Combination of Highly Efficient Electrocatalytic Water Oxidation with Selective Oxygenation of Organic Substrates using Manganese Borophosphates

Abstract One of the key catalytic reactions for life on earth, the oxidation of water to molecular oxygen, occurs in the oxygen‐evolving complex of the photosystem II (PSII) mediated by a manganese‐containing cluster. Considerable efforts in this research area embrace the development of efficient artificial manganese‐based catalysts for the oxygen evolution reaction (OER). Using artificial OER catalysts for selective oxygenation of organic substrates to produce value‐added chemicals is a worthwhile objective. However, unsatisfying catalytic performance and poor stability have been a fundamental bottleneck in the field of artificial PSII analogs. Herein, for the first time, a manganese‐based anode material is developed and paired up for combining electrocatalytic water oxidation and selective oxygenations of organics delivering the highest efficiency reported to date. This can be achieved by employing helical manganese borophosphates, representing a new class of materials. The uniquely high catalytic activity and durability (over 5 months) of the latter precursors in alkaline media are attributed to its unexpected surface transformation into an amorphous MnO_x phase with a birnessite‐like short‐range order and surface‐stabilized Mn^III sites under extended electrical bias, as unequivocally demonstrated by a combination of in situ Raman and quasi in situ X‐ray absorption spectroscopy as well as ex situ methods.