NH3 molecule adsorption on spinel-type ZnFe2O4 surface: A DFT and experimental comparison study

Ammonia (NH3) is a caustic environment pollutant which contributes to haze formation and water pollution. Zinc ferrite (ZnFe2O4) exhibits good catalytic activity in NH3 removal. The density functional theory (DFT) was applied to explore the interaction mechanism of NH3 molecule adsorption on spinel-type ZnFe2O4 (1 1 0) surface with GGA-PW91 method in atomic and electronic level. The results indicated that NH3 molecule preferred to adsorb on surface Zn atom with the formation of H3NZn coordinate bond over ZnFe2O4 (1 1 0) surface. The H3NZn state was exothermic process with adsorption energy of −203.125 kJ/mol. About 0.157e were transferred from NH3 molecule to the surface which resulted in strong interaction. Higher activation degree occurred in H3NZn configuration with two NH bonds elongated and NH3 structure became more flat on the surface. The PDOS change of NH3 molecule was consistent with the result of adsorption energy. It was concluded that s orbital of NH3 (N) and s, p orbitals of Zn atom overlapped at −0.619 Ha. The p orbital of NH3 (N) has interaction with d orbital of Zn atom suggesting the hybridization between them. Based on NH3 removal experimental and XPS spectra results, NH3ZnFe2O4 interaction was mainly depended on the coordination between Zn atom and NH3 molecule. The DFT calculations have deepened our understanding on NH3ZnFe2O4 interaction system.