TY - JOUR
T1 - Investigation of the reaction mechanism of the hydrodeoxygenation of propionic acid over a Rh(1 1 1) surface
T2 - A first principles study
AU - Yang, Wenqiang
AU - Solomon, Rajadurai Vijay
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 (most of the gas phase data and models). J.Q.B. acknowledges financial support from the National Science Foundation DMREF-1534269 . This work was also supported by the South Carolina State Center for Strategic Approaches to the Generation of Electricity (SAGE). 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 on the CASCADE cluster of the Environmental Molecular Sciences Laboratory (EMSL) are also acknowledged for some of the DFT calculations. Finally, computing resources from the USC High Performance Computing Group are gratefully acknowledged.
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 (most of the gas phase data and models). J.Q.B. acknowledges financial support from the National Science Foundation DMREF-1534269. This work was also supported by the South Carolina State Center for Strategic Approaches to the Generation of Electricity (SAGE). 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 on the CASCADE cluster of the Environmental Molecular Sciences Laboratory (EMSL) are also acknowledged for some of the DFT calculations. Finally, computing resources from the USC High Performance Computing Group are gratefully acknowledged.
PY - 2020/11
Y1 - 2020/11
N2 - Microkinetic models based on first principles calculations have been used to study the vapor and liquid phase hydrodeoxygenation of propionic acid on a Rh(1 1 1) surface. Calculations suggest that both decarboxylation and decarbonylation do not occur at an appreciable rate under all reaction environments. Propanol and propionaldehyde are the main products on this surface and they are produced at similar rates in both vapor and liquid phase environments. While a condensed phase can shift the reaction rate, the dominant pathways and selectivity towards the various products are hardly affected. At 473 K, the turnover frequency is increased by about a factor of 1.5 in liquid water relative to the gas phase. In liquid 1,4-dioxane, the turnover frequency is also slightly increased relative to the gas phase. Given the uncertainty in Rh cavity radius in the liquid phase calculations, computations with different cavity radii have been performed. With larger Rh cavity radius, the promotional effect of the solvents on the turnover frequency becomes more significant, while practically no changes are observed for a smaller cavity radius.
AB - Microkinetic models based on first principles calculations have been used to study the vapor and liquid phase hydrodeoxygenation of propionic acid on a Rh(1 1 1) surface. Calculations suggest that both decarboxylation and decarbonylation do not occur at an appreciable rate under all reaction environments. Propanol and propionaldehyde are the main products on this surface and they are produced at similar rates in both vapor and liquid phase environments. While a condensed phase can shift the reaction rate, the dominant pathways and selectivity towards the various products are hardly affected. At 473 K, the turnover frequency is increased by about a factor of 1.5 in liquid water relative to the gas phase. In liquid 1,4-dioxane, the turnover frequency is also slightly increased relative to the gas phase. Given the uncertainty in Rh cavity radius in the liquid phase calculations, computations with different cavity radii have been performed. With larger Rh cavity radius, the promotional effect of the solvents on the turnover frequency becomes more significant, while practically no changes are observed for a smaller cavity radius.
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.2020.08.015
DO - 10.1016/j.jcat.2020.08.015
M3 - Article
AN - SCOPUS:85090112380
VL - 391
SP - 98
EP - 110
JO - Journal of Catalysis
JF - Journal of Catalysis
SN - 0021-9517
ER -