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Title: Elucidating the roles of metallic Ni and oxygen vacancies in CO 2 hydrogenation over Ni/CeO 2 using isotope exchange and in situ measurements

Abstract

Improvement in processes to convert CO 2 to value-added chemicals requires elucidation of catalytic mechanisms. Previous investigations of CO 2 reduction by hydrogen over CeO2-supported Ni catalysts suggested that the selectivity to CO and CH 4 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 CeO 2 was detected, suggesting that oxygen from CO 2 did not re-oxidize the CeO x. Isotope exchange studies were performed using C 18O 2 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 CeO 2 support occurs beyond the surface layer under CO 2 hydrogenation conditions. Kinetic studies also revealed that the oxygen exchange rate is fast with respect to the CO 2 hydrogenation reaction rate and that the CeO 2 oxygen exchange mechanism is modified by Ni.

Authors:
 [1];  [2];  [3];  [3]; ORCiD logo [4]; ORCiD logo [4];  [5];  [6]
  1. Columbia Univ., New York, NY (United States)
  2. Nankai Univ., Tianjin (China)
  3. Tsinghua Univ., Beijing (China)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Stony Brook Univ., NY (United States)
  6. 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) (SC-22)
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.
@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}
}

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This content will become publicly available on December 28, 2019
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