Carboxyethylsilanetriol-Functionalized Al-MIL-53-Supported Palladium Catalyst for Enhancing Suzuki–Miyaura Cross-Coupling Reaction
The application of metal–organic frameworks (MOFs) has attracted increasing attention in organic synthesis. The modification of MOFs can efficiently tailor the structure and improve the property for meeting ongoing demand in various applications, such as the alteration of gas adsorption and separati...
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2025-02-01
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| author | Yucang Liang Xin Ning Yanzhong Zhen |
| author_facet | Yucang Liang Xin Ning Yanzhong Zhen |
| author_sort | Yucang Liang |
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| description | The application of metal–organic frameworks (MOFs) has attracted increasing attention in organic synthesis. The modification of MOFs can efficiently tailor the structure and improve the property for meeting ongoing demand in various applications, such as the alteration of gas adsorption and separation, catalytic activity, stability, and sustainability or reusability. In this study, carboxyethylsilanetriol (CEST) disodium salt was used as a dual-functional ligand for modified Al-MIL-53 to fabricate CEST-functionalized Al-MIL-53 samples through a hydrothermal reaction of aluminum nitrate, terephthalic acid, and CEST disodium salt by varying the molar ratio of CEST to terephthalic acid and keeping a constant molar ratio of Al<sup>3+</sup>/-COOH of 1:1. The structure, composition, morphology, pore feature, and stability were characterized by XRD, different spectroscopies, electron microscopy, N<sub>2</sub> physisorption, and thermogravimetric analysis. With increasing CEST content, CEST-Al-MIL-53 still preserves an Al-MIL-53-like structure, but the microstructure changed compared with pure Al-MIL-53 due to the integration of CEST. Such a CEST-Al-MIL-53 was used as the support to load Pd particles and afford a catalyst Pd/CEST-Al-MIL-53 for Suzuki–Miyaura C-C cross-coupling reaction of aryl halides and phenylboronic acid under basic conditions. The resulting Pd/CEST-Al-MIL-53 showed a high catalytic activity compared with Pd/Al-MIL-53, due to the nanofibrous structure of silicon species-integrated CEST-Al-MIL-53. The nanofiber microstructure undergoes a remarkable transformation into intricate 3D cross-networks during catalytic reaction, which enables the leachable Pd particles to orientally redeposit and inlay into these networks as the monodisperse spheres and thereby effectively preventing Pd particles from aggregation and leaching, therefore demonstrating a high catalytic performance, long-term stability, and enhanced reusability. Obviously, the integration of CEST into MOFs can effectively prevent the leaching of active Pd species and ensure the re-deposition during catalysis. Moreover, catalytic performance strongly depended on catalyst dosage, temperature, time, solvent, and the type of the substituted group on benzene ring. This work further extends the catalytic application of hybrid metal–organic frameworks. |
| format | Article |
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| institution | OA Journals |
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| spelling | doaj-art-fd3059772fd94d23bf7c2a300fefdb882025-08-20T02:12:28ZengMDPI AGMolecules1420-30492025-02-0130365610.3390/molecules30030656Carboxyethylsilanetriol-Functionalized Al-MIL-53-Supported Palladium Catalyst for Enhancing Suzuki–Miyaura Cross-Coupling ReactionYucang Liang0Xin Ning1Yanzhong Zhen2Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, GermanyInstitut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, GermanyInstitut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, GermanyThe application of metal–organic frameworks (MOFs) has attracted increasing attention in organic synthesis. The modification of MOFs can efficiently tailor the structure and improve the property for meeting ongoing demand in various applications, such as the alteration of gas adsorption and