Systematic Engineering of Single Substitution in Zirconium Metal-Organic Frameworks toward High-Performance Catalysis.
Ning HuangShuai YuanHannah DrakeXinyu YangJiandong PangJunsheng QinJialuo LiYingmu ZhangQi WangDonglin JiangHong-Cai ZhouPublished in: Journal of the American Chemical Society (2017)
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.
Keyphrases
- metal organic framework
- positron emission tomography
- electron transfer
- bone mineral density
- molecular docking
- ionic liquid
- crystal structure
- visible light
- computed tomography
- structure activity relationship
- solar cells
- electron microscopy
- single molecule
- postmenopausal women
- structural basis
- molecularly imprinted
- pet ct
- molecular dynamics simulations