Phosphonates Meet Metal−Organic Frameworks: Towards CO₂ Adsorption

Abstract

Here we report a new highly microporous zirconium phosphonate material synthesized under solvothemal conditions. The specific Brunauer-Emmett-Teller (BET) surface area of the "unconventional metalÀorganic framework" (UMOF) is measured to be~900 m 2 /g, after following an appropriate activation protocol. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) shows that the material bears a free ÀOH functionality on the phosphonate linker that may interact with CO 2 . CO 2 adsorption isotherms were collected and a measured heat of adsorption of 31 kJ/ mol was obtained. In addition, adsorption isotherms of CO 2 , N 2 , and CH 4 at 298 K combined with Ideal Adsorbed Solution Theory (IAST) show that the material can be expected to display high selectivities for uptake of CO 2 versus N 2 or CH 4 .Keywords: metal-organic frameworks · porous phosphonates · carbon dioxide capture · zirconium-based MOFs Experimental Section MaterialsAcetone (Macron, 98 %), N,N-dimethylformamide (DMF), hexanes (Macron, 99.8 %), dichloromethane (Macron, 99.0 %), deuterated dimethyl sulfoxide (d 6 -DMSO) (Cambridge Isotopes, 99 %), and deuterated sulfuric acid (Cambridge Isotopes, 96-98 % solution in D 2 O) were used as received without further purification. 1,3,5-tris(4-bromophenyl)benzene, triethyl[a] C.

Probing Isoreticular Expansions in Phosphonate MOFs and their Applications

“…The systematic synthesis of microporous metal organic frameworks (MOFs) has spawned wide interest in early 2000s for their gas storage properties and sequestration of greenhouse gases , . As MOF research kept growing, distinct applications in diverse fields, such as catalysis, gas adsorption, drug delivery, food transportation, solar cells, conductivity, proton conductivity, biomimetic chemistry, magnetism etc., have emerged . The limitless linker geometries, possibility of attaching reactive organic functional groups around linker scaffolds have created new chemistry namely post synthetic modifications to further optimize the MOF properties .…”

Nanoporous Metal Phosphonate Hybrid Materials as a Novel Platform for Emerging Applications: A Critical Review

“…Gas adsorption is closely related to various aspects of human society, [98][99][100][101] such as the capture of greenhouse gas, the storage of clean fuel gases, and the trapping of toxic gases. Significantly, crystalline porous materials (especially porous metal phosphonates) are propelling the rapid development of gas adsorption due to their unprecedented surface areas, high porosities, and tunable porous structure.…”