Holistic functional biomimetics: a key to make an efficient electrocatalyst for water oxidation

Abstract

Water oxidation is the holy grail reaction of natural and artificial photosynthesis. How to design an efficient water-oxidation catalyst remains a long-term challenge for solar fuel production. The rate of water oxidation in photosystem II by the oxygen-evolving complex (OEC) Mn₄CaO₅ cluster is as high as 100–400 s⁻¹. Mimicking the structures of the OEC is a straightforward strategy to design water-oxidation catalysts. However, the high efficiency of the OEC relies on not only its highly active site but also its holistic system for well-organized electron transfer and proton transport. Lacking such a holistic functional system makes δ-MnO₂ a poor water-oxidation catalyst, although the local structure of δ-MnO₂ is similar to that of the Mn₄CaO₅ cluster. Electrocatalysts simultaneously imitating the catalytically active sites, fast electron transfer, and promoted proton transport in a natural OEC have been rarely reported. The significance of the synergy of a holistic system is underrated in the design of water-oxidation catalysts. In this work, we fabricated holistic functional biomimetic composites of two-dimensional manganese oxide nanosheets and pyridyl-modified graphene (MnO_x-NS/py-G) for electrocatalytic water oxidation. MnO_x-NS/py-G simultaneously imitates the synergy of catalytically active sites, fast electron transfer, and promoted proton transport in a natural OEC, resulting in overall 600 times higher activity than that of typical δ-MnO₂. This work demonstrates the significance of holistic functional biomimetic design and guides the development of highly active electrocatalysts for small molecule activation related to solar energy storage.