Dynamic control and quantification of active sites on ceria for CO activation and hydrogenation

Shao, Weipeng; Zhang, Yi; Zhou, Zhiwen; Li, Na; Jiao, Feng; Ling, Yunjian; Li, Yangsheng; Zhou, Zeyu; Cao, Yunjun; Liu, Zhi; Pan, Xiulian; Fu, Qiang; Wöll, Christof; Liu, Ping; Bao, Xinhe; Yang, Fan

doi:10.1038/s41467-024-53948-1

Dynamic control and quantification of active sites on ceria for CO activation and hydrogenation

Journal Article · Thu Nov 07 00:00:00 EST 2024 · Nature Communications

DOI:https://doi.org/10.1038/s41467-024-53948-1· OSTI ID:2529397

^[1]; Zhang, Yi ^[2]; Zhou, Zhiwen ^[2]; Li, Na ^[2]; ^[2]; ^[3]; Li, Yangsheng ^[3]; Zhou, Zeyu ^[1]; ^[2]; ^[1]; ^[2]; ^[2]; ^[4]; ^[5]; ^[2]; ^[3]

ShanghaiTech Univ. (China)
Dalian Institute of Chemical Physics (China)
ShanghaiTech Univ. (China); Dalian Institute of Chemical Physics (China)
Karlsruhe Inst. of Technology (KIT) (Germany)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

Ceria (CeO₂) is a widely used oxide catalyst, yet the nature of its active sites remains elusive. This study combines model and powder catalyst studies to elucidate the structure-activity relationships in ceria-catalyzed CO activation and hydrogenation. Well-defined ceria clusters are synthesized on planar CeO₂(111) and exhibit dynamic and tunable ranges of Ce coordination numbers, which enhance their interaction with CO. Reduced ceria clusters (e.g., Ce₃O₃) bind CO strongly and facilitate its dissociation, while near-stoichiometric clusters (e.g., Ce₃O₇) adsorb CO weakly and promote oxidation via carbonate formation. Unlike planar ceria surfaces, supported ceria clusters exhibit dynamic properties and enhanced catalytic activity, that mimic those of powder ceria catalysts. Insight from model studies provide a method to quantify active sites on powder ceria and guide further optimization of ceria catalysts for syngas conversion. This work marks a leap toward model-guided catalyst design and highlights the importance of site-specific catalysis.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0012704

OSTI ID:: 2529397

Report Number(s):: BNL--227642-2025-JAAM

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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