Partially fluorinated MIL-101(Cr): from a miniscule structure modification to a huge chemical environment transformation inspected by ¹²⁹Xe NMR

Abstract

Partial fluorine functionalisation of MIL-101(Cr) was successfully achieved.

129Xe NMR on Porous Materials: Basic Principles and Recent Applications

“…The effect of electron‐withdrawing groups was impressively demonstrated by Lima and co‐workers exploiting the high xenon polarizability. [ 112 ] Investigating a mixed linker MIL‐101(Cr) containing terephthalic acid and only 1% tetrafluoroterephthalic acid, they found a chemical shift of xenon adsorbed in the pores shifting downfield by 38 ppm, clearly evidencing the incorporation of the fluorinated linker. In addition, the paramagnetic Cr III centers were found to induce a paramagnetic shift not only to the adsorbed Xe, but also a shift of 10–20 ppm to gas phase xenon in inter‐particle voids.…”

Hydrogen Sulfide (H2S) Removal via MOFs

“…In a recent work, Díaz-Ramírez et al [66] reported the partial functionalization of MIL−101(Cr) with fluorine using 2,3,5,6-tetrafluoro−1,4-benzenedicarboxylate (BDC-4F) providing MIL−101(Cr)-4F(1%). Cyclic voltammetry measurements showed that the acidity of the metal centers of the modified form of the MOF was improved.…”

“…Adsorption capacities of several materials towards H 2 S molecules (green: zeolites, yellow: metal oxides, red: MOFs, blue: activated carbons): (a) Zeolite 13X[64], (b) Zeolite 4A[64], (c) PEI(50)/MCM-48[116], (d) SAPO-43[117], (e) iron sponge[118], (f) Cu 0.5 Zn 0.5 /Al 2 O 3[119], (g) MIL-53(Al)-TDC[114], (h) MIL−101(Cr)[49], (i) MIL−101(Cr)-4F(1%)[66], (j) MIL-47(V)[49], (k) AC (Desorex K43-Na)[120], and (l) AC (Desorex K43-BG)[120].…”

Fluorinated MIL-101 for carbon capture utilisation and storage: uptake and diffusion studies under relevant industrial conditions

“…This material is the result of the successful partial uorination of MIL-101(Cr); which we achieved recently. 18 MIL-101(Cr)-4F(1%) showed an increased hydrophobicity and a higher selectivity towards CO 2 in anhydrous conditions when compared to its pristine form MIL-101(Cr). 18 Furthermore, MIL-101(Cr) based composites have shown outstanding catalytic activity (96.5% yield) in the conversion of terminal alkynes into propiolic acids with CO 2 , as well as in several other carbon conversion reactions.…”