TY - JOUR
T1 - Unraveling the mechanism of the hydrodeoxygenation of propionic acid over a Pt (1 1 1) surface in vapor and liquid phases
AU - Yang, Wenqiang
AU - Solomon, Rajadurai Vijay
AU - Lu, Jianmin
AU - Mamun, Osman
AU - Bond, Jesse Q.
AU - Heyden, Andreas
N1 - Funding Information:
We gratefully acknowledge financial support from the U.S. Department of Energy , Office of Basic Energy Science, Catalysis Science program under Award DE-SC0007167 (most of the liquid phase calculations and models and some of the gas phase data) and the National Science Foundation under Grant No. DMREF-1534260 (some of the gas phase data and models). J.Q.B. acknowledges financial support from the National Science Foundation DMREF-1534269 . Computational resources have been provided by the National Energy Research Scientific Computing Center (NERSC) which is supported by the Office of Science of the U.S. Department of Energy and in part by XSEDE under grant number TG-CTS090100 . Computational resources from CASCADE cluster from Environmental Molecular Sciences Laboratory (EMSL) under Pacific Northwest National Laboratory (PNNL) are also used for the DFT calculations. Finally, computing resources from the USC High Performance Computing Group are gratefully acknowledged. We also gratefully thank the Writing Center of the University of South Carolina for providing suggestions in preparing this paper. Appendix A
Funding Information:
We gratefully acknowledge financial support from the U.S. Department of Energy, Office of Basic Energy Science, Catalysis Science program under Award DE-SC0007167 (most of the liquid phase calculations and models and some of the gas phase data) and the National Science Foundation under Grant No. DMREF-1534260 (some of the gas phase data and models). J.Q.B. acknowledges financial support from the National Science Foundation DMREF-1534269. Computational resources have been provided by the National Energy Research Scientific Computing Center (NERSC) which is supported by the Office of Science of the U.S. Department of Energy and in part by XSEDE under grant number TG-CTS090100. Computational resources from CASCADE cluster from Environmental Molecular Sciences Laboratory (EMSL) under Pacific Northwest National Laboratory (PNNL) are also used for the DFT calculations. Finally, computing resources from the USC High Performance Computing Group are gratefully acknowledged. We also gratefully thank the Writing Center of the University of South Carolina for providing suggestions in preparing this paper.
Publisher Copyright:
© 2019 Elsevier Inc.
PY - 2020/1
Y1 - 2020/1
N2 - Microkinetic models based on first principles calculations have been developed for the vapor and liquid phase hydrodeoxygenation of propionic acid over a Pt (1 1 1) surface. Calculations suggest that decarboxylation does not occur at an appreciable rate. In the vapor phase, decarbonylation products, propanal and propanol are all produced at similar rates. However, in both liquid water and 1,4-dioxane, propanol and propanal are favored over decarbonylation products. While a condensed phase can shift the reaction rate and selectivity significantly, the dominant pathways towards the various products are hardly affected. Only for propanal production do we observe a shift in mechanism. At 473 K, the propionic acid conversion rate is increased by one order of magnitude in liquid 1,4-dioxane relative to the gas phase. In liquid water, the conversion rate is similar to the vapor phase since adsorbed propionic acid blocks a large fraction of the surface sites.
AB - Microkinetic models based on first principles calculations have been developed for the vapor and liquid phase hydrodeoxygenation of propionic acid over a Pt (1 1 1) surface. Calculations suggest that decarboxylation does not occur at an appreciable rate. In the vapor phase, decarbonylation products, propanal and propanol are all produced at similar rates. However, in both liquid water and 1,4-dioxane, propanol and propanal are favored over decarbonylation products. While a condensed phase can shift the reaction rate and selectivity significantly, the dominant pathways towards the various products are hardly affected. Only for propanal production do we observe a shift in mechanism. At 473 K, the propionic acid conversion rate is increased by one order of magnitude in liquid 1,4-dioxane relative to the gas phase. In liquid water, the conversion rate is similar to the vapor phase since adsorbed propionic acid blocks a large fraction of the surface sites.
KW - Hydrodeoxygenation mechanism
KW - Lateral interaction
KW - Microkinetic modeling
KW - Propanol
KW - Propionaldehyde
KW - Propionic acid
KW - Solvent effect
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U2 - 10.1016/j.jcat.2019.11.036
DO - 10.1016/j.jcat.2019.11.036
M3 - Article
AN - SCOPUS:85076496943
SN - 0021-9517
VL - 381
SP - 547
EP - 560
JO - Journal of Catalysis
JF - Journal of Catalysis
ER -