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Photo‐Activating Biomimetic Polyoxomolybdate for Boosting Oxygen Evolution in Neutral Electrolytes

Dahuan Li, Xiaoyue Zhang, Jiangquan Lv, Pingwei Cai, Yan‐Qiong Sun, Cai Sun, Shou‐Tian Zheng

2023Angewandte Chemie International Edition67 citationsDOIOpen Access PDF

Abstract

Abstract Inspired by the metal‐oxo cluster structural feature and charge separation behaviour of the oxygen evolving center (OEC) in photosystem II (PS‐II) under photoirradiation, a new crystalline photochromic polyoxomolybdate, MV 2 [ β ‐Mo 8 O 26 ] ( 1 , MV=methyl viologen cation), is designed as a biomimetic oxygen evolution reaction (OER) catalyst in neutral electrolytes. After photoinduced electron transfer (PIET) with colour change from colourless to grey, it remains in an ultra‐stable charge‐separated state over a year under ambient conditions. The observed overpotential at 10 mA ⋅ cm −2 and Tafel slope decrease by 49 mV and 62.8 mV ⋅ dec −1 after coloration, respectively. The outstanding OER performance of the coloured state in neutral electrolytes even outperforms the commercial RuO 2 benchmark. Experimental and theoretical studies show that oxygen holes within polyanions after irradiation serve as sites for enhancing direct O−O coupling, thus effectively promoting OER. This is the first successful application of electron‐transfer photochromism to realize OER activity gain.

Topics & Concepts

Oxygen evolutionTafel equationElectrolytePhotochromismElectron transferChemistryOverpotentialOxygenPhotosystem IIPhotochemistryElectrochemistryElectrodePhysical chemistryPhotosynthesisBiochemistryOrganic chemistryElectrocatalysts for Energy ConversionAdvanced Nanomaterials in CatalysisPolyoxometalates: Synthesis and Applications