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Title: Highly Active Ceria-Supported Ru Catalyst for the Dry Reforming of Methane: In Situ Identification of Ru δ+ –Ce 3+ Interactions for Enhanced Conversion

Abstract

The metal-oxide interaction changes the surface electronic states of catalysts deployed for chemical conversion, yet details of its influence on the catalytic performance under reaction conditions remain obscure. In this work, we report the high activity/stability of a ceria supported Ru-nanocluster (<1nm) catalyst during the dry reforming of methane. To elucidate the structure-reactivity relationship underlying the catalyst’s remarkable catalytic performance, the active structure and chemical speciation of the catalyst was characterized using in-situ X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS), while the surface chemistry and active intermediates were monitored by in-situ ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Methane activates on the catalyst surface at temperatures as low as 150 °C. Under reaction conditions, the existence of metal-support interactions tunes the electronic properties of the Ru nanoclusters, giving rise to a partially oxidized state of ruthenium stabilized by reduced ceria (Ru δ+-CeO 2-x) to sustain active chemistry, which is found to be very different from that of large Ru nanoparticles supported on ceria. The oxidation of surface carbon is also a crucial step for the completion of the catalytic cycle, and this is strongly correlated with the oxygen transfer governed by themore » Ru δ+-CeO 2-x interactions at higher temperatures (> 300 °C). The possible reaction pathways and stable surface intermediates were identified using DRIFTS including ruthenium carbonyls, carboxylate species, and surface -OH groups while polydentate carbonates may be plain spectators at the measured reaction conditions.« less

Authors:
ORCiD logo [1];  [2];  [1];  [3];  [1];  [1]; ORCiD logo [1];  [4]; ORCiD logo [2];  [1];  [5]; ORCiD logo [6]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Stony Brook Univ., Stony Brook, NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Zhengzhou Univ., Henan (China)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. King Abdullah Univ. of Science and Technology (KAUST), Jeddah (Saudi Arabia)
  6. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1524089
Alternate Identifier(s):
OSTI ID: 1557112
Report Number(s):
BNL-211970-2019-JAAM
Journal ID: ISSN 2155-5435; 152729
Grant/Contract Number:  
AC02-06CH11357; SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 4; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
AP-XPS; DRIFTS; EXAFS; XRD; ceria; methane dry reforming; ruthenium; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; dry reforming of methane

Citation Formats

Liu, Zongyuan, Zhang, Feng, Rui, Ning, Li, Xing, Lin, Lili, Betancourt, Luis E., Su, Dong, Xu, Wenqian, Cen, Jiajie, Attenkofer, Klaus, Idriss, Hicham, Rodriguez, José A., and Senanayake, Sanjaya D. Highly Active Ceria-Supported Ru Catalyst for the Dry Reforming of Methane: In Situ Identification of Ruδ+ –Ce3+ Interactions for Enhanced Conversion. United States: N. p., 2019. Web. doi:10.1021/acscatal.8b05162.
Liu, Zongyuan, Zhang, Feng, Rui, Ning, Li, Xing, Lin, Lili, Betancourt, Luis E., Su, Dong, Xu, Wenqian, Cen, Jiajie, Attenkofer, Klaus, Idriss, Hicham, Rodriguez, José A., & Senanayake, Sanjaya D. Highly Active Ceria-Supported Ru Catalyst for the Dry Reforming of Methane: In Situ Identification of Ruδ+ –Ce3+ Interactions for Enhanced Conversion. United States. doi:10.1021/acscatal.8b05162.
Liu, Zongyuan, Zhang, Feng, Rui, Ning, Li, Xing, Lin, Lili, Betancourt, Luis E., Su, Dong, Xu, Wenqian, Cen, Jiajie, Attenkofer, Klaus, Idriss, Hicham, Rodriguez, José A., and Senanayake, Sanjaya D. Mon . "Highly Active Ceria-Supported Ru Catalyst for the Dry Reforming of Methane: In Situ Identification of Ruδ+ –Ce3+ Interactions for Enhanced Conversion". United States. doi:10.1021/acscatal.8b05162.
@article{osti_1524089,
title = {Highly Active Ceria-Supported Ru Catalyst for the Dry Reforming of Methane: In Situ Identification of Ruδ+ –Ce3+ Interactions for Enhanced Conversion},
author = {Liu, Zongyuan and Zhang, Feng and Rui, Ning and Li, Xing and Lin, Lili and Betancourt, Luis E. and Su, Dong and Xu, Wenqian and Cen, Jiajie and Attenkofer, Klaus and Idriss, Hicham and Rodriguez, José A. and Senanayake, Sanjaya D.},
abstractNote = {The metal-oxide interaction changes the surface electronic states of catalysts deployed for chemical conversion, yet details of its influence on the catalytic performance under reaction conditions remain obscure. In this work, we report the high activity/stability of a ceria supported Ru-nanocluster (<1nm) catalyst during the dry reforming of methane. To elucidate the structure-reactivity relationship underlying the catalyst’s remarkable catalytic performance, the active structure and chemical speciation of the catalyst was characterized using in-situ X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS), while the surface chemistry and active intermediates were monitored by in-situ ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Methane activates on the catalyst surface at temperatures as low as 150 °C. Under reaction conditions, the existence of metal-support interactions tunes the electronic properties of the Ru nanoclusters, giving rise to a partially oxidized state of ruthenium stabilized by reduced ceria (Ruδ+-CeO2-x) to sustain active chemistry, which is found to be very different from that of large Ru nanoparticles supported on ceria. The oxidation of surface carbon is also a crucial step for the completion of the catalytic cycle, and this is strongly correlated with the oxygen transfer governed by the Ruδ+-CeO2-x interactions at higher temperatures (> 300 °C). The possible reaction pathways and stable surface intermediates were identified using DRIFTS including ruthenium carbonyls, carboxylate species, and surface -OH groups while polydentate carbonates may be plain spectators at the measured reaction conditions.},
doi = {10.1021/acscatal.8b05162},
journal = {ACS Catalysis},
number = 4,
volume = 9,
place = {United States},
year = {2019},
month = {3}
}

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