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Critical Hydrogen Coverage Effect on the Hydrogenation of Ethylene Catalyzed by δ-MoC(001): An Ab Initio Thermodynamic and Kinetic Study

Journal Article · · ACS Catalysis
 [1];  [1];  [2];  [3];  [2]
  1. Univ. de Medellin (Columbia)
  2. Univ. of Barcelona (Spain)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations

Highly selective oxidation of methane to methanol has long been challenging in catalysis. Here, we reveal key steps for the promotion by water when tuning the selectivity of a well-defined CeO2/Cu2O/Cu(111) catalyst from CO and CO2 to methanol under a reaction environment with methane, oxygen, and water. Ambient-pressure x-ray photoelectron spectroscopy showed that water added to CH4 and O2 led to surface CH3O and accelerated methanol production. These results were consistent with density functional theory calculations and kinetic Monte Carlo simulations which showed that water preferentially dissociates over the active Ce ions at the CeO2-Cu2O/Cu(111) interface. The adsorbed OH blocked O-O bond cleavage that would dehydrogenate CH3O to CO and CO2, and it directly converted this species to methanol, while O2 now reoxidized the reduced surface. Water adsorption also displaced the produced methanol into the gas phase.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012704
OSTI ID:
1637477
Report Number(s):
BNL--216107-2020-JAAM
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 11 Vol. 10; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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