Catalytic manganese oxide nanostructures for the reverse water gas shift reaction
Abstract
Understanding the fundamental structure–property relationships of nanomaterials is critical for many catalytic applications as they comprise of the catalyst designing principles. In this paper, we develop efficient synthetic methods to prepare various MnO2 structures and investigate their catalytic performance as applied to the reverse Water Gas Shift (rWGS) reaction. We show that the support-free MnO derived from MnO2 1D, 2D and 3D nanostructures are highly selective (100% CO2 to CO), thermally stable catalysts (850 °C) and differently effective in the rWGS. Up to 50% conversion is observed, with a H2/CO2 feed-in ratio of 1 : 1. From both experiments and DFT calculations, we find the MnO2 morphology plays a critical role in governing the catalytic behaviors since it affects the predominant facets exposed under reaction conditions as well as the intercalation of K+ as a structural building block, substantially affecting the gas-solid interactions. The relative adsorption energy of reactant (CO2) and product (CO), ΔE = Eads(CO2) - Eads(CO), is found to correlate linearly with the catalytic activity, implying a structure–function relationship. Lastly, the strong correlation found between Eads(CO2) - Eads(CO), or more generally, Eads(R) - Eads(P), and catalytic activity makes ΔE a useful descriptor for characterization of efficient catalysts involvingmore »
- Authors:
-
[1];
[1];
[1];
[3];
- Yale Univ., New Haven, CT (United States)
- Nankai Univ., Tianjin (China)
- Univ. of Connecticut, Storrs, CT (United States)
- Publication Date:
- Research Org.:
- Univ. of Connecticut, Storrs, CT (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Army Research Laboratory; US Air Force Office of Scientific Research (AFOSR)
- OSTI Identifier:
- 1598231
- Grant/Contract Number:
- FG02-86ER13622; 64935; FA9550-13-1-0020
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nanoscale
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 35; Journal ID: ISSN 2040-3364
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
He, Yulian, Yang, Ke R., Yu, Ziwei, Fishman, Zachary S., Achola, Laura A., Tobin, Zachary M., Heinlein, Jake A., Hu, Shu, Suib, Steven L., Batista, Victor S., and Pfefferle, Lisa D. Catalytic manganese oxide nanostructures for the reverse water gas shift reaction. United States: N. p., 2019.
Web. doi:10.1039/c9nr06078b.
He, Yulian, Yang, Ke R., Yu, Ziwei, Fishman, Zachary S., Achola, Laura A., Tobin, Zachary M., Heinlein, Jake A., Hu, Shu, Suib, Steven L., Batista, Victor S., & Pfefferle, Lisa D. Catalytic manganese oxide nanostructures for the reverse water gas shift reaction. United States. https://doi.org/10.1039/c9nr06078b
He, Yulian, Yang, Ke R., Yu, Ziwei, Fishman, Zachary S., Achola, Laura A., Tobin, Zachary M., Heinlein, Jake A., Hu, Shu, Suib, Steven L., Batista, Victor S., and Pfefferle, Lisa D. Tue .
"Catalytic manganese oxide nanostructures for the reverse water gas shift reaction". United States. https://doi.org/10.1039/c9nr06078b. https://www.osti.gov/servlets/purl/1598231.
@article{osti_1598231,
title = {Catalytic manganese oxide nanostructures for the reverse water gas shift reaction},
author = {He, Yulian and Yang, Ke R. and Yu, Ziwei and Fishman, Zachary S. and Achola, Laura A. and Tobin, Zachary M. and Heinlein, Jake A. and Hu, Shu and Suib, Steven L. and Batista, Victor S. and Pfefferle, Lisa D.},
abstractNote = {Understanding the fundamental structure–property relationships of nanomaterials is critical for many catalytic applications as they comprise of the catalyst designing principles. In this paper, we develop efficient synthetic methods to prepare various MnO2 structures and investigate their catalytic performance as applied to the reverse Water Gas Shift (rWGS) reaction. We show that the support-free MnO derived from MnO2 1D, 2D and 3D nanostructures are highly selective (100% CO2 to CO), thermally stable catalysts (850 °C) and differently effective in the rWGS. Up to 50% conversion is observed, with a H2/CO2 feed-in ratio of 1 : 1. From both experiments and DFT calculations, we find the MnO2 morphology plays a critical role in governing the catalytic behaviors since it affects the predominant facets exposed under reaction conditions as well as the intercalation of K+ as a structural building block, substantially affecting the gas-solid interactions. The relative adsorption energy of reactant (CO2) and product (CO), ΔE = Eads(CO2) - Eads(CO), is found to correlate linearly with the catalytic activity, implying a structure–function relationship. Lastly, the strong correlation found between Eads(CO2) - Eads(CO), or more generally, Eads(R) - Eads(P), and catalytic activity makes ΔE a useful descriptor for characterization of efficient catalysts involving gas-solid interactions beyond the rWGS.},
doi = {10.1039/c9nr06078b},
journal = {Nanoscale},
number = 35,
volume = 11,
place = {United States},
year = {2019},
month = {8}
}
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Figures / Tables:
Fig. 1: SEM, TEM images of (a), (d) nanowires; (b), (e) nanosheets; (c), (f ) nanoflowers. (g) High-resolution TEM image of α-MnO2 nanowire together with the SAED pattern taken at the same location showing a basal spacing of 0.49 nm corresponding to the characteristic plane (200) of α-MnO2. (h) HRTEMmore »
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