Nature of Reactive Hydrogen for Ammonia Synthesis over a Ru/C12A7 Electride Catalyst
Abstract
Recently, there have been renewed interests in exploring new catalysts for ammonia synthesis under mild conditions. Electride-based catalysts are among the emerging ones. Ruthenium particles supported on an electride composed of a mixture of calcium and aluminum oxides (C12A7) have attracted great attention for ammonia synthesis due to their facile ability in activating N2 under ambient pressure. However, the exact nature of the reactive hydrogen species and the role of electride support still remain elusive for this catalytic system. Here, we report for the first time that the surface-adsorbed hydrogen, rather than the hydride encaged in the C12A7 electride, plays a major role in ammonia synthesis over the Ru/C12A7 electride catalyst with the aid of in situ neutron scattering techniques. Combining in situ neutron diffraction, inelastic neutron spectroscopy, density functional theory (DFT) calculation, and temperature-programmed reactions, the results provide direct evidence for not only the presence of encaged hydrides during ammonia synthesis but also the strong thermal and chemical stability of the hydride species in the Ru/C12A7 electride. Steady state isotopic transient kinetic analysis (SSITKA) of ammonia synthesis showed that the coverage of reactive intermediates increased significantly when the Ru particles were promoted by the electride form (coverage up tomore »
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division and Center for Nanophase Materials Sciences (CNMS)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Clemson Univ., SC (United States). Dept. of Materials Science and Engineering
- Clemson Univ., SC (United States). Dept. of Materials Science and Engineering
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
- Sponsoring Org.:
- USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC)
- OSTI Identifier:
- 1649278
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 142; Journal Issue: 16; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; anions; ammonia; mixtures; catalysts; neutron diffraction
Citation Formats
Kammert, James, Moon, Jisue, Cheng, Yongqiang, Daemen, Luke L., Irle, Stephan, Fung, Victor, Liu, Jue, Page, Katharine, Ma, Xiaohan, Phaneuf, Vincent, Tong, Jianhua, Ramirez Cuesta, Anibal, and Wu, Zili. Nature of Reactive Hydrogen for Ammonia Synthesis over a Ru/C12A7 Electride Catalyst. United States: N. p., 2020.
Web. doi:10.1021/jacs.0c02345.
Kammert, James, Moon, Jisue, Cheng, Yongqiang, Daemen, Luke L., Irle, Stephan, Fung, Victor, Liu, Jue, Page, Katharine, Ma, Xiaohan, Phaneuf, Vincent, Tong, Jianhua, Ramirez Cuesta, Anibal, & Wu, Zili. Nature of Reactive Hydrogen for Ammonia Synthesis over a Ru/C12A7 Electride Catalyst. United States. https://doi.org/10.1021/jacs.0c02345
Kammert, James, Moon, Jisue, Cheng, Yongqiang, Daemen, Luke L., Irle, Stephan, Fung, Victor, Liu, Jue, Page, Katharine, Ma, Xiaohan, Phaneuf, Vincent, Tong, Jianhua, Ramirez Cuesta, Anibal, and Wu, Zili. Sat .
"Nature of Reactive Hydrogen for Ammonia Synthesis over a Ru/C12A7 Electride Catalyst". United States. https://doi.org/10.1021/jacs.0c02345. https://www.osti.gov/servlets/purl/1649278.
@article{osti_1649278,
title = {Nature of Reactive Hydrogen for Ammonia Synthesis over a Ru/C12A7 Electride Catalyst},
author = {Kammert, James and Moon, Jisue and Cheng, Yongqiang and Daemen, Luke L. and Irle, Stephan and Fung, Victor and Liu, Jue and Page, Katharine and Ma, Xiaohan and Phaneuf, Vincent and Tong, Jianhua and Ramirez Cuesta, Anibal and Wu, Zili},
abstractNote = {Recently, there have been renewed interests in exploring new catalysts for ammonia synthesis under mild conditions. Electride-based catalysts are among the emerging ones. Ruthenium particles supported on an electride composed of a mixture of calcium and aluminum oxides (C12A7) have attracted great attention for ammonia synthesis due to their facile ability in activating N2 under ambient pressure. However, the exact nature of the reactive hydrogen species and the role of electride support still remain elusive for this catalytic system. Here, we report for the first time that the surface-adsorbed hydrogen, rather than the hydride encaged in the C12A7 electride, plays a major role in ammonia synthesis over the Ru/C12A7 electride catalyst with the aid of in situ neutron scattering techniques. Combining in situ neutron diffraction, inelastic neutron spectroscopy, density functional theory (DFT) calculation, and temperature-programmed reactions, the results provide direct evidence for not only the presence of encaged hydrides during ammonia synthesis but also the strong thermal and chemical stability of the hydride species in the Ru/C12A7 electride. Steady state isotopic transient kinetic analysis (SSITKA) of ammonia synthesis showed that the coverage of reactive intermediates increased significantly when the Ru particles were promoted by the electride form (coverage up to 84%) of the C12A7 support rather than the oxide form (coverage up to 15%). Such a drastic change in the intermediate coverage on the Ru surface is attributed to the positive role of electride support where the H2 poisoning effect is absent during ammonia synthesis over Ru. The finding of this work has significant implications for understanding catalysis by electride-based materials for ammonia synthesis and hydrogenation reactions in general.},
doi = {10.1021/jacs.0c02345},
journal = {Journal of the American Chemical Society},
number = 16,
volume = 142,
place = {United States},
year = {Sat Apr 04 00:00:00 EDT 2020},
month = {Sat Apr 04 00:00:00 EDT 2020}
}
Web of Science
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