Surface chemistry dictates stability and oxidation state of supported single metal catalyst atoms
Abstract
Single atom catalysts receive considerable attention due to reducing noble metal utilization and potentially eliminating certain side reactions. Yet, the rational design of highly reactive and stable single atom catalysts is hampered by the current lack of fundamental insights at the single atom limit. Here, density functional theory calculations are performed for a prototype reaction, namely CO oxidation, over different single metal atoms supported on alumina. The governing reaction mechanisms and scaling relations are identified using microkinetic modeling and principal component analysis, respectively. A large change in the oxophilicity of the supported single metal atom leads to changes in the rate-determining step and the catalyst resting state. Multi-response surfaces are introduced and built cheaply using a descriptor-based, closed form kinetic model to describe simultaneously the activity, stability, and oxidation state of single metal atom catalysts. A double peaked volcano in activity is observed due to competing rate-determining steps and catalytic cycles. Reaction orders of reactants provide excellent kinetic signatures of the catalyst state. Importantly, the surface chemistry determines the stability, oxidation, and resting state of the catalyst.
- Authors:
-
[1];
[1]
- Department of Chemical and Biomolecular Engineering, Catalysis Center for Energy Innovation, University of Delaware, Newark, USA
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Univ. of Delaware, Newark, DE (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); European Union Horizon 2020
- OSTI Identifier:
- 1581202
- Alternate Identifier(s):
- OSTI ID: 1767705
- Grant/Contract Number:
- SC0001004; 686086
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 6; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); biofuels (including algae and biomass); bio-inspired; hydrogen and fuel cells; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)
Citation Formats
Alexopoulos, Konstantinos, and Vlachos, Dionisios G. Surface chemistry dictates stability and oxidation state of supported single metal catalyst atoms. United Kingdom: N. p., 2020.
Web. doi:10.1039/C9SC05944J.
Alexopoulos, Konstantinos, & Vlachos, Dionisios G. Surface chemistry dictates stability and oxidation state of supported single metal catalyst atoms. United Kingdom. https://doi.org/10.1039/C9SC05944J
Alexopoulos, Konstantinos, and Vlachos, Dionisios G. Wed .
"Surface chemistry dictates stability and oxidation state of supported single metal catalyst atoms". United Kingdom. https://doi.org/10.1039/C9SC05944J.
@article{osti_1581202,
title = {Surface chemistry dictates stability and oxidation state of supported single metal catalyst atoms},
author = {Alexopoulos, Konstantinos and Vlachos, Dionisios G.},
abstractNote = {Single atom catalysts receive considerable attention due to reducing noble metal utilization and potentially eliminating certain side reactions. Yet, the rational design of highly reactive and stable single atom catalysts is hampered by the current lack of fundamental insights at the single atom limit. Here, density functional theory calculations are performed for a prototype reaction, namely CO oxidation, over different single metal atoms supported on alumina. The governing reaction mechanisms and scaling relations are identified using microkinetic modeling and principal component analysis, respectively. A large change in the oxophilicity of the supported single metal atom leads to changes in the rate-determining step and the catalyst resting state. Multi-response surfaces are introduced and built cheaply using a descriptor-based, closed form kinetic model to describe simultaneously the activity, stability, and oxidation state of single metal atom catalysts. A double peaked volcano in activity is observed due to competing rate-determining steps and catalytic cycles. Reaction orders of reactants provide excellent kinetic signatures of the catalyst state. Importantly, the surface chemistry determines the stability, oxidation, and resting state of the catalyst.},
doi = {10.1039/C9SC05944J},
journal = {Chemical Science},
number = 6,
volume = 11,
place = {United Kingdom},
year = {Wed Feb 12 00:00:00 EST 2020},
month = {Wed Feb 12 00:00:00 EST 2020}
}
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