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Low-Temperature Activation and Coupling of Methane on MgO Nanostructures Embedded in Cu2O/Cu(111)

Journal Article · · ACS Nano
 [1];  [1];  [2];  [3];  [1];  [4];  [5];  [4];  [4];  [6];  [6]
  1. Brookhaven National Laboratory (BNL), Upton, NY (United States)
  2. Stony Brook Univ., NY (United States)
  3. Universidad Central de Venezuela, Caracas (Venezuela); Zoneca-CENEX, Monterrey (Mexico). R&D Laboratories
  4. Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  5. Univ. of Michigan, Ann Arbor, MI (United States)
  6. Brookhaven National Laboratory (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
+ Show Author Affiliations
Here, the efficient conversion of methane into valuable hydrocarbons such as ethane and ethylene at relatively low temperatures without deactivation issues is crucial for advancing sustainable energy solutions. Herein, AP-XPS and STM studies show that MgO nanostructures (0.2-0.5 nm wide, 0.4-0.6 Å high) embedded in a Cu2O/Cu(111) substrate activate methane at room temperature, mainly dissociating it into CHx (x = 2 or 3) and H adatoms, with minimal conversion to C adatoms. These MgO nanostructures in contact with Cu2O/Cu(111) exhibit unique reactivity, enabling C-C coupling into ethane and ethylene at 500 K, a significantly lower temperature than that required for bulk MgO catalysts (>700 K), with negligible carbon deposition and no deactivation. DFT calculations corroborate these experimental findings. The CH4,gas → *CH3 +*H reaction is a downhill process on MgO/Cu2O/Cu(111) surfaces. The activation of methane is facilitated by an electron transfer from copper to MgO and the existence of Mg and O atoms with a low coordination number in the oxide nanostructures. The formation of O-CH3 and O-H bonds overcomes the energy necessary for the cleavage of a C-H bond in methane. DFT studies reveal that smaller Mg2O2 model clusters provide stronger binding and lower activation barriers for C-H dissociation in CH4, while larger Mg3O3 clusters promote C-C coupling due to weaker *CH3 binding. All these results emphasize the importance of size when optimizing the catalytic performance of MgO nanostructures in the selective conversion of methane.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
Grant/Contract Number:
SC0012704
OSTI ID:
2475473
Report Number(s):
BNL--226297-2024-JAAM
Journal Information:
ACS Nano, Journal Name: ACS Nano Journal Issue: 41 Vol. 18; ISSN 1936-0851
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

36 MATERIALS SCIENCE
Ethane formation
Ethylene formation
Magnesium oxide nanostructures
Methane activation
Methane coupling