Surface oxygen vacancies induced by cu-doping in hexagonal ZnMn2O4 nanoplates for high efficiency photothermocatalytic oxidation of toluene

The exploitation of efficient and stable photothermal catalyst for the deep mineralization of volatile organic compounds (VOCs) is crucial and challenging. Herein, a photothermal catalyst with abundant oxygen defects was prepared for the first time via Cu-doped ZnMn2O4 hexagonal nanoplate. Experimental characterization results reveal that Cu doping enhances not only the ZnMn2O4 defect contents but also the light absorption and thermal conversion ability of ZnMn2O4. Compared to the undoped ZnMn2O4 (ZMO), the ZnMn2O4 with optimal Cu doping amount (ZMO-4Cu) exhibits excellent photothermal catalytic performance (94% toluene conversion and 87% toluene mineralization) and good resistance to low concentration SO2 under full-spectrum light irradiation. Experimental characterizations and theoretical calculations jointly demonstrated that the oxygen vacancies of ZMO-4Cu surface are more conducive to the adsorption of O2, effectively reduce the oxygen dissociation energy of ZMO-4Cu, thus generating abundant active oxygen species and improving the photothermal catalytic activity for toluene oxidation. In situ IR experiments disclosed that photothermal catalysis is more conducive to the toluene deep oxidation than thermal catalysis. This work provides new insights for the design of high efficiency photothermal catalysis for the deep oxidation of VOCs.