A self-adjusting platinum surface for acetone hydrogenation
Abstract
We show that platinum displays a self-adjusting surface that is active for the hydrogenation of acetone over a wide range of reaction conditions. Reaction kinetics measurements under steady-state and transient conditions at temperatures near 350 K, electronic structure calculations employing density-functional theory, and microkinetic modeling were employed to study this behavior over supported platinum catalysts. The importance of surface coverage effects was highlighted by evaluating the transient response of isopropanol formation following either removal of the reactant ketone from the feed, or its substitution with a similarly structured species. The extent to which adsorbed intermediates that lead to the formation of isopropanol were removed from the catalytic surface was observed to be higher following ketone substitution in comparison to its removal, indicating that surface species leading to isopropanol become more strongly adsorbed on the surface as the coverage decreases during the desorption experiment. This phenomenon occurs as a result of adsorbate–adsorbate repulsive interactions on the catalyst surface which adjust with respect to the reaction conditions. Reaction kinetics parameters obtained experimentally were in agreement with those predicted by microkinetic modeling when the binding energies, activation energies, and entropies of adsorbed species and transition states were expressed as a function of surfacemore »
- Authors:
-
[1];
[2];
[2];
[1];
[2];
[2];
[1]
- Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering, and Dept. of Energy, Great Lakes Bioenergy Research Center
- Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
- Publication Date:
- Research Org.:
- Great Lakes Bioenergy Research Center (GLBRC), Madison, WI (United States); Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1600938
- Alternate Identifier(s):
- OSTI ID: 1778259
- Grant/Contract Number:
- SC0018409; SC0014058; FG02-05ER15731
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Volume: 117; Journal Issue: 7; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Hydrogenation; platinum; reaction kinetics; surface coverage; Platinum, acetone hydrogenation, DFT, SSITKA, microkinetic modeling
Citation Formats
Demir, Benginur, Kropp, Thomas, Rivera-Dones, Keishla R., Gilcher, Elise B., Huber, George W., Mavrikakis, Manos, and Dumesic, James A. A self-adjusting platinum surface for acetone hydrogenation. United States: N. p., 2020.
Web. doi:10.1073/pnas.1917110117.
Demir, Benginur, Kropp, Thomas, Rivera-Dones, Keishla R., Gilcher, Elise B., Huber, George W., Mavrikakis, Manos, & Dumesic, James A. A self-adjusting platinum surface for acetone hydrogenation. United States. https://doi.org/10.1073/pnas.1917110117
Demir, Benginur, Kropp, Thomas, Rivera-Dones, Keishla R., Gilcher, Elise B., Huber, George W., Mavrikakis, Manos, and Dumesic, James A. Fri .
"A self-adjusting platinum surface for acetone hydrogenation". United States. https://doi.org/10.1073/pnas.1917110117. https://www.osti.gov/servlets/purl/1600938.
@article{osti_1600938,
title = {A self-adjusting platinum surface for acetone hydrogenation},
author = {Demir, Benginur and Kropp, Thomas and Rivera-Dones, Keishla R. and Gilcher, Elise B. and Huber, George W. and Mavrikakis, Manos and Dumesic, James A.},
abstractNote = {We show that platinum displays a self-adjusting surface that is active for the hydrogenation of acetone over a wide range of reaction conditions. Reaction kinetics measurements under steady-state and transient conditions at temperatures near 350 K, electronic structure calculations employing density-functional theory, and microkinetic modeling were employed to study this behavior over supported platinum catalysts. The importance of surface coverage effects was highlighted by evaluating the transient response of isopropanol formation following either removal of the reactant ketone from the feed, or its substitution with a similarly structured species. The extent to which adsorbed intermediates that lead to the formation of isopropanol were removed from the catalytic surface was observed to be higher following ketone substitution in comparison to its removal, indicating that surface species leading to isopropanol become more strongly adsorbed on the surface as the coverage decreases during the desorption experiment. This phenomenon occurs as a result of adsorbate–adsorbate repulsive interactions on the catalyst surface which adjust with respect to the reaction conditions. Reaction kinetics parameters obtained experimentally were in agreement with those predicted by microkinetic modeling when the binding energies, activation energies, and entropies of adsorbed species and transition states were expressed as a function of surface coverage of the most abundant surface intermediate (MASI, C3H6OH*). It is important that these effects of surface coverage be incorporated dynamically in the microkinetic model (e.g., using the Bragg–Williams approximation) to describe the experimental data over a wide range of acetone partial pressures.},
doi = {10.1073/pnas.1917110117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 7,
volume = 117,
place = {United States},
year = {2020},
month = {1}
}
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