4.7 Article

Ceria supported Ru0-Ruδ+ clusters as efficient catalyst for arenes hydrogenation

Journal

CHINESE CHEMICAL LETTERS
Volume 32, Issue 2, Pages 770-774

Publisher

ELSEVIER SCIENCE INC
DOI: 10.1016/j.cclet.2020.05.045

Keywords

Ceria; Ruthenium; Clusters; Amines; Hydrogenation

Funding

  1. Youth Innovation Promotion Association CAS [2018453]
  2. National Natural Science Foundation of China [91645118, 21773270]
  3. NSF of Jiangsu Province [BK20180249]

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A Ru-0-Ru delta+/CeO2 catalyst with solid frustrated Lewis pairs was developed for selective hydrogenation of aromatic amines, showing excellent activity and selectivity towards cyclohexylamine. The catalyst structure and reaction mechanism were characterized by various techniques, and a volcano curve describing the activity and Ru state was found.
Selective hydrogenation of aromatic amines, especially chemicals such as aniline and bis(4-aminocyclohexyl)methane for non-yellowing polyurethane, is of particular interests due to the extensive applications. To conquer the existing difficulties in selective hydrogenation, the Ru-0-Ru delta+/CeO2 catalyst with solid frustrated Lewis pairs was developed for aromatic amines hydrogenation with excellent activity and selectivity under relative milder conditions. The morphology, electronic and chemical properties, especially the Ru-0-Ru delta+ clusters and reducible ceria were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS), CO2 temperature programmed desorption (CO2-TPD), H-2 temperature programmed reduction (H-2-TPR), H-2 diffuse reflectance Fourier transform infrared spectroscopy (H2DRIFT), Raman, etc. The 2% Ru/CeO2 catalyst exhibited good conversion of 95% and selectivity greater than 99% toward cyclohexylamine. The volcano curve describing the activity and Ru state was found. Owning to the acidic site isolation by surrounding alkaline sites, condensation between the neighboring amine molecules could be effectively suppressed. The catalyst also showed good stability and applicability for other aromatic amines and heteroarenes containing different functional groups. (C) 2020 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.

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