Exploitation of Intrinsic Confinement Effects of MOFs in Catalysis

Abstract

In catalysis research the design of bio‐inspired,'artificial enzymes‘ is a field of huge interest. These catalysts are distinguished by their high catalytic efficiency resulting from a close proximity of several active sites and secondary substrate‐catalyst interactions enabled by functional groups in the catalytic pocket. A class of materials which meets these requirements are metal‐organic frameworks (MOFs). Here, the pores confine a reaction environment where several functionalities can be incorporated and spatially positioned in a tunable fashion. Recently, a number of reports revealed the importance of such confinement effects for the control of catalytic activity and selectivity by exploiting the intrinsic properties like pore size and neighboring group effects and the alignment and distance of different active sites within one MOF pore. Thus, this concept aims to accentuate the potential of the exploitation of those effects in MOFs for the design of sophisticated catalysts.

MOF-enabled confinement and related effects for chemical catalyst presentation and utilization

“…Finally, in selecting papers for highlighting we have necessarily omitted other clearly relevant papers, including papers by groups led by Rahul Banerjee, 425 Silvia Bordiga, 426 Avelino Corma, [427][428][429][430][431] Deanna M. D'Alessandro, 432 Zhengping Dong, 433 Mohamed Eddaoudi, 434 Roland A. Fischer, 277,435,436 Jorge Gascon, [437][438][439] Stefan Kaskel, 440,441 Hiroshi Kitagawa, 442,443 Susumu Kitagawa, 444 Jing Li, 445 Yangyang Liu, 446,447 Tian-fu Liu, 448 Jeffery Long, 449 Connie C. Lu, 450 Amanda J. Morris, 451 Ali Morsali, 254,452,453 Unni Olsbye, 454 W. L. Queen, 455 Matthew Rosseinsky, 456 Natalia B. Shustova, 457 Berend Smit, 458,459 Norbert Stock, [460][461][462][463] Shane G. Telfer, [464][465][466] Fernando Uribe-Romo, 467 Jenny G. Vitillo,…”

Which factors govern the adsorption of peptides to Zr(iv)-based metal–organic frameworks?

“…30 MOFs' emerging catalytic applications towards biomolecules are also dependent of substrate-solid surface interaction, and deeper molecular insights into the adsorption phenomena are essential for the development of their catalytic reactivity. [31][32][33][34] In this area, we have been particularly interested in the development of Zr 6 O 8 -based MOFs (Zr-MOFs) as nanozymes for the formation 35 and cleavage [36][37][38] of peptide bonds, including the selective hydrolysis of proteins which generates fragments in the optimal range for the emerging area of middle-down proteomics. [39][40][41] However, the use of MOFs as a new generation of nanozymes has been hampered by the strong MOF-protein (fragments) interactions, which precludes further analysis of the protein digest.…”

Highly effective CS2 conversion with aziridines catalyzed by novel [Dy24] nano-cages in MOFs under mild conditions

“…Metal–organic frameworks (MOFs) are emerging as prospective candidates for use as catalysts because their porous structures can serve as nanoreactors to promote the catalytic reaction by the confinement effect. 10–14 In addition, using metal clusters as nodes in the MOFs can further improve their stability and regenerability, 15–17 and furthermore, using the cluster-based MOFs as catalysts can efficiently convert CO 2 into various organic intermediates, such as cyclic carbonates, 18–23 propiolic acid, 24 oxazolidinone, 25–27 and so on. 28–32 However, no MOFs have been employed for such a reaction so far, and therefore it is a challenge to explore the use of novel MOFs as catalysts for CS 2 conversion with aziridines.…”