Systematic Engineering of Single Substitution in Zirconium Metal-Organic Frameworks toward High-Performance Catalysis.
Zirconium-based metal -- organic frameworks (Zr-MOFs) exhibit great structural tunability and outstanding chemical stability, rendering them promising candidates for a wide range of practical applications. In this work, we synthesized a series of isostructural PCN- 224 analogues functionalized by et...
| Published in: | Journal of the American Chemical Society Vol. 139; no. 51; pp. 18590 - 18598 |
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| Main Authors: | , , , , , , , , , , |
| Format: | Article |
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American Chemical Society
12/27/2017
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=127082127&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 127082127 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 12/27/2017 vid: 139 iid: 51 pid: 997 pub: American Chemical Society artinfo: ui: 127082127 10.1021/jacs.7b09553 ppf: 18590 ppct: 8 formats: tig: atl: Systematic Engineering of Single Substitution in Zirconium Metal-Organic Frameworks toward High-Performance Catalysis. aug: au: Huang, Ning Yuan, Shuai Drake, Hannah Yang, Xinyu Pang, Jiandong Qin, Junsheng Li, Jialuo Zhang, Yingmu Wang, Qi Jiang, Donglin Zhou, Hong-Cai affil: Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States Field of Environment and Energy, School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi 923-1292, Japan su: Metal-organic frameworks Structural frames Oxidation Catalysis Crystallinity Porosity sug: subj: Metal-organic frameworks Structural frames Oxidation Catalysis Crystallinity Porosity ab: Zirconium-based metal -- organic frameworks (Zr-MOFs) exhibit great structural tunability and outstanding chemical stability, rendering them promising candidates for a wide range of practical applications. In this work, we synthesized a series of isostructural PCN- 224 analogues functionalized by ethyl, bromo, chloro, and fluoro groups on the porphyrin unit, which allowed us to explicitly study the effects of electron-donating and electron-withdrawing substituents on catalytic performance in MOFs. Owing to the different electronic properties of ethyl, bromo, chloro, and fluoro substitutes, the molecular-level control over the chemical environment surrounding a catalytic center could be readily achieved in our MOFs. To investigate the effects of these substitutes on catalytic activity and selectivity, the oxidation of 3-methylpentane to corresponding alcohols and ketones was utilized as a model reaction. Within these five analogues of PCN- 224, an extremely high turnover number of 7680 and turnover frequency of 10 240 h was achieved by simply altering the substitutes on porphyrin rings. Moreover, a remarkable 99% selectivity of the tertiary alcohol over the five other possible byproducts are realized. We demonstrate that this strategy can be used to efficiently screen a suitable peripheral environment around catalytic cores in MOFs for catalysis. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2017 holdings: @attributes: islocal: N |
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