Journal article
Postsynthetic Oxidation of the Coordination Site in a Heterometallic Metal-Organic Framework: Tuning Catalytic Behaviors
Chemistry of materials, Vol.32(12), pp.5192-5199
06/23/2020
DOI: 10.1021/acs.chemmater.0c01267
Abstract
Postsynthetic modification (PSM) in metal-organic frameworks (MOFs) can introduce multiple functionalities and alter the structural function for the desired application. However, the PSM of the coordination site faces the challenges of structural collapse or incompatibility between the original metal site and the newly formed coordination group. Herein, we developed a novel concept of introducing "primary" and "secondary" nodes, coexisting in a water-stable, Zr-based heterometallic MOF, [Zr-6(mu(3)-OH)(8)(OH)(8)][Cu4(I)(L-1)(4)](2) (1-SH-a, H2L1 = 6-mercaptopyridine-3-carboxylic acid). The postsynthetic oxidation at the coordination site was successfully achieved in the secondary nodes [Cu-4(1)(L-1)(4)](4-), while the robust primary nodes [Zr-6(mu(3)-OH)(8)(OH)(8)](8+) stabilized the whole framework to form [Zr-6(mu(3)-(OH)(8)(OH)(8)][((Cu0.04Cu0.56II)-Cu-I(OH)(0.56))(4)(L-2)(4)](2) (1-SO3H, H2L2 = 6-sulfonicotinic acid). Attempts to directly synthesize 1-SO3H through the reactions of Zr(IV), Cu(II), and H2L2 failed. Furthermore, the PSM of 1-SH-a to form 1-SO3H was utilized to tune the catalytic behaviors toward the styrene oxide ring-opening reaction to give an improved regioselectivity of the primary alcohol (A) of similar to 99% compared with that of 1-SH-a (similar to 71%).
Details
- Title: Subtitle
- Postsynthetic Oxidation of the Coordination Site in a Heterometallic Metal-Organic Framework: Tuning Catalytic Behaviors
- Creators
- Yi Han - Qingdao University of Science and TechnologyMichael A. Sinnwell - Pacific Northwest National LaboratoryRobert G. Surbella - Pacific Northwest National LaboratoryWenjuan Xue - Tiangong UniversityHongliang Huang - Tiangong UniversityJian Zheng - Pacific Northwest National LaboratoryBo Peng - Pacific Northwest National LaboratoryGaurav Verma - University of South FloridaYang Yang - Pacific Northwest National LaboratoryLili Liu - Pacific Northwest National LaboratoryShengqian Ma - University of South FloridaPraveen K. Thallapally - Pacific Northwest National Laboratory
- Resource Type
- Journal article
- Publication Details
- Chemistry of materials, Vol.32(12), pp.5192-5199
- DOI
- 10.1021/acs.chemmater.0c01267
- ISSN
- 0897-4756
- eISSN
- 1520-5002
- Publisher
- Amer Chemical Soc
- Number of pages
- 8
- Grant note
- KC020105-FWP12152 / U.S. DOE, Office of Science, Basic Energy Sciences, Division of Materials Sciences and Engineering; United States Department of Energy (DOE) DE-AC05-76RL01830 / U.S. Memorial Institute ZR2016BQ34 / NSF of Shandong Province 18-2-2-32-jch / Scientific and Technical Development Project of Qingdao 21601102 / NSF of China; National Natural Science Foundation of China (NSFC) Linus Pauling Distinguished Postdoctoral Fellowship program at PNNL 20170035 / International Postdoctoral Exchange Fellowship Program
- Language
- English
- Date published
- 06/23/2020
- Academic Unit
- Chemistry
- Record Identifier
- 9984936617702771
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