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Systematic Engineering of Single Substitution in Zirconium Metal–Organic Frameworks toward High-Performance Catalysis
journal contribution
posted on 2017-11-24, 00:00 authored by Ning Huang, Shuai Yuan, Hannah Drake, Xinyu Yang, Jiandong Pang, Junsheng Qin, Jialuo Li, Yingmu Zhang, Qi Wang, Donglin Jiang, Hong-Cai ZhouZirconium-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–1 was achieved by simply altering the substitutes on porphyrin rings.
Moreover, a remarkable 99% selectivity of the tertiary alcohol over
the five other possible by-products are realized. We demonstrate that
this strategy can be used to efficiently screen a suitable peripheral
environment around catalytic cores in MOFs for catalysis.
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Keywords
turnover frequencyporphyrin unitporphyrin ringschemical stabilitySystematic Engineeringselectivityisostructural PCN -224 analogues functionalizedMOFfluoro substitutesfluoro groupschemical environment10 240model reaction3- methylpentaneturnover numberSingle Substitutionchlorobromoelectron-withdrawing substituentsmolecular-level control