In Situ Elucidation of the Active State of Co–CeOx Catalysts in the Dry Reforming of Methane: The Important Role of the Reducible Oxide Support and Interactions with Cobalt
Abstract
The activation of methane and its dry reforming with CO2 was systematically studied over a series (2-30 wt %) of CO2 (similar to 5 nm in size) loaded CeO2 catalysts, with an effort to elucidate the interplay between Co and CeO2 during the catalytic process using in situ methods. The results of in situ time-resolved X-ray diffraction (TR-XRD) show a strong interaction of methane with the CoOx-CeO2 systems at temperatures between 200 and 350 degrees C. The hydrogen produced by the dissociation of C H bonds in methane leads to a full reduction of Co oxide, Co3O4 -> CoO -> Co, and a partial reduction of ceria with the formation of some Ce3+. Upon the addition of CO2, a catalytic cycle for dry reforming of methane (DRM) was achieved on the CoOx-CeO2 powder catalysts at temperatures below 500 degrees C. A 10 wt % Co-CeO2 catalyst was found to possess the best catalytic activity among various cobalt loading catalysts, and it exhibits a desirable stability for the DRM with a accumulation. The phase transitions and the nature of active components in the catalyst were investigated under reaction conditions by in situ time-resolved XRD and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). Thesemore »
- Authors:
-
- Stony Brook Univ., NY (United States). Materials Science and Chemical Engineering Dept.
- Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
- Stony Brook Univ., NY (United States). Dept. of Chemistry
- Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry; Stony Brook Univ., NY (United States). Dept. of Chemistry
- Technical Univ. of Catalonia, Barcelona (Spain). Inst. of Energy Technologies, Dept. of Chemical Engineering and Barcelona Research Center in Multiscale Science and Engineering
- Seoul National Univ. (Korea, Republic of). School of Chemical and Biological Engineering, Inst. of Chemical Processes
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-ray Science Division
- Stony Brook Univ., NY (United States). Materials Science and Chemical Engineering Dept.; Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1462401
- Alternate Identifier(s):
- OSTI ID: 1473677
- Report Number(s):
- BNL-207864-2018-JAAM
Journal ID: ISSN 2155-5435
- Grant/Contract Number:
- SC0012704; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 4; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AP-XPS; ceria; cobalt; in situ XRD; methane dry reforming; in-situ XRD
Citation Formats
Zhang, Feng, Liu, Zongyuan, Zhang, Shuhao, Akter, Nusnin, Palomino, Robert M., Vovchok, Dimitriy, Orozco, Ivan, Salazar, David, Rodriguez, Jose A., Llorca, Jordi, Lee, Jaeha, Kim, DoHeui, Xu, Wenqian, Frenkel, Anatoly I., Li, Yuanyuan, Kim, Taejin, and Senanayake, Sanjaya D. In Situ Elucidation of the Active State of Co–CeOx Catalysts in the Dry Reforming of Methane: The Important Role of the Reducible Oxide Support and Interactions with Cobalt. United States: N. p., 2018.
Web. doi:10.1021/acscatal.7b03640.
Zhang, Feng, Liu, Zongyuan, Zhang, Shuhao, Akter, Nusnin, Palomino, Robert M., Vovchok, Dimitriy, Orozco, Ivan, Salazar, David, Rodriguez, Jose A., Llorca, Jordi, Lee, Jaeha, Kim, DoHeui, Xu, Wenqian, Frenkel, Anatoly I., Li, Yuanyuan, Kim, Taejin, & Senanayake, Sanjaya D. In Situ Elucidation of the Active State of Co–CeOx Catalysts in the Dry Reforming of Methane: The Important Role of the Reducible Oxide Support and Interactions with Cobalt. United States. https://doi.org/10.1021/acscatal.7b03640
Zhang, Feng, Liu, Zongyuan, Zhang, Shuhao, Akter, Nusnin, Palomino, Robert M., Vovchok, Dimitriy, Orozco, Ivan, Salazar, David, Rodriguez, Jose A., Llorca, Jordi, Lee, Jaeha, Kim, DoHeui, Xu, Wenqian, Frenkel, Anatoly I., Li, Yuanyuan, Kim, Taejin, and Senanayake, Sanjaya D. Mon .
"In Situ Elucidation of the Active State of Co–CeOx Catalysts in the Dry Reforming of Methane: The Important Role of the Reducible Oxide Support and Interactions with Cobalt". United States. https://doi.org/10.1021/acscatal.7b03640. https://www.osti.gov/servlets/purl/1462401.
@article{osti_1462401,
title = {In Situ Elucidation of the Active State of Co–CeOx Catalysts in the Dry Reforming of Methane: The Important Role of the Reducible Oxide Support and Interactions with Cobalt},
author = {Zhang, Feng and Liu, Zongyuan and Zhang, Shuhao and Akter, Nusnin and Palomino, Robert M. and Vovchok, Dimitriy and Orozco, Ivan and Salazar, David and Rodriguez, Jose A. and Llorca, Jordi and Lee, Jaeha and Kim, DoHeui and Xu, Wenqian and Frenkel, Anatoly I. and Li, Yuanyuan and Kim, Taejin and Senanayake, Sanjaya D.},
abstractNote = {The activation of methane and its dry reforming with CO2 was systematically studied over a series (2-30 wt %) of CO2 (similar to 5 nm in size) loaded CeO2 catalysts, with an effort to elucidate the interplay between Co and CeO2 during the catalytic process using in situ methods. The results of in situ time-resolved X-ray diffraction (TR-XRD) show a strong interaction of methane with the CoOx-CeO2 systems at temperatures between 200 and 350 degrees C. The hydrogen produced by the dissociation of C H bonds in methane leads to a full reduction of Co oxide, Co3O4 -> CoO -> Co, and a partial reduction of ceria with the formation of some Ce3+. Upon the addition of CO2, a catalytic cycle for dry reforming of methane (DRM) was achieved on the CoOx-CeO2 powder catalysts at temperatures below 500 degrees C. A 10 wt % Co-CeO2 catalyst was found to possess the best catalytic activity among various cobalt loading catalysts, and it exhibits a desirable stability for the DRM with a accumulation. The phase transitions and the nature of active components in the catalyst were investigated under reaction conditions by in situ time-resolved XRD and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). These studies showed dynamic evolutions in the chemical composition of the catalysts under reaction conditions. CO2 attenuated the reducing effects of methane. Under optimum CO- and H-2-producing conditions, both XRD and AP-XPS indicated that the active phase involved a majority of metallic Co with a small amount of CoO, both supported on a partially reduced ceria (Ce3+/Ce4+). We identified the importance of dispersing Co, anchoring it onto the ceria surface sites, and then utilizing the redox properties of CeO2 for activating and then oxidatively converting methane while inhibiting coke formation. Furthermore, a synergistic effect between cobalt and ceria and likely the interfacial sitee are essential to successfully close the catalytic cycle.},
doi = {10.1021/acscatal.7b03640},
journal = {ACS Catalysis},
number = 4,
volume = 8,
place = {United States},
year = {Mon Mar 12 00:00:00 EDT 2018},
month = {Mon Mar 12 00:00:00 EDT 2018}
}
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