Cobalt-based materials have been considered as promising candidates to electrocatalyze water oxidation. However, the structure-performance correlation remains largely elusive, due to the complex material structures and diverse performance-influencing factors in those Co-based catalysts. In this work, we designed two cobalt phosphates with distinct Co symmetry to explore the effect of coordination symmetry on electrocatalytic water oxidation. The two analogues have similar morphology, Co valence and 6-coordinated Co octahedron, but with different coordination symmetry. In contrast to symmetric Co₃(PO₄)₂·8H₂O, asymmetric NH₄CoPO₄·H₂O exhibited enhanced electrocatalytic water oxidation activity in a neutral aqueous solution. It is proven that, by experimental and theoretical studies, the asymmetric Co coordination sites can facilitate the surface reconstruction under anodic polarization to boost the electrocatalysis. Based on this contrastive platform with distinct symmetry differences, the preferred configuration in cobalt-oxygen octahedrons for water oxidation has been straightforwardly assigned.

钴基材料被认为是电催化水氧化的有希望的候选材料。然而，由于这些钴基催化剂中复杂的材料结构和不同的性能影响因素，结构-性能相关性在很大程度上仍然难以捉摸。在这项工作中，我们设计了两种具有不同 Co 对称性的磷酸钴，以探索配位对称性对电催化水氧化的影响。这两种类似物具有相似的形态，共价和6配位Co八面体，但配位对称性不同。与对称Co ₃ (PO ₄ ) ₂ ·8H ₂ O相比，非对称NH ₄ CoPO ₄ ·H ₂O 在中性水溶液中表现出增强的电催化水氧化活性。通过实验和理论研究证明，不对称的Co配位点可以促进阳极极化下的表面重建，从而促进电催化。基于这种具有明显对称性差异的对比平台，直接指定了用于水氧化的钴氧八面体的优选构型。