Enhanced formaldehyde oxidation over MnO₂ and doped manganese-based catalysts: Experimental and theoretical Insights...

Thermal catalytic degradation of formaldehyde (HCHO) over manganese-based catalysts is garnering significant attention. In this study, both theoretical simulations and experimental methods were employed to elucidate the primary reaction pathways of HCHO on the MnO₂(110) surface. Specifically, the effects of doping MnO₂ with elements such as Fe, Ce, Ni, Co, and Cu on the HCHO oxidation properties were evaluated. Advanced characterization techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET), and X-ray photoelectron spectroscopy (XPS), were employed to discern the physical properties and chemical states of the active components on the catalyst surface. The comprehensive oxidation pathway of HCHO on the MnO₂(110) surface includes O₂ adsorption and dissociation, HCHO adsorption and dehydrogenation, CO₂ desorption, H₂O formation and desorption, oxygen vacancy supplementation, and other elementary reactions. The pivotal rate-determining step was identified as the hydrogen migration process, characterized by an energy barrier of 234.19 kJ mol^-1. Notably, HCHOO and *CHOO emerged as crucial intermediates during the reaction. Among the doped catalysts, Fe-doped MnO₂ outperformed its counterparts doped with Ce, Ni, Co, and Cu. The optimal degradation rate and selectivity were achieved at a molar ratio of Fe: Mn = 0.1. The superior performance of the Fe-doped MnO₂ can be ascribed to its large specific surface area, conducive pore structure for HCHO molecular transport, rich surface-adsorbed oxygen species, and a significant presence of oxygen vacancies.