Theoretical insights into the selective oxidation of methane to methanol in copper-exchanged mordenite

Zhao, Zhi -Jian; Kulkarni, Ambarish; Vilella, Laia; Nørskov, Jens K.; Studt, Felix

doi:10.1021/acscatal.6b00440

Theoretical insights into the selective oxidation of methane to methanol in copper-exchanged mordenite

Journal Article · Mon May 02 00:00:00 EDT 2016 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.6b00440· OSTI ID:1349409

Zhao, Zhi -Jian ^[1]; Kulkarni, Ambarish ^[2]; Vilella, Laia ^[3]; Nørskov, Jens K. ^[2]; Studt, Felix ^[2]

SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Tianjin Univ., Tianjin (People's Republic of China)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Univ. Autonoma de Barcelona, Barcelona (Spain)

Selective oxidation of methane to methanol is one of the most difficult chemical processes to perform. A potential group of catalysts to achieve CH₄ partial oxidation are Cu-exchanged zeolites mimicking the active structure of the enzyme methane monooxygenase. However, the details of this conversion, including the structure of the active site, are still under debate. In this contribution, periodic density functional theory (DFT) methods were employed to explore the molecular features of the selective oxidation of methane to methanol catalyzed by Cu-exchanged mordenite (Cu-MOR). We focused on two types of previously suggested active species, CuOCu and CuOOCu. Our calculations indicate that the formation of CuOCu is more feasible than that of CuOOCu. In addition, a much lower C–H dissociation barrier is located on the former active site, indicating that C–H bond activation is easily achieved with CuOCu. We calculated the energy barriers of all elementary steps for the entire process, including catalyst activation, CH₄ activation, and CH₃OH desorption. Finally, our calculations are in agreement with experimental observations and present the first theoretical study examining the entire process of selective oxidation of methane to methanol.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1349409

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 6 Vol. 6; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
copper
density functional theory
methane activation
methanol
mordenite
zeolite

Theoretical insights into the selective oxidation of methane to methanol in copper-exchanged mordenite

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