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Mechanistic Insights into the Synthesis of Higher Alcohols from Syngas on CuCo Alloys

Journal Article · · ACS Catalysis
 [1];  [2];  [2];  [2];  [2];  [2];  [3];  [2];  [2]
  1. Tianjin Univ., Tianjin (People's Republic of China); SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  3. Tianjin Univ., Tianjin (People’s Republic of China)
+ Show Author Affiliations
Synthesis gas (CO + H2) conversion is an important process in the transformation of coal, natural gas, or biomass into higher-value products. The explicit conversion into C2+ oxygenates on transition-metal-based catalysts suffers from a low selectivity, being a consequence of an imperative integration of C–O bond splitting and C–C coupling reactions. Recently, it has been demonstrated that a bimetallic CuCo catalyst has high higher alcohol selectivity under mild reaction conditions, but the details of the reaction mechanism on the surface are still elusive. In this work, we studied the formation of methane, methanol, and ethanol from syngas on a close-packed (111) and a stepped (211) CuCo surface combining density functional theory (DFT) and microkinetic modeling. We found the CuCo alloy to be a promising candidate catalyst, displaying the required coverage of CO and CHx on the surface to facilitate C–C coupling. In addition, we found the selectivity to be very structure sensitive: the CuCo (211) surface is selective toward ethanol under certain reaction conditions, while the (111) surface is selective toward methanol. As a result, we identified the much lower C–O dissociation barrier and the higher rate of CHx–CO coupling as the reason for the high activity and selectivity toward ethanol on the (211) surface.
Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1490982
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 11 Vol. 8; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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36 MATERIALS SCIENCE
CuCo alloy
DFT
higher alcohol synthesis
microkinetic modeling
synthesis gas conversion