Magnesium Oxide-Supported Single Atoms with Fine-Modulated Steric Location for Polymerization Transfer Removal of Water Pollutants

Abstract

Organic pollutants removal via a polymerization transfer (PT) pathway based on the use of single-atom catalysts (SACs) promises efficient water purification with minimal energy/chemical inputs. However, the precise engineering of such catalytic systems toward PT decontamination is still challenging, and the conventional SACs are plagued by low structural stability of carbon material support. Here, we adopted magnesium oxide (MgO) as a structurally stable alternative for loading single copper (Cu) atoms to drive peroxymonosulfate-based Fenton-like reactions. Through fine-tuning the Cu atom steric location from lattice-embedding to surface-loading, the system exhibited a fundamental transition in the catalytic pathways toward the PT process and drastically improved decontamination efficiency. The catalytic pathway change was mainly ascribed to a downshifted d-band center of the Cu atoms. The optimized catalyst achieved complete, rapid removal of phenolic compounds from water via nearly 100% PT pathway, accompanied by high oxidant utilization efficiency surpassing most state-of-the-art SACs. Moreover, it showed excellent structural stability and environmental robustness and was successfully used for the treatment of lake water and industrial coking wastewater. The adaptability of the spatial engineering strategy to other MgO-supported single atoms, including Fe, Co, and Ni SACs, was also demonstrated. Our work lays a foundation for further advancing SACs-based advanced oxidation technologies toward sustainable water purification applications.