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Combination of Highly Efficient Electrocatalytic Water Oxidation with Selective Oxygenation of Organic Substrates using Manganese Borophosphates
Author(s) -
Menezes Prashanth W.,
Walter Carsten,
Chakraborty Biswarup,
Hausmann Jan Niklas,
Zaharieva Ivelina,
Frick Achidi,
Hauff Elizabeth,
Dau Holger,
Driess Matthias
Publication year - 2021
Publication title -
advanced materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.707
H-Index - 527
eISSN - 1521-4095
pISSN - 0935-9648
DOI - 10.1002/adma.202004098
Subject(s) - manganese , catalysis , oxygen evolution , materials science , birnessite , inorganic chemistry , chemical engineering , chemistry , electrochemistry , organic chemistry , manganese oxide , electrode , engineering , metallurgy
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.