this dual‐phase glass‐ceramic exhibits a remarkably lowered overpotential and boosted OER kinetics after surface reconstruction, rivaling most of state‐of‐the‐art electrocatalysts. The residual PO43− and intrinsic VO sites induce redistribution of electron states, thus optimizing the adsorption of OH* and OOH* intermediates on metal oxyhydroxides and promoting the OER 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 (NiPx, NiSx, and NiSex) to in-situ construct different oxyanion-coordinated amorphous nickel oxyhydroxides (NiOOH-TOx), among which NiOOH-POx 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-POx 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.