Search

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 TM−O covalency in governing the intrinsic catalytic activity of Co3−xMnxO4 spinel oxides. Experimental and theoretical analysis reveals that the Co sites significantly raises the Mn valence and enlarges Mn−O covalency in octahedral configuration, thereby lowering the charge transfer energy to favor MnOh–PMS interaction. With appropriate MnIV/MnIII ratio to balance PMS adsorption and MnIV reduction, the Co1.1Mn1.9O4 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. [ABSTRACT FROM AUTHOR]

Innentitelbild: Mn-O Covalency Governs the Intrinsic Activity of Co-Mn Spinel Oxides for Boosted Peroxymonosulfate Activation (Angew. Keywords: bimetal; covalency; octahedron; peroxymonosulfate (PMS); spinel oxides EN bimetal covalency octahedron peroxymonosulfate (PMS) spinel oxides 2 2 1 12/24/20 20210104 NES 210104 B Bimetallische Spinelloxide b sind effiziente Katalysatoren für die Aktivierung von Peroxymonosulfat (PMS), der katalytische Mechanismus ist jedoch unklar. Co verstärkt die Mn-O-Kovalenz in der oktaedrischen Konfiguration von Co SB 3-x sb Mn SB x sb O SB 4 sb , was die Ladungstransferenergie der Mn SB Oh sb -PMS-Wechselwirkung senkt und die Mn SP VI sp /Mn SP III sp -Redoxzyklen drastisch beschleunigt. [Extracted from the article]