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

Journal Article · · Applied Catalysis B: Environmental
 [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.
+ Show Author Affiliations

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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Harvard Univ., Cambridge, MA (United States). Center for Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC52-07NA27344; SC0012573; 1541959
OSTI ID:
1458624
Alternate ID(s):
OSTI ID: 1419112
Report Number(s):
LLNL-JRNL-741641; 896020
Journal Information:
Applied Catalysis B: Environmental, Vol. 205, Issue C; ISSN 0926-3373
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 110 works
Citation information provided by
Web of Science

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Cited By (7)

Atomic‐Local Environments of Single‐Atom Catalysts: Synthesis, Electronic Structure, and Activity journal October 2019
A study of ethanol conversion over zinc aluminate catalyst journal March 2018
Cu–Ca–Al catalysts derived from hydrocalumite and their application to ethanol dehydrogenation journal December 2018
First-Principle Microkinetic Modeling of Ethanol Dehydrogenation on Metal Catalyst Surfaces in Non-oxidative Environment: Design of Bimetallic Alloys journal August 2018
Production of acetic acid from ethanol over CuCr catalysts via dehydrogenation-(aldehyde–water shift) reaction journal January 2017
A nickel–iridium alloy as an efficient heterogeneous catalyst for hydrogenation of olefins journal January 2019
Dehydrogenation of Ethanol to Acetaldehyde over Different Metals Supported on Carbon Catalysts journal January 2019

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Single atom alloys
Nickel
Copper
Ethanol dehydrogenation
Acetaldehyde
Hydrogen