Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage

Abstract

A strategy based on reticulating metal ions and organic carboxylate links into extended networks has been advanced to a point that allowed the design of porous structures in which pore size and functionality could be varied systematically. Metal-organic framework (MOF-5), a prototype of a new class of porous materials and one that is constructed from octahedral Zn-O-C clusters and benzene links, was used to demonstrate that its three-dimensional porous system can be functionalized with the organic groups -Br, -NH2, -OC3H7, -OC5H11, -C2H4, and -C4H4 and that its pore size can be expanded with the long molecular struts biphenyl, tetrahydropyrene, pyrene, and terphenyl. We synthesized an isoreticular series (one that has the same framework topology) of 16 highly crystalline materials whose open space represented up to 91.1% of the crystal volume, as well as homogeneous periodic pores that can be incrementally varied from 3.8 to 28.8 angstroms. One member of this series exhibited a high capacity for methane storage (240 cubic centimeters at standard temperature and pressure per gram at 36 atmospheres and ambient temperature), and others the lowest densities (0.41 to 0.21 gram per cubic centimeter) for a crystalline material at room temperature.

Molecular simulation of hydrogen diffusion in interpenetrated metal–organic frameworks

“…The guest-free framework structures of the IRMOFs were constructed from their corresponding experimental single-crystal X-ray diffraction (XRD) data 15 using Materials Studio Visualizer, 16 as shown in Fig. 1.…”

A Porous Metal–Organic Framework Assembled by [Cu30] Nanocages: Serving as Recyclable Catalysts for CO2 Fixation with Aziridines

“…On the other hand, porous metal–organic frameworks (MOFs) can be considered as a promising candidate for the catalytic reaction as they have designable structures and modifiable functional groups, well‐defined pores and high surface area, significant capability for CO 2 adsorption and excellent recyclable catalytic performance 7, 8, 9, 10. The utilization of MOFs as catalysts for CO 2 conversion therefore has received tremendous attention, and several MOFs have already shown high catalytic activity in CO 2 conversion with the terminal alkyne activation, the hydroboration and cycloaddition of epoxides 11.…”

Probing the Lewis Acidity and Catalytic Activity of the Metal–Organic Framework [Cu3(btc)2] (BTC=Benzene‐1,3,5‐tricarboxylate)

“…[1][2][3][4] In literature, the term MOF covers a wide assembly of hybrid compounds. [4,5] Because of the exceptionally high pore volume and surface area of MOFs, many research efforts have been spent to their application in the sorption of light gases, either as such [6][7][8][9][10] or after modification with, for example, Ba 2 + . [11] As porous materials, MOFs may also find applications in catalysis.…”

“…[12][13][14] The pores of MOFs can theoretically be tailored in a systematic way and hence optimized to a specific catalytic application. [3,9] Besides the high metal content of MOFs, one of their greatest advantages is that all active sites are identical, because of the highly crystalline nature of the material. [3,13,14] However, other elements might hamper application of MOFs in catalysis.…”