TY - JOUR
T1 - First-principle investigation on catalytic hydrogenation of benzaldehyde over Pt-group metals
AU - Yuk, Simuck F.
AU - Lee, Mal Soon
AU - Akhade, Sneha A.
AU - Nguyen, Manh Thuong
AU - Glezakou, Vassiliki Alexandra
AU - Rousseau, Roger
N1 - Funding Information:
This work was supported by Chemical Transformation Initiative, funded by the Laboratory Directed Research and Development (LDRD) program at Pacific Northwest National Laboratory (PNNL) . PNNL is operated by Battelle for the US Department of Energy under Contract DE-AC05-76RL01830. Computational Resources were provided by PNNL Research Computing. Writing of the manuscript by SAA was performed under the auspices of the US Department of Energy by Lawrence Livermore National Laboratory (LLNL) under Contract DEAC52-07NA27344.
PY - 2020
Y1 - 2020
N2 - 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 investigated 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 H2 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.
AB - 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 investigated 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 H2 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.
KW - Ab initio molecular dynamics
KW - Catalytic hydrogenation
KW - Hydrogen adsorption
KW - Metal catalyst
KW - Solid/liquid interface
UR - http://www.scopus.com/inward/record.url?scp=85089251239&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85089251239&partnerID=8YFLogxK
U2 - 10.1016/j.cattod.2020.07.039
DO - 10.1016/j.cattod.2020.07.039
M3 - Article
AN - SCOPUS:85089251239
JO - Catalysis Today
JF - Catalysis Today
SN - 0920-5861
ER -