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Updated: May 22, 2026

Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
Published on: August 7, 2018
Elucidating the Oxygen-Activation Mechanism in Nonheme MnII-, FeII-, or CoII-Containing MOFs Mimicking
Ziyue Huang1, Yingqi Li1, Xiaotian Zhang1
1Jiangsu Key Laboratory of Biofunctional Materials, School of Chemistry and Materials Science, Ministry-of-Education Key Laboratory of Numerical Simulation of Large-Scale Complex Systems, Nanjing Normal University, Nanjing, Jiangsu 210023, China.
Abstract:
A Fe/Zn metal-organic framework (MOF) that mimics the FeII/2-oxoglutarate-dependent complex (FeII/2-OGDC) was reported previously, but its oxygen-activation mechanism remains unclear. In the present research, density functional theory (DFT) calculations were used to study this Fe-based system and its Mn- and Co-substituted analogues. We found that all three systems follow the general oxygen-activation chemistry of FeII/2-OGDC but show clear metal-dependent differences. The Fe and Co systems generate high-spin TMIV-oxo complexes, whereas the Mn system forms high-spin MnIII-oxyl complexes. The energy profiles further show that the formation of the key oxidizing intermediate is more favorable in the Fe and Mn systems than in the Co system. Overall, this work explains how changing the metal center affects oxygen activation in MOF-based enzyme mimics and highlights Mn as a more promising substitute for Fe than Co.
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