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Water-promoted interfacial pathways in methane oxidation to methanol on a CeO 2 -Cu 2 O catalyst

Journal Article · · Science
 [1];  [2];  [2];  [2];  [1];  [1];  [3];  [4];  [5];  [1];  [6];  [6];  [1]
  1. Chemistry Division, Brookhaven National Laboratory, Upton, NY 11973, USA.
  2. Chemistry Department, Stony Brook University, Stony Brook, NY 11794, USA.
  3. Peter-Grünberg-Institut 6, Forschungszentrum Jülich, 52425 Jülich, Germany.
  4. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
  5. Diamond Light Source Limited, Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, UK.
  6. Chemistry Division, Brookhaven National Laboratory, Upton, NY 11973, USA., Chemistry Department, Stony Brook University, Stony Brook, NY 11794, USA.
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Highly selective oxidation of methane to methanol has long been challenging in catalysis. Here, we reveal key steps for the pro­motion of this reaction by water when tuning the selectivity of a well-defined CeO 2 /Cu 2 O/Cu(111) catalyst from carbon monoxide and carbon dioxide to methanol under a reaction environment with methane, oxygen, and water. Ambient-pressure x-ray photoelectron spectroscopy showed that water added to methane and oxygen led to surface methoxy groups 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 cerium ions at the CeO 2 –Cu 2 O/Cu(111) interface. The adsorbed hydroxyl species blocked O-O bond cleavage that would dehydrogenate methoxy groups to carbon monoxide and carbon dioxide, and it directly converted this species to methanol, while oxygen 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:
1616649
Alternate ID(s):
OSTI ID: 1617684
Report Number(s):
BNL--215912-2020-JAAM; /sci/368/6490/513.atom
Journal Information:
Science, Journal Name: Science Journal Issue: 6490 Vol. 368; ISSN 0036-8075
Publisher:
AAASCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY