An experimental approach for controlling confinement effects at catalyst interfaces
Abstract
Catalysts are conventionally designed with a focus on enthalpic effects, manipulating the Arrhenius activation energy. This approach ignores the possibility of designing materials to control the entropic factors that determine the pre-exponential factor. Here we investigate a new method of designing supported Pt catalysts with varying degrees of molecular confinement at the active site. Combining these with fast and precise online measurements, we analyse the kinetics of a model reaction, the platinum-catalysed hydrolysis of ammonia borane. We control the environment around the Pt particles by erecting organophosphonic acid barriers of different heights and at different distances. This is done by first coating the particles with organothiols, then coating the surface with organophosphonic acids, and finally removing the thiols. The result is a set of catalysts with well-defined “empty areas” surrounding the active sites. Generating Arrhenius plots with >300 points each, we then compare the effects of each confinement scenario. We show experimentally that confining the reaction influences mainly the entropy part of the enthalpy/entropy trade-off, leaving the enthalpy unchanged. Furthermore, we find this entropy contribution is only relevant at very small distances (<3 Å for ammonia borane), where the “empty space” is of a similar size to the reactant molecule.more »
- Authors:
-
[1];
[1];
[2];
[1]
- Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam 1098 XH, The Netherlands
- Department of Chemical and Biological Engineering, University of Colorado Boulder, Boulder, USA
- Publication Date:
- Research Org.:
- Univ. of Colorado, Boulder, CO (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
- OSTI Identifier:
- 1659525
- Alternate Identifier(s):
- OSTI ID: 1817123
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 40; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Slot, Thierry K., Riley, Nathan, Shiju, N. Raveendran, Medlin, J. Will, and Rothenberg, Gadi. An experimental approach for controlling confinement effects at catalyst interfaces. United Kingdom: N. p., 2020.
Web. doi:10.1039/D0SC04118A.
Slot, Thierry K., Riley, Nathan, Shiju, N. Raveendran, Medlin, J. Will, & Rothenberg, Gadi. An experimental approach for controlling confinement effects at catalyst interfaces. United Kingdom. https://doi.org/10.1039/D0SC04118A
Slot, Thierry K., Riley, Nathan, Shiju, N. Raveendran, Medlin, J. Will, and Rothenberg, Gadi. Wed .
"An experimental approach for controlling confinement effects at catalyst interfaces". United Kingdom. https://doi.org/10.1039/D0SC04118A.
@article{osti_1659525,
title = {An experimental approach for controlling confinement effects at catalyst interfaces},
author = {Slot, Thierry K. and Riley, Nathan and Shiju, N. Raveendran and Medlin, J. Will and Rothenberg, Gadi},
abstractNote = {Catalysts are conventionally designed with a focus on enthalpic effects, manipulating the Arrhenius activation energy. This approach ignores the possibility of designing materials to control the entropic factors that determine the pre-exponential factor. Here we investigate a new method of designing supported Pt catalysts with varying degrees of molecular confinement at the active site. Combining these with fast and precise online measurements, we analyse the kinetics of a model reaction, the platinum-catalysed hydrolysis of ammonia borane. We control the environment around the Pt particles by erecting organophosphonic acid barriers of different heights and at different distances. This is done by first coating the particles with organothiols, then coating the surface with organophosphonic acids, and finally removing the thiols. The result is a set of catalysts with well-defined “empty areas” surrounding the active sites. Generating Arrhenius plots with >300 points each, we then compare the effects of each confinement scenario. We show experimentally that confining the reaction influences mainly the entropy part of the enthalpy/entropy trade-off, leaving the enthalpy unchanged. Furthermore, we find this entropy contribution is only relevant at very small distances (<3 Å for ammonia borane), where the “empty space” is of a similar size to the reactant molecule. This suggests that confinement effects observed over larger distances must be enthalpic in nature.},
doi = {10.1039/D0SC04118A},
journal = {Chemical Science},
number = 40,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {10}
}
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