Oxidation mechanism of HCHO on copper-manganese composite oxides catalyst

Formaldehyde (HCHO) is a typical air pollutant that severely endangers human health. The Cu-Mn spinel-structure catalyst exhibits good catalytic oxidation activity for HCHO removal. Theoretical calculation study of density functional theory (DFT) was performed to provide an atomic-scale understanding for the oxidation mechanism of HCHO over CuMn2O4 surface. The results indicate that the (110) surface containing alternating three-coordinated Cu atom and three-coordinated Mn atom is more active for HCHO and O2 adsorption than the (100) surface. The Mars-van-Krevelen mechanism is dominant for HCHO catalytic oxidation. This reaction pathway of MvK mechanism includes HCHO adsorption and dehydrogenation dissociation, CO2 formation and desorption, O2 adsorption, H2O formation and surface restoration. In the complete catalytic cycle of HCHO oxidation, the second dehydrogenation (CHO* -> CO* + H*) shows the highest energy barrier and is recognized as the rate-limiting step. The relationship of temperature and reaction rate constant is found to be positive by the kinetic analysis. The minimum activation energy of the MvK mechanism via the direct dehydrogenation pathway is 1.29 eV. This theoretical work provides an insight into the catalytic mechanism of HCHO oxidation over CuMn2O4 spinel.

Automated summary

Formaldehyde (HCHO) is a harmful air pollutant. Cu-Mn spinel-structure catalyst shows good oxidation activity for HCHO removal. Density functional theory (DFT) calculations reveal the atomic-scale oxidation mechanism of HCHO on CuMn2O4 surface. The Mars-van-Krevelen mechanism dominates the HCHO catalytic oxidation, with the second dehydrogenation step identified as rate-limiting.