期刊
CATALYSIS TODAY
卷 388, 期 -, 页码 208-215出版社
ELSEVIER
DOI: 10.1016/j.cattod.2020.07.039
关键词
Hydrogen adsorption; Catalytic hydrogenation; Metal catalyst; Solid/liquid interface; Ab initio molecular dynamics
资金
- Chemical Transformation Initiative - Laboratory Directed Research and Development (LDRD) program at Pacific Northwest National Laboratory (PNNL)
- US Department of Energy [DE-AC05-76RL01830, DE-AC52-07NA27344]
Understanding the hydrogenation of organic compounds in the aqueous phase is crucial for carbon neutral pathways. This study investigated the thermodynamic and kinetic profiles of benzaldehyde hydrogenation over Pd(111) and Pt(111) metal surfaces. The presence of surface charge and solvent greatly influenced the reaction.
Understanding the hydrogenation of organic compounds in the aqueous phase has always been fundamentally important for improving carbon neutral pathways to fuels and value-added chemicals. In this study, we inves-tigated both thermodynamic and kinetic profiles of benzaldehyde hydrogenation over the Pd(111) and Pt(111) metal surfaces using density functional theory (DFT) and ab initio molecular dynamic (AIMD) simulations. The adsorption of H-2 shows the mixed preference of H adsorption sites on the Pt(111), while the fcc adsorption site is dominant for H on the Pd(111). When benzaldehyde is added to the systems, we observe a strong reduction of benzaldehyde on charged Pd (111) surface compared with that on neutral surface. In contrast, charged state of the Pt(111) surface does not change their interaction. Subsequent hydrogenation reaction of benzaldehyde over Pd(111), proceeding via Langmuir-Hinshelwood mechanism, is affected by two major factors: the presence of H2O solvent and surface charge. The presence of H2O solvent greatly reduces the activation energy of C-H and O-H bond formation during the hydrogenation process. Furthermore, the hydrogenation step via C-H bond formation is preferred thermodynamically and kinetically over O-H bond formation during thermocatalytic hydrogenation, while the opposite trend holds true during electrocatalytic hydrogenation.
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