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.:
- Univ. of Wisconsin, Madison, WI (United States). Dept. of Energy, Great Lakes Bioenergy Research Center; 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. https://doi.org/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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Works referenced in this record:
Metal-support effects on acetone hydrogenation over platinum catalysts
journal, September 1988
- Sen, B.
- Journal of Catalysis, Vol. 113, Issue 1
End-On and Side-On Bonding of Ketones to Surfaces: Acetone on the Ru(001) and Pt(111) Surfaces
journal, August 1983
- Avery, N. R.; Weinberg, W. H.; Anton, A. B.
- Physical Review Letters, Vol. 51, Issue 8
On the Scientific Heritage of Mikhail Isaakovich Temkin
journal, July 2019
- Murzin, D. Yu.
- Kinetics and Catalysis, Vol. 60, Issue 4
Density-functional theory studies of acetone and propanal hydrogenation on Pt(111)
journal, May 2002
- Alcalá, R.; Greeley, J.; Mavrikakis, M.
- The Journal of Chemical Physics, Vol. 116, Issue 20
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Finding the Rate-Determining Step in a Mechanism
journal, December 2001
- Campbell, Charles T.
- Journal of Catalysis, Vol. 204, Issue 2
Kinetics of acetone hydrogenation over Pt/Al2O3 catalysts
journal, July 1985
- Rositani, F.; Galvagno, S.; Poltarzewski, Z.
- Journal of Chemical Technology and Biotechnology. Chemical Technology, Vol. 35, Issue 5
Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals
journal, February 2010
- Grabow, Lars C.; Hvolbæk, Britt; Nørskov, Jens K.
- Topics in Catalysis, Vol. 53, Issue 5-6
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Characterization of Catalytic Surfaces by Isotopic-Transient Kinetics during Steady-State Reaction
journal, May 1995
- Shannon, Schohn L.; Goodwin, James G.
- Chemical Reviews, Vol. 95, Issue 3
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Chemical Routes for the Transformation of Biomass into Chemicals
journal, June 2007
- Corma, Avelino; Iborra, Sara; Velty, Alexandra
- Chemical Reviews, Vol. 107, Issue 6, p. 2411-2502
Methane Conversion to Ethylene and Aromatics on PtSn Catalysts
journal, February 2017
- Gerceker, Duygu; Motagamwala, Ali Hussain; Rivera-Dones, Keishla R.
- ACS Catalysis, Vol. 7, Issue 3
A RAIRS and HREELS study of acetone on Pt(111)
journal, August 1991
- Vannice, M. A.; Erley, W.; Ibach, H.
- Surface Science, Vol. 254, Issue 1-3
Recent Approaches in Mechanistic and Kinetic Studies of Catalytic Reactions Using SSITKA Technique
journal, November 2014
- Ledesma, Cristian; Yang, Jia; Chen, De
- ACS Catalysis, Vol. 4, Issue 12
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Future Directions and Industrial Perspectives Micro- and macro-kinetics: Their relationship in heterogeneous catalysis
journal, September 1994
- Campbell, Charles T.
- Topics in Catalysis, Vol. 1, Issue 3-4
Hydrogenation of carbonylic compounds
journal, January 2000
- van Druten, G. M. R.; Ponec, V.
- Applied Catalysis A: General, Vol. 191, Issue 1-2
Microkinetic Analysis and Scaling Relations for Catalyst Design
journal, June 2018
- Motagamwala, Ali Hussain; Ball, Madelyn R.; Dumesic, James A.
- Annual Review of Chemical and Biomolecular Engineering, Vol. 9, Issue 1
Role of Surface Hydroxyl Species in Copper-Catalyzed Hydrogenation of Ketones
journal, July 2018
- De Vrieze, Jenoff E.; Thybaut, Joris W.; Saeys, Mark
- ACS Catalysis, Vol. 8, Issue 8
Microkinetic analysis of acetone hydrogenation over Pt/SiO2
journal, June 2019
- Gao, Xin; Heyden, Andreas; Abdelrahman, Omar A.
- Journal of Catalysis, Vol. 374
Application of semiempirical long-range dispersion corrections to periodic systems in density functional theory
journal, October 2008
- Kerber, Torsten; Sierka, Marek; Sauer, Joachim
- Journal of Computational Chemistry, Vol. 29, Issue 13
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
On the role of promoters in hydrogenations on metals; α,β-unsaturated aldehydes and ketones
journal, January 1997
- Ponec, V.
- Applied Catalysis A: General, Vol. 149, Issue 1
Microkinetic analysis of C3–C5 ketone hydrogenation over supported Ru catalysts
journal, April 2017
- Abdelrahman, Omar Ali; Heyden, Andreas; Bond, Jesse Q.
- Journal of Catalysis, Vol. 348
Role of water in metal catalyst performance for ketone hydrogenation: a joint experimental and theoretical study on levulinic acid conversion into gamma-valerolactone
journal, January 2014
- Michel, Carine; Zaffran, Jérémie; Ruppert, Agnieszka M.
- Chem. Commun., Vol. 50, Issue 83
Mechanism of the Water Gas Shift Reaction on Pt: First Principles, Experiments, and Microkinetic Modeling
journal, March 2008
- Grabow, Lars C.; Gokhale, Amit A.; Evans, Steven T.
- The Journal of Physical Chemistry C, Vol. 112, Issue 12