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

Journal Article · · Applied Catalysis B: Environmental
 [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
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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.

Research Organization:
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 Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; SC0012573; DESC0012573
OSTI ID:
1439883
Alternate ID(s):
OSTI ID: 1496353
Journal Information:
Applied Catalysis B: Environmental, Vol. 226, Issue C; ISSN 0926-3373
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 95 works
Citation information provided by
Web of Science

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Cited By (7)

First-Principle Microkinetic Modeling of Ethanol Dehydrogenation on Metal Catalyst Surfaces in Non-oxidative Environment: Design of Bimetallic Alloys journal August 2018
Graphene Supported Single Atom Transition Metal Catalysts for Methane Activation journal May 2018
A nickel–iridium alloy as an efficient heterogeneous catalyst for hydrogenation of olefins journal January 2019
Anchoring ultrafine PtNi nanoparticles on N-doped graphene for highly efficient hydrogen evolution reaction journal January 2019
Intermetallic Compounds as an Alternative to Single‐atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X‐ray Spectroscopies and Computational Studies journal January 2020
Atomic‐Local Environments of Single‐Atom Catalysts: Synthesis, Electronic Structure, and Activity journal October 2019
Ultrafine PtRu Dilute Alloy Nanodendrites for Enhanced Electrocatalytic Methanol Oxidation journal October 2019

Figures / Tables (12)

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
77 NANOSCIENCE AND NANOTECHNOLOGY
Copper
Nickel
ethanol dehydrogenation
single atom alloys
C-H bond activation