Elucidating the roles of metallic Ni and oxygen vacancies in CO2 hydrogenation over Ni/CeO2 using isotope exchange and in situ measurements

doi:10.1016/j.apcatb.2018.12.069

Title: 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 CeO_x. 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:

Winter, Lea R. ^[1]; Chen, Rui ^[2]; Chen, Xin ^[3]; Chang, Kuan ^[3];

^[4];

^[4]; Ebrahim, Amani M. ^[5]; Chen, Jingguang G. ^[6]

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:: 2018-12-28

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.

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                    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.

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                    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.

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@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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DOI: 10.1016/j.apcatb.2018.12.069

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Works referencing / citing this record:

The effects of bimetallic interactions for CO ₂ ‐assisted oxidative dehydrogenation and dry reforming of propane
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Gomez, Elaine; Xie, Zhenhua; Chen, Jingguang G.
AIChE Journal, Vol. 65, Issue 8
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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
DOI: 10.3390/nano9121739

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Title: Elucidating the roles of metallic Ni and oxygen vacancies in CO2 hydrogenation over Ni/CeO2 using isotope exchange and in situ measurements

Abstract

Citation Formats

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Title: Elucidating the roles of metallic Ni and oxygen vacancies in CO₂ hydrogenation over Ni/CeO₂ using isotope exchange and in situ measurements

The effects of bimetallic interactions for CO ₂ ‐assisted oxidative dehydrogenation and dry reforming of propane
journal, June 2019

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journal, December 2019