Theoretical study on nitrobenzene hydrogenation to aniline catalyzed by M1/CeO2-(111) single-atom catalysts
Haohao Wang1, Min Pu1, Ming Lei1
1State Key Laboratory of Chemical Resource Engineering, Institute of Computational Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China. leim@mail.buct.edu.cn.
Abstract:
The hydrogenation of nitrobenzene to aniline is a critical process in the production of numerous chemical intermediates and pharmaceuticals. Developing efficient catalysts for this reaction is essential to improve reaction rates and selectivity. A density functional theory (DFT) study was performed to investigate the catalytic activity of twelve late transition metal-doped ceria (M1/CeO2-(111)) single-atom catalysts for the hydrogenation of nitrobenzene to aniline. Firstly, the stabilities and oxidation states of doped metal atoms on M1/CeO2-(111) surfaces were studied. Subsequently, the reactivity of two possible rate-determining steps on M1/CeO2-(111) surfaces, H2 dissociation and the fourth hydrogen transfer step in the direct route of nitrobenzene hydrogenation (PhNHO* + H* → PhNHOH*), was further investigated. The Brønsted-Evans-Polanyi (BEP) relationship between reaction energies (ΔE) and activation energies (Ea) and the volcano plot between the energies of PhNHOH* (EPhNHOH*) and the activation energies (Ea) of the fourth hydrogen transfer step were identified. The calculated results indicate that the fourth hydrogen transfer step is the rate-determining step in the overall reaction, and that the Ru1/CeO2-(111) single-atom catalyst could be one of the most promising catalysts with good catalytic activity for the nitrobenzene hydrogenation.
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Catalysis
