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Title: Effects of Zr Doping into Ceria for the Dry Reforming of Methane over Ni/CeZrO2 Catalysts: In Situ Studies with XRD, XAFS, and AP-XPS

Abstract

The methane activation and methane dry reforming reactions were studied and compared over 4 wt % Ni/CeO2 and 4 wt % Ni/CeZrO2 (containing 20 wt % Zr) catalysts. Upon the incorporation of Zr into the ceria support, the catalyst exhibited a significantly improved activity and H-2 selectivity. To understand the effects of the Zr dopant on Ni and CeO2 during the dry reforming of methane (DRM) reaction and to probe the structure-reactivity relationship underlying the enhanced catalytic performance of the mixed-oxide system, in situ time-resolved X-ray diffraction (TR-XRD), X-ray absorption fine structure (XAFS), and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) were employed to characterize the catalysts under reaction conditions. TR-XRD and AP-XPS indicate that ceria-zirconia supported Ni (Ni/CeZrO2) is of higher reducibility than the pure ceria supported Ni (Ni/CeO2) upon the reaction with pure CH4 or for the methane dry reforming reaction. The active state of Ni/CeZrO2 under optimum DRM conditions (700 degrees C) was identified as Ni, Ce3+/Ce4+, and Zr4+. The particle size of both nickel and the ceria support under reaction conditions was analyzed by Rietveld refinement and extended XAFS fitting. Zr in the ceria support prevents particle sintering and maintains small particle sizes for both metallic nickel andmore » the partially reduced ceria support under reaction conditions through a stronger-metal support interaction. Additionally, Zr prevents Ni migration from the surface into ceria forming a Ce1-xNixO2-y solid solution, which is seen in Ni/CeO2, thus helping to preserve the active Ni-0 on the Ni/CeZrO2 surface.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [2];  [2];  [2];  [4];  [4];  [5]; ORCiD logo [6]; ORCiD logo [7];  [7]; ORCiD logo [7]; ORCiD logo [2]
  1. Stony Brook Univ., NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. State Univ. of New York (SUNY), Binghamton, NY (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  6. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
  7. National Inst. of Chemistry, Ljubljana (Slovenia). Dept. of Inorganic Chemistry and Technology
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Slovenian Research Agency (ARRS); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1603284
Alternate Identifier(s):
OSTI ID: 1631970
Report Number(s):
BNL-213666-2020-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: 10; Journal Issue: 5; 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; nickel; ceria; zirconia; CeZrO2 solid solution; XRD; XAFS; AP-XPS; dry reforming of methane; CeZrO2 solid solution

Citation Formats

Zhang, Feng, Liu, Zongyuan, Chen, Xiaobo, Rui, Ning, Betancourt, Luis E., Lin, Lili, Xu, Wenqian, Sun, Cheng-jun, Abeykoon, A. M. Milinda, Rodriguez, José A., Teržan, Janvit, Lorber, Kristijan, Djinović, Petar, and Senanayake, Sanjaya D. Effects of Zr Doping into Ceria for the Dry Reforming of Methane over Ni/CeZrO2 Catalysts: In Situ Studies with XRD, XAFS, and AP-XPS. United States: N. p., 2020. Web. doi:10.1021/acscatal.9b04451.
Zhang, Feng, Liu, Zongyuan, Chen, Xiaobo, Rui, Ning, Betancourt, Luis E., Lin, Lili, Xu, Wenqian, Sun, Cheng-jun, Abeykoon, A. M. Milinda, Rodriguez, José A., Teržan, Janvit, Lorber, Kristijan, Djinović, Petar, & Senanayake, Sanjaya D. Effects of Zr Doping into Ceria for the Dry Reforming of Methane over Ni/CeZrO2 Catalysts: In Situ Studies with XRD, XAFS, and AP-XPS. United States. doi:https://doi.org/10.1021/acscatal.9b04451
Zhang, Feng, Liu, Zongyuan, Chen, Xiaobo, Rui, Ning, Betancourt, Luis E., Lin, Lili, Xu, Wenqian, Sun, Cheng-jun, Abeykoon, A. M. Milinda, Rodriguez, José A., Teržan, Janvit, Lorber, Kristijan, Djinović, Petar, and Senanayake, Sanjaya D. Mon . "Effects of Zr Doping into Ceria for the Dry Reforming of Methane over Ni/CeZrO2 Catalysts: In Situ Studies with XRD, XAFS, and AP-XPS". United States. doi:https://doi.org/10.1021/acscatal.9b04451. https://www.osti.gov/servlets/purl/1603284.
@article{osti_1603284,
title = {Effects of Zr Doping into Ceria for the Dry Reforming of Methane over Ni/CeZrO2 Catalysts: In Situ Studies with XRD, XAFS, and AP-XPS},
author = {Zhang, Feng and Liu, Zongyuan and Chen, Xiaobo and Rui, Ning and Betancourt, Luis E. and Lin, Lili and Xu, Wenqian and Sun, Cheng-jun and Abeykoon, A. M. Milinda and Rodriguez, José A. and Teržan, Janvit and Lorber, Kristijan and Djinović, Petar and Senanayake, Sanjaya D.},
abstractNote = {The methane activation and methane dry reforming reactions were studied and compared over 4 wt % Ni/CeO2 and 4 wt % Ni/CeZrO2 (containing 20 wt % Zr) catalysts. Upon the incorporation of Zr into the ceria support, the catalyst exhibited a significantly improved activity and H-2 selectivity. To understand the effects of the Zr dopant on Ni and CeO2 during the dry reforming of methane (DRM) reaction and to probe the structure-reactivity relationship underlying the enhanced catalytic performance of the mixed-oxide system, in situ time-resolved X-ray diffraction (TR-XRD), X-ray absorption fine structure (XAFS), and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) were employed to characterize the catalysts under reaction conditions. TR-XRD and AP-XPS indicate that ceria-zirconia supported Ni (Ni/CeZrO2) is of higher reducibility than the pure ceria supported Ni (Ni/CeO2) upon the reaction with pure CH4 or for the methane dry reforming reaction. The active state of Ni/CeZrO2 under optimum DRM conditions (700 degrees C) was identified as Ni, Ce3+/Ce4+, and Zr4+. The particle size of both nickel and the ceria support under reaction conditions was analyzed by Rietveld refinement and extended XAFS fitting. Zr in the ceria support prevents particle sintering and maintains small particle sizes for both metallic nickel and the partially reduced ceria support under reaction conditions through a stronger-metal support interaction. Additionally, Zr prevents Ni migration from the surface into ceria forming a Ce1-xNixO2-y solid solution, which is seen in Ni/CeO2, thus helping to preserve the active Ni-0 on the Ni/CeZrO2 surface.},
doi = {10.1021/acscatal.9b04451},
journal = {ACS Catalysis},
number = 5,
volume = 10,
place = {United States},
year = {2020},
month = {1}
}

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