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Title: Selective non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen on highly dilute NiCu alloys

Abstract

The non-oxidative dehydrogenation of ethanol to acetaldehyde has long been considered as an important method to produce acetaldehyde and clean hydrogen gas. Although monometallic Cu nanoparticles have high activity in the non-oxidative dehydrogenation of ethanol, they quickly deactivate due to sintering of Cu. In this paper, we show that adding a small amount of Ni (Ni 0.01Cu - Ni 0.001Cu) into Cu to form highly dilute NiCu alloys dramatically increases the catalytic activity and increases their long-term stability. The kinetic studies show that the apparent activation energy decreases from ~70 kJ/mol over Cu to ~45 kJ/mol over the dilute NiCu alloys. The improved performance is observed both for nanoparticles and nanoporous NiCu alloys. The improvement in the long-term stability of the catalysts is attributed to the stabilization of Cu against sintering. Our characterization data show that Ni is atomically dispersed in Cu. The comparison of the catalytic performance of highly dilute alloy nanoparticles with nanoporous materials is useful to guide the design of novel mesoporous catalyst architectures for selective dehydrogenation reactions.

Authors:
 [1];  [2];  [1];  [1];  [3];  [3];  [3];  [3];  [2];  [1]
  1. Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering
  2. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Nanoscale Synthesis and Characterization Lab.
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Harvard Univ., Cambridge, MA (United States). Center for Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1458624
Alternate Identifier(s):
OSTI ID: 1419112
Report Number(s):
LLNL-JRNL-741641
Journal ID: ISSN 0926-3373; 896020
Grant/Contract Number:  
AC52-07NA27344; SC0012573; 1541959
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Applied Catalysis. B, Environmental
Additional Journal Information:
Journal Volume: 205; Journal Issue: C; Journal ID: ISSN 0926-3373
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Single atom alloys; Nickel; Copper; Ethanol dehydrogenation; Acetaldehyde; Hydrogen

Citation Formats

Shan, Junjun, Janvelyan, Nare, Li, Hang, Liu, Jilei, Egle, Tobias M., Ye, Jianchao, Biener, Monika M., Biener, Juergen, Friend, Cynthia M., and Flytzani-Stephanopoulos, Maria. Selective non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen on highly dilute NiCu alloys. United States: N. p., 2016. Web. doi:10.1016/j.apcatb.2016.12.045.
Shan, Junjun, Janvelyan, Nare, Li, Hang, Liu, Jilei, Egle, Tobias M., Ye, Jianchao, Biener, Monika M., Biener, Juergen, Friend, Cynthia M., & Flytzani-Stephanopoulos, Maria. Selective non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen on highly dilute NiCu alloys. United States. doi:10.1016/j.apcatb.2016.12.045.
Shan, Junjun, Janvelyan, Nare, Li, Hang, Liu, Jilei, Egle, Tobias M., Ye, Jianchao, Biener, Monika M., Biener, Juergen, Friend, Cynthia M., and Flytzani-Stephanopoulos, Maria. Sat . "Selective non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen on highly dilute NiCu alloys". United States. doi:10.1016/j.apcatb.2016.12.045. https://www.osti.gov/servlets/purl/1458624.
@article{osti_1458624,
title = {Selective non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen on highly dilute NiCu alloys},
author = {Shan, Junjun and Janvelyan, Nare and Li, Hang and Liu, Jilei and Egle, Tobias M. and Ye, Jianchao and Biener, Monika M. and Biener, Juergen and Friend, Cynthia M. and Flytzani-Stephanopoulos, Maria},
abstractNote = {The non-oxidative dehydrogenation of ethanol to acetaldehyde has long been considered as an important method to produce acetaldehyde and clean hydrogen gas. Although monometallic Cu nanoparticles have high activity in the non-oxidative dehydrogenation of ethanol, they quickly deactivate due to sintering of Cu. In this paper, we show that adding a small amount of Ni (Ni0.01Cu - Ni0.001Cu) into Cu to form highly dilute NiCu alloys dramatically increases the catalytic activity and increases their long-term stability. The kinetic studies show that the apparent activation energy decreases from ~70 kJ/mol over Cu to ~45 kJ/mol over the dilute NiCu alloys. The improved performance is observed both for nanoparticles and nanoporous NiCu alloys. The improvement in the long-term stability of the catalysts is attributed to the stabilization of Cu against sintering. Our characterization data show that Ni is atomically dispersed in Cu. The comparison of the catalytic performance of highly dilute alloy nanoparticles with nanoporous materials is useful to guide the design of novel mesoporous catalyst architectures for selective dehydrogenation reactions.},
doi = {10.1016/j.apcatb.2016.12.045},
journal = {Applied Catalysis. B, Environmental},
number = C,
volume = 205,
place = {United States},
year = {Sat Dec 31 00:00:00 EST 2016},
month = {Sat Dec 31 00:00:00 EST 2016}
}

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