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Title: Theoretical Insights into Direct Methane to Methanol Conversion over Supported Dicopper Oxo Nanoclusters

Abstract

In this study, the prospect of using copper oxide nanoclusters grown by atomic layer deposition on a porphyrin support for selective oxidation of methane to methanol was examined by means of density functional theory (DFT) calculations. Ab initio thermodynamic analysis indicates that an active site in the form of Cu(μ-O)Cu can be stabilized by activation in O2 at 465K. Furthermore, a moderate methane activation energy barrier (Ea=54kJ/mol) is predicted, and the hydrogen abstraction activity of the active site could be attributed to the radical character of the bridging oxygen. Methanol extraction in this system is limited by a thermodynamic barrier to desorption of ΔG=57kJ/mol at 473K; however, desorption can be facilitated by the addition of water in a “stepped conversion” process. Overall, our results indicate similar activity between porphyrin-supported copper oxide nanoclusters and existing Cu-exchanged zeolites and provide a computational proof-of-concept for utilizing functionalized organic linkers in metal-organic frameworks (MOFs) for selective oxidation of methane to methanol.

Authors:
 [1];  [2];  [2];  [2];  [1]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemical and Biological Engineering
  2. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1432374
Grant/Contract Number:  
SC0012702; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Catalysis Today
Additional Journal Information:
Journal Volume: 312; Journal ID: ISSN 0920-5861
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
03 NATURAL GAS; 77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Doan, Hieu A., Li, Zhanyong, Farha, Omar K., Hupp, Joseph T., and Snurr, Randall Q. Theoretical Insights into Direct Methane to Methanol Conversion over Supported Dicopper Oxo Nanoclusters. United States: N. p., 2018. Web. doi:10.1016/j.cattod.2018.03.063.
Doan, Hieu A., Li, Zhanyong, Farha, Omar K., Hupp, Joseph T., & Snurr, Randall Q. Theoretical Insights into Direct Methane to Methanol Conversion over Supported Dicopper Oxo Nanoclusters. United States. doi:10.1016/j.cattod.2018.03.063.
Doan, Hieu A., Li, Zhanyong, Farha, Omar K., Hupp, Joseph T., and Snurr, Randall Q. Sun . "Theoretical Insights into Direct Methane to Methanol Conversion over Supported Dicopper Oxo Nanoclusters". United States. doi:10.1016/j.cattod.2018.03.063. https://www.osti.gov/servlets/purl/1432374.
@article{osti_1432374,
title = {Theoretical Insights into Direct Methane to Methanol Conversion over Supported Dicopper Oxo Nanoclusters},
author = {Doan, Hieu A. and Li, Zhanyong and Farha, Omar K. and Hupp, Joseph T. and Snurr, Randall Q.},
abstractNote = {In this study, the prospect of using copper oxide nanoclusters grown by atomic layer deposition on a porphyrin support for selective oxidation of methane to methanol was examined by means of density functional theory (DFT) calculations. Ab initio thermodynamic analysis indicates that an active site in the form of Cu(μ-O)Cu can be stabilized by activation in O2 at 465K. Furthermore, a moderate methane activation energy barrier (Ea=54kJ/mol) is predicted, and the hydrogen abstraction activity of the active site could be attributed to the radical character of the bridging oxygen. Methanol extraction in this system is limited by a thermodynamic barrier to desorption of ΔG=57kJ/mol at 473K; however, desorption can be facilitated by the addition of water in a “stepped conversion” process. Overall, our results indicate similar activity between porphyrin-supported copper oxide nanoclusters and existing Cu-exchanged zeolites and provide a computational proof-of-concept for utilizing functionalized organic linkers in metal-organic frameworks (MOFs) for selective oxidation of methane to methanol.},
doi = {10.1016/j.cattod.2018.03.063},
journal = {Catalysis Today},
issn = {0920-5861},
number = ,
volume = 312,
place = {United States},
year = {2018},
month = {4}
}

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