DFT Calculation Screening of Transition Metal (TM) Doped MgO Catalyzed Dry Reforming of Methane Reaction and Related Experimental Verification

Theoretical calculations can quickly screen for effective catalyst systems, and experimental verification is also essential. This paper uses density functional theory (DFT) to construct a transition metal (TM)-doped MgO structure. By studying the effects of TM doping on key steps in dry reforming of methane (DRM) reaction, including CO₂ adsorption and catalytic CO₂ dissociation, a comprehensive screening of 30 TMs was conducted. It indicates that TM atoms can promote the adsorption of CO₂ by MgO due to the presence of electron deficient d orbitals, and TM can also serve as main adsorption site to attract CO₂. After stability analysis of TM/MgO, calculation of CO₂ adsorption and dissociation, and comprehensive consideration of adsorption energy (<i>E</i>_ads) and energy barrier (<i>E</i>_a), it was screened from 30 systems that Mo/MgO had the lowest catalytic reaction <i>E</i>_a, Zr/MgO had the best <i>E</i>_ads, and Fe/MgO had the most balanced comprehensive properties. Based on theoretical calculations, Fe/MgO, Zr/MgO, and Mo/MgO were synthesized, characterized, and applied to catalyze DRM reaction. The reaction mechanism of TM/MgO(TM = Fe, Zr, Mo) catalyzing DRM was analyzed and compared from the perspectives of catalytic activity, stability, and types and quantities of carbon deposits, achieving the goal of theoretical calculations guiding experimental synthesis.