Mn-O Covalency Governs the Intrinsic Activity of Co-Mn Spinel Oxides for Boosted Peroxymonosulfate Activation.

题目：Mn-O Covalency Governs the Intrinsic Activity of Co-Mn Spinel Oxides for Boosted Peroxymonosulfate Activation

作者：Zhi-Yan Guo, Chen-Xuan Li, Miao Gao, Xiao Han, Ying-Jie Zhang, Wen-Jun Zhang, and Wen-Wei Li*

摘要：Transition metal (TM)-based bimetallic spinel oxides can efficiently activate peroxymonosulfate (PMS) presumably attributed to enhanced electron transfer between TMs, but the existing model cannot fully explain the efficient TM redox cycling. Here, we discover a critical role of TMO covalency in governing the intrinsic catalytic activity of Co_3-xMn_xO₄ spinel oxides. Experimental and theoretical analysis reveals that the Co sites significantly raises the Mn valence and enlarges MnO covalency in octahedral configuration, thereby lowering the charge transfer energy to favor Mn_Oh–PMS interaction. With appropriate Mn^IV/Mn^III ratio to balance PMS adsorption and Mn^IV reduction, the Co_1.1Mn_1.9O₄ exhibits remarkable catalytic activities for PMS activation and pollutant degradation, outperforming all the reported TM spinel oxides. The improved understandings on the origins of spinel oxides activity for PMS activation may inspire the

development of more active and robust metal oxide catalysts.

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全文链接：https://doi.org/10.1002/anie.202010828