Unveiling the Effects of Linker Substitution in Suzuki Coupling with Palladium Nanoparticles in Metal–Organic Frameworks [Unveiling the Effects of Linker Substitution in Suzuki Coupling Reaction with Palladium Nanoparticles in Metal–Organic Frameworks]
Abstract
The establishment of structure–property relationships in heterogeneous catalysis is of prime importance but remains a formidable challenge. Metal–organic frameworks (MOFs) featuring excellent chemical tunability are emerging as an auspicious platform for the atomic-level control of heterogeneous catalysis. Herein, we encapsulate palladium nanoparticles (Pd NPs) in a series of isoreticular mixed-linker MOFs, and the obtained MOF-Pd NPs catalysts were used to unveil the electronic and steric effects of linker substitution on the activity of these catalysts in the Suzuki–Miyaura cross-coupling reactions. Significantly, m-6,6'-Me2bpy-MOF-Pd exhibits a remarkable enhancement in the activity compared to non-functionalized m-bpy-MOF-Pd and m-4,4'-Me2bpy-MOF-Pd. This study unambiguously demonstrates that the stereoelectronic properties of linker units are crucial to the catalytic activity of nanoparticles encapsulated in MOFs. More interestingly, the trend of activity change is consistent with our previous work on catalytic sites generated in situ from Pd(II) coordinated in MOFs bearing the same functional groups, which suggests that both MOF-Pd NPs and MOF-Pd(II) catalysts generate similar active centers during Suzuki–Miyaura coupling reactions. Lastly, this work paves a new avenue to the fabrication of advanced and tunable MOF-based catalysts through rational linker engineering.
- Authors:
-
- Ames Lab. and Iowa State Univ., Ames, IA (United States)
- Iowa State Univ., Ames, IA (United States)
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1434313
- Report Number(s):
- IS-J-9636
Journal ID: ISSN 1011-372X; PII: 2289
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Catalysis Letters
- Additional Journal Information:
- Journal Volume: 148; Journal Issue: 3; Journal ID: ISSN 1011-372X
- Publisher:
- Springer
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Isoreticular metal–organic frameworks; Heterogeneous catalysis; Suzuki–Miyaura cross-coupling; Structure–activity relationship
Citation Formats
Li, Xinle, Zhang, Biying, Van Zeeland, Ryan, Tang, Linlin, Pei, Yuchen, Qi, Zhiyuan, Goh, Tian Wei, Stanley, Levi M., and Huang, Wenyu. Unveiling the Effects of Linker Substitution in Suzuki Coupling with Palladium Nanoparticles in Metal–Organic Frameworks [Unveiling the Effects of Linker Substitution in Suzuki Coupling Reaction with Palladium Nanoparticles in Metal–Organic Frameworks]. United States: N. p., 2018.
Web. doi:10.1007/s10562-017-2289-9.
Li, Xinle, Zhang, Biying, Van Zeeland, Ryan, Tang, Linlin, Pei, Yuchen, Qi, Zhiyuan, Goh, Tian Wei, Stanley, Levi M., & Huang, Wenyu. Unveiling the Effects of Linker Substitution in Suzuki Coupling with Palladium Nanoparticles in Metal–Organic Frameworks [Unveiling the Effects of Linker Substitution in Suzuki Coupling Reaction with Palladium Nanoparticles in Metal–Organic Frameworks]. United States. https://doi.org/10.1007/s10562-017-2289-9
Li, Xinle, Zhang, Biying, Van Zeeland, Ryan, Tang, Linlin, Pei, Yuchen, Qi, Zhiyuan, Goh, Tian Wei, Stanley, Levi M., and Huang, Wenyu. Thu .
"Unveiling the Effects of Linker Substitution in Suzuki Coupling with Palladium Nanoparticles in Metal–Organic Frameworks [Unveiling the Effects of Linker Substitution in Suzuki Coupling Reaction with Palladium Nanoparticles in Metal–Organic Frameworks]". United States. https://doi.org/10.1007/s10562-017-2289-9. https://www.osti.gov/servlets/purl/1434313.
@article{osti_1434313,
title = {Unveiling the Effects of Linker Substitution in Suzuki Coupling with Palladium Nanoparticles in Metal–Organic Frameworks [Unveiling the Effects of Linker Substitution in Suzuki Coupling Reaction with Palladium Nanoparticles in Metal–Organic Frameworks]},
author = {Li, Xinle and Zhang, Biying and Van Zeeland, Ryan and Tang, Linlin and Pei, Yuchen and Qi, Zhiyuan and Goh, Tian Wei and Stanley, Levi M. and Huang, Wenyu},
abstractNote = {The establishment of structure–property relationships in heterogeneous catalysis is of prime importance but remains a formidable challenge. Metal–organic frameworks (MOFs) featuring excellent chemical tunability are emerging as an auspicious platform for the atomic-level control of heterogeneous catalysis. Herein, we encapsulate palladium nanoparticles (Pd NPs) in a series of isoreticular mixed-linker MOFs, and the obtained MOF-Pd NPs catalysts were used to unveil the electronic and steric effects of linker substitution on the activity of these catalysts in the Suzuki–Miyaura cross-coupling reactions. Significantly, m-6,6'-Me2bpy-MOF-Pd exhibits a remarkable enhancement in the activity compared to non-functionalized m-bpy-MOF-Pd and m-4,4'-Me2bpy-MOF-Pd. This study unambiguously demonstrates that the stereoelectronic properties of linker units are crucial to the catalytic activity of nanoparticles encapsulated in MOFs. More interestingly, the trend of activity change is consistent with our previous work on catalytic sites generated in situ from Pd(II) coordinated in MOFs bearing the same functional groups, which suggests that both MOF-Pd NPs and MOF-Pd(II) catalysts generate similar active centers during Suzuki–Miyaura coupling reactions. Lastly, this work paves a new avenue to the fabrication of advanced and tunable MOF-based catalysts through rational linker engineering.},
doi = {10.1007/s10562-017-2289-9},
journal = {Catalysis Letters},
number = 3,
volume = 148,
place = {United States},
year = {2018},
month = {1}
}
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Figures / Tables:
Scheme 1: Schematic representation of the synthesis of Pd NPs encapsulated in isoreticular mbpy- MOFs. Green sphere and octahedra represent Zr clusters, while orange spheres represent Pd NPs.
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