Highly Active Ceria-Supported Ru Catalyst for the Dry Reforming of Methane: In Situ Identification of Ruδ+ –Ce3+ Interactions for Enhanced Conversion

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.

doi:10.1021/acscatal.8b05162

Title: Highly Active Ceria-Supported Ru Catalyst for the Dry Reforming of Methane: In Situ Identification of Ru^δ+ –Ce³⁺ Interactions for Enhanced Conversion

Journal Article · Mon Mar 04 00:00:00 EST 2019 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.8b05162· OSTI ID:1524089

^[1]; Zhang, Feng ^[2]; Rui, Ning ^[1]; Li, Xing ^[3]; Lin, Lili ^[1]; Betancourt, Luis E. ^[1];

^[1]; Xu, Wenqian ^[4];

^[2]; Attenkofer, Klaus ^[1]; Idriss, Hicham ^[5];

^[6];

^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States)
Stony Brook Univ., Stony Brook, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States); Zhengzhou Univ., Henan (China)
Argonne National Lab. (ANL), Argonne, IL (United States)
King Abdullah Univ. of Science and Technology (KAUST), Jeddah (Saudi Arabia)
Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)

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 the 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.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; SC0012704

OSTI ID:: 1524089

Alternate ID(s):: OSTI ID: 1557112

Report Number(s):: BNL-211970-2019-JAAM; 152729

Journal Information:: ACS Catalysis, Vol. 9, Issue 4; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 82 works

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Title: Highly Active Ceria-Supported Ru Catalyst for the Dry Reforming of Methane: In Situ Identification of Ruδ+ –Ce3+ Interactions for Enhanced Conversion

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Title: Highly Active Ceria-Supported Ru Catalyst for the Dry Reforming of Methane: In Situ Identification of Ru^δ+ –Ce³⁺ Interactions for Enhanced Conversion