separation, catalytic activity, stability, and sustainability or reusability. In this study, carboxyethylsilanetriol (CEST) disodium salt was used as a dual-functional ligand for modified Al-MIL-53 to fabricate CEST-functionalized Al-MIL-53 samples through a hydrothermal reaction of aluminum nitrate, terephthalic acid, and CEST disodium salt by varying the molar ratio of CEST to terephthalic acid and keeping a constant molar ratio of Al<sup>3+</sup>/-COOH of 1:1. The structure, composition, morphology, pore feature, and stability were characterized by XRD, different spectroscopies, electron microscopy, N<sub>2</sub> physisorption, and thermogravimetric analysis. With increasing CEST content, CEST-Al-MIL-53 still preserves an Al-MIL-53-like structure, but the microstructure changed compared with pure Al-MIL-53 due to the integration of CEST. Such a CEST-Al-MIL-53 was used as the support to load Pd particles and afford a catalyst Pd/CEST-Al-MIL-53 for Suzuki–Miyaura C-C cross-coupling reaction of aryl halides and phenylboronic acid under basic conditions. The resulting Pd/CEST-Al-MIL-53 showed a high catalytic activity compared with Pd/Al-MIL-53, due to the nanofibrous structure of silicon species-integrated CEST-Al-MIL-53. The nanofiber microstructure undergoes a remarkable transformation into intricate 3D cross-networks during catalytic reaction, which enables the leachable Pd particles to orientally redeposit and inlay into these networks as the monodisperse spheres and thereby effectively preventing Pd particles from aggregation and leaching, therefore demonstrating a high catalytic performance, long-term stability, and enhanced reusability. Obviously, the integration of CEST into MOFs can effectively prevent the leaching of active Pd species and ensure the re-deposition during catalysis. Moreover, catalytic performance strongly depended on catalyst dosage, temperature, time, solvent, and the type of the substituted group on benzene ring. This work further extends the catalytic application of hybrid metal–organic frameworks.https://www.mdpi.com/1420-3049/30/3/656microporous Al-metal–organic frameworkstructure functionalizationpalladium heterogeneous catalysisC-C cross-coupling reactionreusability |
| spellingShingle | Yucang Liang Xin Ning Yanzhong Zhen Carboxyethylsilanetriol-Functionalized Al-MIL-53-Supported Palladium Catalyst for Enhancing Suzuki–Miyaura Cross-Coupling Reaction Molecules microporous Al-metal–organic framework structure functionalization palladium heterogeneous catalysis C-C cross-coupling reaction reusability |
| title | Carboxyethylsilanetriol-Functionalized Al-MIL-53-Supported Palladium Catalyst for Enhancing Suzuki–Miyaura Cross-Coupling Reaction |
| title_full | Carboxyethylsilanetriol-Functionalized Al-MIL-53-Supported Palladium Catalyst for Enhancing Suzuki–Miyaura Cross-Coupling Reaction |
| title_fullStr | Carboxyethylsilanetriol-Functionalized Al-MIL-53-Supported Palladium Catalyst for Enhancing Suzuki–Miyaura Cross-Coupling Reaction |
| title_full_unstemmed | Carboxyethylsilanetriol-Functionalized Al-MIL-53-Supported Palladium Catalyst for Enhancing Suzuki–Miyaura Cross-Coupling Reaction |
| title_short | Carboxyethylsilanetriol-Functionalized Al-MIL-53-Supported Palladium Catalyst for Enhancing Suzuki–Miyaura Cross-Coupling Reaction |
| title_sort | carboxyethylsilanetriol functionalized al mil 53 supported palladium catalyst for enhancing suzuki miyaura cross coupling reaction |
| topic | microporous Al-metal–organic framework structure functionalization palladium heterogeneous catalysis C-C cross-coupling reaction reusability |
| url | https://www.mdpi.com/1420-3049/30/3/656 |
| work_keys_str_mv | AT yucangliang carboxyethylsilanetriolfunctionalizedalmil53supportedpalladiumcatalystforenhancingsuzukimiyauracrosscouplingreaction AT xinning carboxyethylsilanetriolfunctionalizedalmil53supportedpalladiumcatalystforenhancingsuzukimiyauracrosscouplingreaction AT yanzhongzhen carboxyethylsilanetriolfunctionalizedalmil53supportedpalladiumcatalystforenhancingsuzukimiyauracrosscouplingreaction |