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Title: In-situ Characterization of Cu/CeO 2 Nanocatalysts during CO 2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity

Here, a combination of time-resolved X-ray diffraction (TR-XRD), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to carry out an in-situ characterization of Cu/CeO 2 nanocatalysts during the hydrogenation of CO 2. Morphological effects of the ceria supports on the catalytic performances were investigated by examining the behavior of copper/ceria-nanorods (NR) and nanospheres (NS). At atmospheric pressures, the hydrogenation of CO 2 on the copper-ceria catalysts produced mainly CO through the reverse-water gas shift reaction (RWGS) and a negligible amount of methanol. The Cu/CeO 2-NR catalyst displayed the higher activity, which demonstrates that the RWGS is a structure sensitive reaction. In-situ TR-XRD and AP-XPS characterization showed significant changes in the chemical state of the catalysts under reaction conditions with the copper being fully reduced and a partial Ce 4+ to Ce 3+ transformation occurring. A more effective CO 2 dissociative activation at high temperature and a preferential formation of active bidentate carbonate and formate intermediates over CeO 2(110) terminations are probably the main reasons for the better performance of the Cu/CeO 2-NR catalyst in the RWGS reaction.
Authors:
 [1] ;  [2] ;  [2] ;  [3] ;  [2] ;  [3] ;  [4] ;  [4] ;  [3] ;  [2] ;  [2] ;  [5] ; ORCiD logo [6]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Peking Univ., Beijing (China)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. State Univ. of New York at Stony Brook, Stony Brook, NY (United States)
  4. Instituto de Catalisis y Petroleoquimica, Madrid (Spain)
  5. Peking Univ., Beijing (China)
  6. Brookhaven National Lab. (BNL), Upton, NY (United States); State Univ. of New York at Stony Brook, Stony Brook, NY (United States)
Publication Date:
Report Number(s):
BNL-205724-2018-JAAM
Journal ID: ISSN 1932-7447
Grant/Contract Number:
SC0012704
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. C; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1440347

Lin, Lili, Yao, Siyu, Liu, Zongyuan, Zhang, Feng, Na, Li, Vovchok, Dimitriy, Martinez-Arias, Arturo, Castaneda, Rafael, Lin, Jin Ying, Senanayake, Sanjaya D., Su, Dong, Ma, Ding, and Rodriguez, Jose A.. In-situ Characterization of Cu/CeO2 Nanocatalysts during CO2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity. United States: N. p., Web. doi:10.1021/acs.jpcc.8b03596.
Lin, Lili, Yao, Siyu, Liu, Zongyuan, Zhang, Feng, Na, Li, Vovchok, Dimitriy, Martinez-Arias, Arturo, Castaneda, Rafael, Lin, Jin Ying, Senanayake, Sanjaya D., Su, Dong, Ma, Ding, & Rodriguez, Jose A.. In-situ Characterization of Cu/CeO2 Nanocatalysts during CO2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity. United States. doi:10.1021/acs.jpcc.8b03596.
Lin, Lili, Yao, Siyu, Liu, Zongyuan, Zhang, Feng, Na, Li, Vovchok, Dimitriy, Martinez-Arias, Arturo, Castaneda, Rafael, Lin, Jin Ying, Senanayake, Sanjaya D., Su, Dong, Ma, Ding, and Rodriguez, Jose A.. 2018. "In-situ Characterization of Cu/CeO2 Nanocatalysts during CO2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity". United States. doi:10.1021/acs.jpcc.8b03596.
@article{osti_1440347,
title = {In-situ Characterization of Cu/CeO2 Nanocatalysts during CO2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity},
author = {Lin, Lili and Yao, Siyu and Liu, Zongyuan and Zhang, Feng and Na, Li and Vovchok, Dimitriy and Martinez-Arias, Arturo and Castaneda, Rafael and Lin, Jin Ying and Senanayake, Sanjaya D. and Su, Dong and Ma, Ding and Rodriguez, Jose A.},
abstractNote = {Here, a combination of time-resolved X-ray diffraction (TR-XRD), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to carry out an in-situ characterization of Cu/CeO2 nanocatalysts during the hydrogenation of CO2. Morphological effects of the ceria supports on the catalytic performances were investigated by examining the behavior of copper/ceria-nanorods (NR) and nanospheres (NS). At atmospheric pressures, the hydrogenation of CO2 on the copper-ceria catalysts produced mainly CO through the reverse-water gas shift reaction (RWGS) and a negligible amount of methanol. The Cu/CeO2-NR catalyst displayed the higher activity, which demonstrates that the RWGS is a structure sensitive reaction. In-situ TR-XRD and AP-XPS characterization showed significant changes in the chemical state of the catalysts under reaction conditions with the copper being fully reduced and a partial Ce4+ to Ce3+ transformation occurring. A more effective CO2 dissociative activation at high temperature and a preferential formation of active bidentate carbonate and formate intermediates over CeO2(110) terminations are probably the main reasons for the better performance of the Cu/CeO2-NR catalyst in the RWGS reaction.},
doi = {10.1021/acs.jpcc.8b03596},
journal = {Journal of Physical Chemistry. C},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {5}
}