Ultrafine Pd Nanoparticles Anchored on Spherical Covalent Triazine Frameworks for the Selective Tandem Hydrogenation of Nitrobenzene and Benzaldehyde to Secondary Amines
The selective tandem one-pot synthesis of secondary amines via nitrobenzene and benzaldehyde coupling–hydrogenation is challenging due to side reactions. Herein, a covalent organic framework (COF)-based catalyst was fabricated by anchoring ultrafine Pd nanoparticles on a spherical COF material (Pd/D...
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Published in | ACS sustainable chemistry & engineering Vol. 12; no. 40; pp. 14732 - 14746 |
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Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
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American Chemical Society
07.10.2024
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Abstract | The selective tandem one-pot synthesis of secondary amines via nitrobenzene and benzaldehyde coupling–hydrogenation is challenging due to side reactions. Herein, a covalent organic framework (COF)-based catalyst was fabricated by anchoring ultrafine Pd nanoparticles on a spherical COF material (Pd/DHTA-COF-P123). The surfactant P123 was used as a template during solvothermal synthesis to control the morphology of DHTA-COF-P123 via micellar encapsulation, which endowed the material with a large surface area. The spherical DHTA-COF-P123 support strengthened the metal–support interactions (SMSIs) and regulated the electronic state of Pd species to an electron-rich state, thereby improving catalytic hydrogenation. During Pd/DHTA-COF-P123-catalyzed nitrobenzene and benzaldehyde coupling–hydrogenation, 99.9% conversion of nitrobenzene and 99.6% selectivity for N-benzylaniline were obtained under mild reaction conditions. Theoretical calculations confirmed that the stronger SMSIs were responsible for the excellent activity of Pd/DHTA-COF-P123 in the tandem reaction, and the hydrogenation process was exothermic, which strengthened absorption. This work proposes a green strategy to fabricate an electron-rich Pd-based catalyst by enhancing SMSIs to catalyze the synthesis of secondary amines. |
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AbstractList | The selective tandem one-pot synthesis of secondary amines via nitrobenzene and benzaldehyde coupling–hydrogenation is challenging due to side reactions. Herein, a covalent organic framework (COF)-based catalyst was fabricated by anchoring ultrafine Pd nanoparticles on a spherical COF material (Pd/DHTA-COF-P123). The surfactant P123 was used as a template during solvothermal synthesis to control the morphology of DHTA-COF-P123 via micellar encapsulation, which endowed the material with a large surface area. The spherical DHTA-COF-P123 support strengthened the metal–support interactions (SMSIs) and regulated the electronic state of Pd species to an electron-rich state, thereby improving catalytic hydrogenation. During Pd/DHTA-COF-P123-catalyzed nitrobenzene and benzaldehyde coupling–hydrogenation, 99.9% conversion of nitrobenzene and 99.6% selectivity for N-benzylaniline were obtained under mild reaction conditions. Theoretical calculations confirmed that the stronger SMSIs were responsible for the excellent activity of Pd/DHTA-COF-P123 in the tandem reaction, and the hydrogenation process was exothermic, which strengthened absorption. This work proposes a green strategy to fabricate an electron-rich Pd-based catalyst by enhancing SMSIs to catalyze the synthesis of secondary amines. |
Author | Long, Xiao Wang, Shiyong Dong, Zhengping Guo, Zhen Yuan, Kun Gao, Mengmeng He, Guoqiang |
AuthorAffiliation | Key Laboratory for New Molecule Materials Design and Function of Gansu Universities, College of Chemical Engineering and Technology College of Chemical Engineering State Key Laboratory of Applied Organic Chemistry, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering |
AuthorAffiliation_xml | – name: Key Laboratory for New Molecule Materials Design and Function of Gansu Universities, College of Chemical Engineering and Technology – name: College of Chemical Engineering – name: State Key Laboratory of Applied Organic Chemistry, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering |
Author_xml | – sequence: 1 givenname: Mengmeng surname: Gao fullname: Gao, Mengmeng organization: State Key Laboratory of Applied Organic Chemistry, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering – sequence: 2 givenname: Guoqiang surname: He fullname: He, Guoqiang organization: State Key Laboratory of Applied Organic Chemistry, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering – sequence: 3 givenname: Xiao surname: Long fullname: Long, Xiao organization: State Key Laboratory of Applied Organic Chemistry, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering – sequence: 4 givenname: Shiyong surname: Wang fullname: Wang, Shiyong organization: State Key Laboratory of Applied Organic Chemistry, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering – sequence: 5 givenname: Zhen surname: Guo fullname: Guo, Zhen organization: College of Chemical Engineering – sequence: 6 givenname: Zhengping orcidid: 0000-0003-0775-1133 surname: Dong fullname: Dong, Zhengping email: dongzhp@lzu.edu.cn organization: State Key Laboratory of Applied Organic Chemistry, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering – sequence: 7 givenname: Kun orcidid: 0000-0001-5552-4424 surname: Yuan fullname: Yuan, Kun email: yuankun@tsnu.edu.cn organization: Key Laboratory for New Molecule Materials Design and Function of Gansu Universities, College of Chemical Engineering and Technology |
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Title | Ultrafine Pd Nanoparticles Anchored on Spherical Covalent Triazine Frameworks for the Selective Tandem Hydrogenation of Nitrobenzene and Benzaldehyde to Secondary Amines |
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