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Title: Mechanistic Insights into Nonoxidative Ethanol Dehydrogenation on NiCu Single-Atom Alloys

Abstract

Ethanol dehydrogenation presents a promising pathway towards the production of acetaldehyde, a valuable building block in chemicals production. Under non-oxidative conditions, the reaction is facilitated by supported Cu nanoparticles which afford reasonable activity and high selectivity. The stability issues associated with Cu nanoparticle sintering can be addressed by the addition of small amounts of Ni, which further boost reactivity while retaining selectivity. Despite the promise of NiCu single-atom alloys for non-oxidative ethanol dehydrogenation, little is known about the role of each component and the pathway of this mechanistically complex process. Herein, kinetic investigations from reactor tests identify C-H bond scission as the rate limiting step, while 1-hydroxyethyl is detected as the intermediate via IR spectroscopy. Temperature program desorption studies are employed to examine the effect of Ni coverage and to demonstrate that Ni atoms activate ethanol selectively at lower temperatures, resulting in higher acetaldehyde yield than pure Cu. Temperature program desorption experiments also reveal the spillover of intermediates from the Ni atom to neighboring Cu sites as a relevant step in the reaction pathway. Density functional theory calculations are used to investigate the 2 reaction energetics and to confirm that C-H bond scission is the initial reaction step, while amore » clear effect of H2 partial pressure on the reaction pathway is realized. Further, counter to the expected behavior that all reaction steps take place on the Ni atoms, our degree of rate control analysis reveals that a mechanism involving spillover of the 1-hydroxyethyl intermediate from the Ni atom to the Cu surface, where it will dehydrogenate further, is more likely. Furthermore, our combined kinetic, spectroscopic, and theoretical approach sheds light on this complex reaction mechanism and represents a promising method for the understanding and designing of highly active, selective, and stable single-atom alloys for other multistep catalytic processes.« less

Authors:
 [1];  [1];  [2];  [2];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Tufts University, Medford, MA (United States)
  2. University of California, Los Angeles, CA (United States)
Publication Date:
Research Org.:
Harvard Univ., Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1996123
Grant/Contract Number:  
SC0012573; SC0004738; ACI-1548562; TG-CHE170060
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 13; Journal Issue: 7; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Heterogeneous catalysis; bimetallic alloy; surface science; single-site catalysis; acetaldehyde; catalysts; chemical reactions; ethanol; organic reactions

Citation Formats

Patel, Dipna A., Giannakakis, Georgios, Yan, George, Ngan, Hio Tong, Yu, Peng, Hannagan, Ryan T., Kress, Paul L., Shan, Junjun, Deshlahra, Prashant, Sautet, Philippe, and Sykes, E. Charles H. Mechanistic Insights into Nonoxidative Ethanol Dehydrogenation on NiCu Single-Atom Alloys. United States: N. p., 2023. Web. doi:10.1021/acscatal.3c00275.
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Patel, Dipna A., Giannakakis, Georgios, Yan, George, Ngan, Hio Tong, Yu, Peng, Hannagan, Ryan T., Kress, Paul L., Shan, Junjun, Deshlahra, Prashant, Sautet, Philippe, & Sykes, E. Charles H. Mechanistic Insights into Nonoxidative Ethanol Dehydrogenation on NiCu Single-Atom Alloys. United States. https://doi.org/10.1021/acscatal.3c00275
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Patel, Dipna A., Giannakakis, Georgios, Yan, George, Ngan, Hio Tong, Yu, Peng, Hannagan, Ryan T., Kress, Paul L., Shan, Junjun, Deshlahra, Prashant, Sautet, Philippe, and Sykes, E. Charles H. Tue . "Mechanistic Insights into Nonoxidative Ethanol Dehydrogenation on NiCu Single-Atom Alloys". United States. https://doi.org/10.1021/acscatal.3c00275. https://www.osti.gov/servlets/purl/1996123.
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@article{osti_1996123,
title = {Mechanistic Insights into Nonoxidative Ethanol Dehydrogenation on NiCu Single-Atom Alloys},
author = {Patel, Dipna A. and Giannakakis, Georgios and Yan, George and Ngan, Hio Tong and Yu, Peng and Hannagan, Ryan T. and Kress, Paul L. and Shan, Junjun and Deshlahra, Prashant and Sautet, Philippe and Sykes, E. Charles H.},
abstractNote = {Ethanol dehydrogenation presents a promising pathway towards the production of acetaldehyde, a valuable building block in chemicals production. Under non-oxidative conditions, the reaction is facilitated by supported Cu nanoparticles which afford reasonable activity and high selectivity. The stability issues associated with Cu nanoparticle sintering can be addressed by the addition of small amounts of Ni, which further boost reactivity while retaining selectivity. Despite the promise of NiCu single-atom alloys for non-oxidative ethanol dehydrogenation, little is known about the role of each component and the pathway of this mechanistically complex process. Herein, kinetic investigations from reactor tests identify C-H bond scission as the rate limiting step, while 1-hydroxyethyl is detected as the intermediate via IR spectroscopy. Temperature program desorption studies are employed to examine the effect of Ni coverage and to demonstrate that Ni atoms activate ethanol selectively at lower temperatures, resulting in higher acetaldehyde yield than pure Cu. Temperature program desorption experiments also reveal the spillover of intermediates from the Ni atom to neighboring Cu sites as a relevant step in the reaction pathway. Density functional theory calculations are used to investigate the 2 reaction energetics and to confirm that C-H bond scission is the initial reaction step, while a clear effect of H2 partial pressure on the reaction pathway is realized. Further, counter to the expected behavior that all reaction steps take place on the Ni atoms, our degree of rate control analysis reveals that a mechanism involving spillover of the 1-hydroxyethyl intermediate from the Ni atom to the Cu surface, where it will dehydrogenate further, is more likely. Furthermore, our combined kinetic, spectroscopic, and theoretical approach sheds light on this complex reaction mechanism and represents a promising method for the understanding and designing of highly active, selective, and stable single-atom alloys for other multistep catalytic processes.},
doi = {10.1021/acscatal.3c00275},
journal = {ACS Catalysis},
number = 7,
volume = 13,
place = {United States},
year = {Tue Mar 14 00:00:00 EDT 2023},
month = {Tue Mar 14 00:00:00 EDT 2023}
}
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