Synergistic Effects of Phosphorus Doping and Oxygen Vacancies on Formaldehyde Oxidation over CeO$_2$(111): A First Principles Investigation

Abstract

Using a combination of static and dynamic density functional theory simulations, we systematically investigated how phosphorus doping and oxygen vacancies on the CeO$_2$(111) surface influence the oxidation mechanisms of formaldehyde (HCHO). Our results reveal that P cations (P$^{5+}$) substitutionally replace Ce$^{4+}$ in the lattice, forming Ce$-$O$-$P bonds that reduce the band gap (from 2.26 eV to 2.09 eV) and generate localized Ce$^{3+}$ states through charge redistribution. This synergistic effect of P doping combined with oxygen vacancy strengthens HCHO adsorption by decreasing the adsorption energy from -0.62 eV on pristine CeO$_2$(111) to -2.65 eV on the defective P-doped surface. Importantly, P doping lowers the C$-$H bond cleavage barrier by 0.84 eV relative to pristine CeO$_2$(111), accelerating formaldehyde oxidation on the defective surface. In addition, the rapid desorption of CO$_2$ and H$_2$O ($τ\sim 0.59 s$ at 300 K) indicates weak product-surface interactions, which favor efficient catalyst regeneration during continuous operation. These findings highlight P-doped CeO$_2$(111) as a promising system for low-temperature HCHO oxidation and provide insights into the design of ceria-based catalytic materials.