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[Display omitted] • Abundant electron-rich Co centers generated by Mg doping enhanced PMS activation. • MCO@PES membrane/PMS system achieved instant contaminants elimination. • The highly accessible SO 4 −, OH, and 1O 2 were the responsible reactive species. • Catalyst recovery and enhanced mass transfer in membrane provided the application value. The practical application of heterogeneous Fenton-like processes in wastewater treatment is limited by inadequate catalyst recovery and limited mass transfer in traditional batch mode. Consequently, a catalytic membrane composed of inert magnesium (Mg)-doped Co 3 O 4 spinel (MCO) was crafted to activate peroxymonosulfate (PMS) for the elimination of organic contaminants. The incorporation of the less electronegative Mg induced electronic polarization on the MCO surface, resulting in the generation of sufficient electron-rich Co centers, thereby amplifying its electron-donating properties in PMS activation and enhancing the inherent catalytic activity of the spinel. Regarding the catalytic membrane, the stacked porous structure of the MCO layer achieved reactive sites exposure, mass transfer enhancement, and reactive species availability. Remarkably, the MCO@polyethersulfone (PES) membrane/PMS system instantaneously activated PMS, displaying an elimination kinetic constant of 0.039 ms−1 for tetracycline. The MCO@PES membrane exhibited exceptional catalytic performance and stability in long-term operational studies. Mechanistic investigations elucidated that the highly accessible SO 4 −, OH, and 1O 2 within the catalytic membrane facilitated the immediate elimination of contaminants. This study serves as a valuable reference for the application of transition metal spinel-based catalytic membranes in wastewater treatment. [ABSTRACT FROM AUTHOR]

Co–Zn–N–C catalyst (MCZC) with neighboring Co and Zn pairs anchored on hollow carbon nitride was constructed by the direct etching of zeolitic imidazolate frameworks assembled with Co and Zn. Adequate characterizations and density functional theory (DFT) studies confirmed the successful construction of non-bonding Co and Zn pairs with enhanced electron transfer on Co sites by adjacent Zn sites. Based on the synergy of adjacent Co and Zn atom pairs, the MCZC/Perxymosulfate (PMS) system achieved 99.6% Tetracycline (TC) degradation in 24 min with a mineralization rate of 55.8% and PMS decomposition efficiency of 73.1%. DFT calculation based on the Fukui index identified the sites susceptible to attack by the active species. TC degradation pathways could be inferred, and reduced toxicity of intermediates was observed. This work provides new insights into the design of MOF-derived bimetallic catalysts and the importance of the interaction between adjacent metal active sites to catalytic performance. [Display omitted] • Co, Zn doped hollow carbon nitride catalyst was synthesized by etching Co 0.5 Zn 0.5 -ZIF. • Co sites were highly activated by adjacent Zn atoms via non-bonding interaction. • MCZC/PMS system achieved efficient tetracycline degradation and risk control. • The unique structure provides MCZC catalyst with high stability and low metal leaching. [ABSTRACT FROM AUTHOR]