Manganese(ii) phosphate nanosheet assembly with native out-of-plane Mn centres for electrocatalytic water oxidation

Abstract

Nature selects Mn-clusters as catalysts for water oxidation, which is a significant reaction in photosynthesis. Thus, it is of critical importance to develop Mn-based superstructures and study their catalytic details for water-splitting-based renewable energy research. Herein, we report a manganese(II) phosphate nanosheet assembly with asymmetric out-of-plane Mn centers from the transformation of amine-intercalated nanoplates for efficient electrocatalytic water oxidation in neutral aqueous solutions. From structural and computational studies, it is found that the native out-of-plane Mn centers with terminal water ligands are accessible and preferential oxidation sites to form active intermediates for water oxidation. In addition, the asymmetry can stabilize the key Mn^III intermediate, as demonstrated by electrochemical and spectrometric studies. This study delivers a convenient strategy to prepare unique nanosheet assemblies for electrocatalysis and fundamental understandings of oxygen evolution chemistry.