NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction
Abstract
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.
- Authors:
-
- Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering; NICE America Research, Inc, Mountain View, CA (United States)
- Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering
- Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); 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)
- OSTI Identifier:
- 1439883
- Alternate Identifier(s):
- OSTI ID: 1496353
- Grant/Contract Number:
- AC02-06CH11357; SC0012573; DESC0012573
- Resource 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
- 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
Citation Formats
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., 2017.
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. https://doi.org/10.1016/j.apcatb.2017.12.059
Shan, Junjun, Liu, Jilei, Li, Mengwei, Lustig, Sylvia, Lee, Sungsik, and Flytzani-Stephanopoulos, Maria. Fri .
"NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction". United States. https://doi.org/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 = {Fri Dec 29 00:00:00 EST 2017},
month = {Fri Dec 29 00:00:00 EST 2017}
}
Web of Science
Figures / Tables:
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