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Title: NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction

Here, NiCu single atom alloy (SAA) nanoparticles supported on silica are reported to catalyze the non-oxidative dehydrogenation of ethanol, selectively to acetaldehyde and hydrogen products by facilitating the C—H bond cleavage. The activity and selectivity of the NiCu SAA catalysts were compared to monometallic copper and to PtCu and PdCu single atom alloys, in a flow reactor at moderate temperatures. In-situ DRIFTS showed that the silica support facilitates the O—H bond cleavage of ethanol to form ethoxy intermediates over all the supported alloy catalysts. However, these remain unreactive up to 250°C for the Cu/SiO 2 monometallic nanoparticles, while in the NiCu SAA, acetaldehyde is formed at much lower temperatures, below 150°C. In situ DRIFTS was also used to identify the C—H activation step as the rate determining step of this reaction on all the copper catalysts we examined. The presence of atomically dispersed Ni in Cu significantly lowers the C—H bond activation barrier, whereas Pt and Pd atoms were found less effective. This work provides direct evidence that the C—H bond cleavage is the rate determining step in ethanol dehydrogenation over this type catalyst.
Authors:
 [1] ;  [2] ;  [2] ;  [2] ;  [3] ;  [2]
  1. Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering; NICE America Research, Inc, Mountain View, CA (United States)
  2. Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering
  3. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
Publication Date:
Grant/Contract Number:
AC02-06CH11357; SC0012573
Type:
Accepted Manuscript
Journal Name:
Applied Catalysis. B, Environmental
Additional Journal Information:
Journal Volume: 226; Journal Issue: C; Journal ID: ISSN 0926-3373
Publisher:
Elsevier
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Harvard Univ., Boston, MA (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; Copper; Nickel; ethanol dehydrogenation; single atom alloys; C-H bond activation
OSTI Identifier:
1439883

Shan, Junjun, Liu, Jilei, Li, Mengwei, Lustig, Sylvia, Lee, Sungsik, and Flytzani-Stephanopoulos, Maria. NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction. United States: N. p., Web. doi:10.1016/j.apcatb.2017.12.059.
Shan, Junjun, Liu, Jilei, Li, Mengwei, Lustig, Sylvia, Lee, Sungsik, & Flytzani-Stephanopoulos, Maria. NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction. United States. doi:10.1016/j.apcatb.2017.12.059.
Shan, Junjun, Liu, Jilei, Li, Mengwei, Lustig, Sylvia, Lee, Sungsik, and Flytzani-Stephanopoulos, Maria. 2017. "NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction". United States. doi:10.1016/j.apcatb.2017.12.059. https://www.osti.gov/servlets/purl/1439883.
@article{osti_1439883,
title = {NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction},
author = {Shan, Junjun and Liu, Jilei and Li, Mengwei and Lustig, Sylvia and Lee, Sungsik and Flytzani-Stephanopoulos, Maria},
abstractNote = {Here, NiCu single atom alloy (SAA) nanoparticles supported on silica are reported to catalyze the non-oxidative dehydrogenation of ethanol, selectively to acetaldehyde and hydrogen products by facilitating the C—H bond cleavage. The activity and selectivity of the NiCu SAA catalysts were compared to monometallic copper and to PtCu and PdCu single atom alloys, in a flow reactor at moderate temperatures. In-situ DRIFTS showed that the silica support facilitates the O—H bond cleavage of ethanol to form ethoxy intermediates over all the supported alloy catalysts. However, these remain unreactive up to 250°C for the Cu/SiO2 monometallic nanoparticles, while in the NiCu SAA, acetaldehyde is formed at much lower temperatures, below 150°C. In situ DRIFTS was also used to identify the C—H activation step as the rate determining step of this reaction on all the copper catalysts we examined. The presence of atomically dispersed Ni in Cu significantly lowers the C—H bond activation barrier, whereas Pt and Pd atoms were found less effective. This work provides direct evidence that the C—H bond cleavage is the rate determining step in ethanol dehydrogenation over this type catalyst.},
doi = {10.1016/j.apcatb.2017.12.059},
journal = {Applied Catalysis. B, Environmental},
number = C,
volume = 226,
place = {United States},
year = {2017},
month = {12}
}