Systematic Engineering of Single Substitution in Zirconium Metal-Organic Frameworks toward High-Performance Catalysis. Academic Article uri icon


  • 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 10240 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.

published proceedings

  • J Am Chem Soc

altmetric score

  • 5.25

author list (cited authors)

  • Huang, N., Yuan, S., Drake, H., Yang, X., Pang, J., Qin, J., ... Zhou, H.

citation count

  • 84

complete list of authors

  • Huang, Ning||Yuan, Shuai||Drake, Hannah||Yang, Xinyu||Pang, Jiandong||Qin, Junsheng||Li, Jialuo||Zhang, Yingmu||Wang, Qi||Jiang, Donglin||Zhou, Hong-Cai

publication date

  • December 2017