Autologous Cobalt Phosphates with Modulated Coordination Sites for Electrocatalytic Water Oxidation

The correlation between metal coordination and electrocatalytic water oxidation performance is elusive in many cobalt‐based materials. Herein, we designed an ideal Co phosphate‐based platform to explore the effect of coordination environment on oxygen evolution reaction (OER) activity. The cobalt geometry was modulated from octahedral to tetrahedral by simple removal of water ligands in Co3(PO4)2⋅8 H2O. Other features except the coordination structure in the two autologous materials remain similar. The two analogues display the same OER kinetics, but the anhydrous Co3(PO4)2 exhibits a greatly enhanced OER activity. On the basis of Raman and operando XAS results, the higher intrinsic activity of the Co tetrahedral sites is because they facilitate the formation of active high valent cobalt (hydr)oxide intermediates during OER. This work not only brings insights of OER on Co‐based electrocatalysts but also provides a reference system to study the effect of metal geometry on electrocatalysis. Origins of OER: The metal geometry in cobalt phosphates was modulated from octahedral to tetrahedral by the simple removal of crystal water in Co3(PO4)2⋅8 H2O. The two materials form an ideal platform for the study the oxygen evolution reaction (OER) related to the metal coordination structure.