Understanding trends in C–H bond activation in heterogeneous catalysis
Abstract
While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed. Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C-H activation barriers using a single universal descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.
- Authors:
-
[1];
- Stanford Univ., Stanford, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Center on Nanostructuring for Efficient Energy Conversion (CNEEC); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1349287
- Alternate Identifier(s):
- OSTI ID: 1468339
- Grant/Contract Number:
- AC02-76SF00515; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Materials
- Additional Journal Information:
- Journal Volume: 16; Journal Issue: 2; Journal ID: ISSN 1476-1122
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Latimer, Allegra A., Kulkarni, Ambarish R., Aljama, Hassan, Montoya, Joseph H., Yoo, Jong Suk, Tsai, Charlie, Abild-Pedersen, Frank, Studt, Felix, and Nørskov, Jens K. Understanding trends in C–H bond activation in heterogeneous catalysis. United States: N. p., 2016.
Web. doi:10.1038/nmat4760.
Latimer, Allegra A., Kulkarni, Ambarish R., Aljama, Hassan, Montoya, Joseph H., Yoo, Jong Suk, Tsai, Charlie, Abild-Pedersen, Frank, Studt, Felix, & Nørskov, Jens K. Understanding trends in C–H bond activation in heterogeneous catalysis. United States. https://doi.org/10.1038/nmat4760
Latimer, Allegra A., Kulkarni, Ambarish R., Aljama, Hassan, Montoya, Joseph H., Yoo, Jong Suk, Tsai, Charlie, Abild-Pedersen, Frank, Studt, Felix, and Nørskov, Jens K. Mon .
"Understanding trends in C–H bond activation in heterogeneous catalysis". United States. https://doi.org/10.1038/nmat4760. https://www.osti.gov/servlets/purl/1349287.
@article{osti_1349287,
title = {Understanding trends in C–H bond activation in heterogeneous catalysis},
author = {Latimer, Allegra A. and Kulkarni, Ambarish R. and Aljama, Hassan and Montoya, Joseph H. and Yoo, Jong Suk and Tsai, Charlie and Abild-Pedersen, Frank and Studt, Felix and Nørskov, Jens K.},
abstractNote = {While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed. Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C-H activation barriers using a single universal descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.},
doi = {10.1038/nmat4760},
journal = {Nature Materials},
number = 2,
volume = 16,
place = {United States},
year = {Mon Oct 10 00:00:00 EDT 2016},
month = {Mon Oct 10 00:00:00 EDT 2016}
}
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