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Manganese Catalyzed Partial Oxidation of Light Alkanes

Coutard, Nathan and Musgrave, Charles B., III and Moon, Jisue and Liebov, Nichole S. and Nielsen, Robert M. and Goldberg, Jonathan M. and Li, Meijun and Jia, Xiaofan and Lee, Sungsik and Dickie, Diane A. and Schinski, William L. and Wu, Zili and Groves, John T. and Goddard, William A., III and Gunnoe, T. Brent (2022) Manganese Catalyzed Partial Oxidation of Light Alkanes. ACS Catalysis, 12 (9). pp. 5356-5370. ISSN 2155-5435. doi:10.1021/acscatal.2c00982. https://resolver.caltech.edu/CaltechAUTHORS:20220430-000256257

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Abstract

The catalytic partial oxidation of methane is achieved at low temperatures (<200 °C) using manganese oxides and manganese salts in mixtures of trifluoroacetic acid and trifluoroacetic anhydride. Dioxygen is used as the in situ terminal oxidant. For Mn oxides (e.g., MnO₂, Mn₂O₃, and Mn₃O₄), we studied stoichiometric methane partial oxidation in HTFA (TFA = trifluoroacetate). Using a Mn trifluoroacetate salt, at 180 °C and under 25 psig of methane, product selectivity for the mono-oxidized product methyl trifluoroacetate (MeTFA) is observed to be >90% at ∼35% methane conversion at approximately 6 turnovers. Under our catalytic methane oxidation reaction conditions, MeTFA is stable against overoxidation, which explains the likely high selectivity at conversions >15%. Using combined experimental studies and DFT calculations, a mechanism involving soluble and molecular Mn species in the catalytic cycle is proposed. The proposed reaction pathway involves initial activation of Mnᴵᴵ by dioxygen, cleavage of a methane C–H bond by a Mnᴵᴵᴵ hydroxo intermediate, rebound of the methyl radical to generate MeTFA, and finally regeneration of the starting MnII complex. Also, this process is shown to be applicable to the oxidation of ethane, favoring the mono-oxidized product ethyl trifluoroacetate (EtTFA) and reaching ∼46% conversion.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acscatal.2c00982DOIArticle
ORCID:
AuthorORCID
Coutard, Nathan0000-0001-6526-5630
Musgrave, Charles B., III0000-0002-3432-0817
Moon, Jisue0000-0002-1210-6342
Liebov, Nichole S.0000-0002-5115-2771
Nielsen, Robert M.0000-0002-7962-0186
Jia, Xiaofan0000-0003-0425-5089
Dickie, Diane A.0000-0003-0939-3309
Wu, Zili0000-0002-4468-3240
Groves, John T.0000-0002-9944-5899
Goddard, William A., III0000-0003-0097-5716
Gunnoe, T. Brent0000-0001-5714-3887
Additional Information:© 2022 American Chemical Society. Received: February 24, 2022; Revised: April 7, 2022; Published: April 19, 2022. This research was sponsored by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office, under contract DE-AC05-00OR22725 with UT-Battelle, LLC. Utilization of the PHI Versaprobe III XPS within UVa’s Nanoscale Materials Characterization Facility (NMCF) was fundamental to this project; we acknowledge NSF MRI award #1626201 for the acquisition of this instrument, and we acknowledge the assistance of Catherine A. Dukes for equipment training. Partial support of this research during the writing by the National Science Foundation (CHE-1464578 to JTG) is gratefully acknowledged. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. Author Contributions: (N.C., C.B.M.) These authors contributed equally to this work. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC05-00OR22725
NSFDMR-1626201
NSFCHE-1464578
Department of Energy (DOE)DE-AC02-06CH11357
Subject Keywords:methane functionalization, manganese, partial oxidation, natural gas, methanol, oxy-esterification
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1517
Issue or Number:9
DOI:10.1021/acscatal.2c00982
Record Number:CaltechAUTHORS:20220430-000256257
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220430-000256257
Official Citation:Manganese Catalyzed Partial Oxidation of Light Alkanes. Nathan Coutard, Charles B. Musgrave, Jisue Moon, Nichole S. Liebov, Robert M. Nielsen, Jonathan M. Goldberg, Meijun Li, Xiaofan Jia, Sungsik Lee, Diane A. Dickie, William L. Schinski, Zili Wu, John T. Groves, William A. Goddard, and T. Brent Gunnoe. ACS Catalysis 2022 12 (9), 5356-5370; DOI: 10.1021/acscatal.2c00982
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114535
Collection:CaltechAUTHORS
Deposited By: Donna Wrublewski
Deposited On:03 May 2022 20:37
Last Modified:24 May 2022 20:26

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