Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 51, Pages 18590-18597Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b09553
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Funding
- Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0001015]
- Hydrogen and Fuel Cell Program [DE-EE-0007049]
- U.S. Department of Energy Office of Fossil Energy, National Energy Technology Laboratory [DE-FE0026472]
- Qatar National Research Fund [NPRP9-377-1-080]
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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(-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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