Project Info

Porous Organic Cages: Understanding Crystal Growth and Emerging Catalytic Applications for C-H Bond Activation Reactions

Moises Carreon | mcarreon@mines.edu and Brian Trewyn | btrewyn@mines.edu

The proposed work aims at developing novel catalytic systems composed of metal nanoparticle-porous organic cages for C-H bond activation reactions. Fundamentally, POCs display distinctive structural, compositional, adsorption and transport properties than those of conventional porous materials making them highly appealing for catalytic applications. We aim at elucidating the formation mechanisms of porous organic cages (POC), as well as to their structure-catalytic relationships (when metal functionalized) for C-H bond activation reactions.
With the substantial growth in the development of C-H bond activation systems and very recent advances in heterogeneous catalyst mediated reactions, we propose to use POC crystals as supports for metal nanoparticles (MNPs) that catalyze the activation of C-H bonds. Utilizing POC crystals as catalyst supports give the advantage of controlled NP size, lack of organic stabilizing ligands and interference from structural metals, and high effective metal concentration. We initially propose to incorporate Pd and AuPd alloy NPs into the cages of POC crystals via modified methods for incorporating MNPs in metal organic framework materials. Two different model C-H bond activation reactions will be testing with these materials: oxidative esterification of arenes and arylation of heterocycles. The proposed research will lead to the development of rationally designed catalysts displaying tailored structural, compositional, and morphological properties for reactions involving C-H bond activation, which is a key reaction step for a variety of reactions relevant to the petrochemical industry.

Elucidate the interdisciplinary nature of the project

This a truly interdisciplinary project in which Carreon group (Chem. Eng.) will focus on the development , and crystal growth studies of selected porous organic cages, and Trewyn group (Chemistry) will focus on the systematic evaluation of these materials for reactions involving C-H bond activation.

More Information

[1] Tozawa1,T.; Jones, J.T.A.; Swamy, S.I.; Jiang, S.; Adams, D.J.; Shakespeare, S.; Clowes, R.; Bradshaw, D.; Hasell, T.; Chong, S.Y.; Tang, C.; Thompson, S.; Parker, J.; Trewin, A.; Bacsa, J.; Slawin, A.M.Z.; Steiner, A.; Cooper. A.I. Porous Organic Cages Nature Materials 2009, 8, 973-978.
[2] J. Lucero, S.K. Elsaidi, R. Anderson, T. Wu, D. Gomez Gualdron, P.K. Thallapally, M.A. Carreon*, “Time Dependent Structural Evolution of Porous Organic Cage CC3”, Crystal Growth & Design 2018, 18, 2, 921-927.
[3] Kandel, K.; Althaus, S. M.; Peeraphatdit, C.; Kobayashi, T.; Trewyn, B. G.; Pruski, M.; Slowing, I. I., Solvent-Induced Reversal of Activities between Two Closely Related Heterogeneous Catalysts in the Aldol Reaction. ACS Catal. 2013, 3 (2), 265-271.
[4] Munz, D.; Wang, D. Y.; Moyer, M. M.; Webster-Gardiner, M. S.; Kunal, P.; Watts, D.; Trewyn, B. G.; Vedernikov, A. N.; Gunnoe, T. B., Aerobic Epoxidation of Olefin by Platinum Catalysts Supported on Mesoporous Silica. ACS Catal. 2016, 6 (7), 4584-4593.

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