Elucidating the roles of metallic Ni and oxygen vacancies in CO2 hydrogenation over Ni/CeO2 using isotope exchange and in situ measurements
Abstract
Improvement in processes to convert CO2 to value-added chemicals requires elucidation of catalytic mechanisms. Previous investigations of CO2 reduction by hydrogen over CeO2-supported Ni catalysts suggested that the selectivity to CO and CH4 was related to the Ni loading. In this work we utilized near ambient pressure X-ray photoelectron spectroscopy to confirm that Ni remained metallic under reaction conditions at different Ni loadings. The presence of partially reduced CeO2 was detected, suggesting that oxygen from CO2 did not re-oxidize the CeOx. Isotope exchange studies were performed using C18O2 in a batch reactor equipped with Fourier transform infrared spectroscopy and mass spectrometry to determine the involvement of surface and lattice oxygen. Our results demonstrate that oxygen exchange with the CeO2 support occurs beyond the surface layer under CO2 hydrogenation conditions. Kinetic studies also revealed that the oxygen exchange rate is fast with respect to the CO2 hydrogenation reaction rate and that the CeO2 oxygen exchange mechanism is modified by Ni.
- Authors:
-
- Columbia Univ., New York, NY (United States)
- Nankai Univ., Tianjin (China)
- Tsinghua Univ., Beijing (China)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Stony Brook Univ., NY (United States)
- Columbia Univ., New York, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1543402
- Report Number(s):
- BNL-211862-2019-JAAM
Journal ID: ISSN 0926-3373
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Applied Catalysis B: Environmental
- Additional Journal Information:
- Journal Volume: 245; Journal Issue: C; Journal ID: ISSN 0926-3373
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CO2 hydrogenation; CeO2 reduction; metallic Ni; oxygen exchange; AP-XPS
Citation Formats
Winter, Lea R., Chen, Rui, Chen, Xin, Chang, Kuan, Liu, Zongyuan, Senanayake, Sanjaya D., Ebrahim, Amani M., and Chen, Jingguang G. Elucidating the roles of metallic Ni and oxygen vacancies in CO2 hydrogenation over Ni/CeO2 using isotope exchange and in situ measurements. United States: N. p., 2018.
Web. doi:10.1016/j.apcatb.2018.12.069.
Winter, Lea R., Chen, Rui, Chen, Xin, Chang, Kuan, Liu, Zongyuan, Senanayake, Sanjaya D., Ebrahim, Amani M., & Chen, Jingguang G. Elucidating the roles of metallic Ni and oxygen vacancies in CO2 hydrogenation over Ni/CeO2 using isotope exchange and in situ measurements. United States. doi:10.1016/j.apcatb.2018.12.069.
Winter, Lea R., Chen, Rui, Chen, Xin, Chang, Kuan, Liu, Zongyuan, Senanayake, Sanjaya D., Ebrahim, Amani M., and Chen, Jingguang G. Fri .
"Elucidating the roles of metallic Ni and oxygen vacancies in CO2 hydrogenation over Ni/CeO2 using isotope exchange and in situ measurements". United States. doi:10.1016/j.apcatb.2018.12.069. https://www.osti.gov/servlets/purl/1543402.
@article{osti_1543402,
title = {Elucidating the roles of metallic Ni and oxygen vacancies in CO2 hydrogenation over Ni/CeO2 using isotope exchange and in situ measurements},
author = {Winter, Lea R. and Chen, Rui and Chen, Xin and Chang, Kuan and Liu, Zongyuan and Senanayake, Sanjaya D. and Ebrahim, Amani M. and Chen, Jingguang G.},
abstractNote = {Improvement in processes to convert CO2 to value-added chemicals requires elucidation of catalytic mechanisms. Previous investigations of CO2 reduction by hydrogen over CeO2-supported Ni catalysts suggested that the selectivity to CO and CH4 was related to the Ni loading. In this work we utilized near ambient pressure X-ray photoelectron spectroscopy to confirm that Ni remained metallic under reaction conditions at different Ni loadings. The presence of partially reduced CeO2 was detected, suggesting that oxygen from CO2 did not re-oxidize the CeOx. Isotope exchange studies were performed using C18O2 in a batch reactor equipped with Fourier transform infrared spectroscopy and mass spectrometry to determine the involvement of surface and lattice oxygen. Our results demonstrate that oxygen exchange with the CeO2 support occurs beyond the surface layer under CO2 hydrogenation conditions. Kinetic studies also revealed that the oxygen exchange rate is fast with respect to the CO2 hydrogenation reaction rate and that the CeO2 oxygen exchange mechanism is modified by Ni.},
doi = {10.1016/j.apcatb.2018.12.069},
journal = {Applied Catalysis B: Environmental},
number = C,
volume = 245,
place = {United States},
year = {2018},
month = {12}
}
Web of Science
Works referencing / citing this record:
The effects of bimetallic interactions for CO 2 ‐assisted oxidative dehydrogenation and dry reforming of propane
journal, June 2019
- Gomez, Elaine; Xie, Zhenhua; Chen, Jingguang G.
- AIChE Journal, Vol. 65, Issue 8
CO2 Hydrogenation over Nanoceria-Supported Transition Metal Catalysts: Role of Ceria Morphology (Nanorods versus Nanocubes) and Active Phase Nature (Co versus Cu)
journal, December 2019
- Konsolakis, Michalis; Lykaki, Maria; Stefa, Sofia
- Nanomaterials, Vol. 9, Issue 12