Synergy of Oxygen Vacancies and Base Sites for Transfer Hydrogenation of Nitroarenes on Ceria Nanorods

Yuan, Ziliang; Huang, Liang; Liu, Yuanshuai; Sun, Yong; Wang, Guanghui; Li, Xun; Lercher, Johannes A.; Zhang, Zehui

doi:10.1002/anie.202317339

Title: Synergy of Oxygen Vacancies and Base Sites for Transfer Hydrogenation of Nitroarenes on Ceria Nanorods

Journal Article · 12 December 2023 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202317339 · OSTI ID:2409374

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^[4]; Wang, Guanghui ^[2]; Li, Xun ^[5];

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South-Central Minzu University, Wuhan (China); Wuhan Univ. of Science and Technology (China)
Wuhan Univ. of Science and Technology (China)
Chinese Academy of Sciences (CAS), Qingdao (China). Qingdao Institute of Bioenergy and Bioprocess Technology
Xiamen University (China)
South-Central Minzu University, Wuhan (China)
Technische Univ. München, Garching (Germany); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Institute for Integrated Catalysis

CeO₂ nanorod based catalysts for the base-free synthesis of azoxy-aromatics via transfer hydrogenation of nitroarenes with ethanol as hydrogen donor have been synthesized and investigated. The oxygen vacancies (O_v) and base sites are critical for their excellent catalytic properties. The O_v, i.e., undercoordinated Ce cations, serve as the sites to activate ethanol and nitroarenes by lowering the energy barrier to transfer hydrogen from α–C_sp3–H in ethanol to the nitro group coupling it to the redox reactions between Ce³⁺ and Ce⁴⁺. At the same time, the base sites catalyze the condensation step to selectively produce azoxy-aromatics. Finally, the catalytic route opens a much improved way to use non-noble metal oxides without additives for the selective functional group reduction and coupling reactions.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); Natural Science Foundation of Hubei Province; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2409374

Report Number(s):: PNNL-SA--197838

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 9 Vol. 63; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
azoxy-aromatics
biomass-derived ethanol
ceria catalysts
nitroarenes

Title: Synergy of Oxygen Vacancies and Base Sites for Transfer Hydrogenation of Nitroarenes on Ceria Nanorods

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