Journal
JOURNAL OF MATERIALS CHEMISTRY A
Volume 7, Issue 25, Pages 15101-15112Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9ta02237f
Keywords
-
Funding
- PAPIIT UNAM Mexico [206218, IN101517]
- CONACyT [236879, 270279, 276862, 289042, 1789, 220625]
- CONTex [2018-36B]
Ask authors/readers for more resources
The partial functionalisation of MIL-101(Cr) with fluorine was successfully achieved, for the first time, with 2,3,5,6-tetrafluoro-1,4-benzenedicarboxylate (BDC-4F) affording MIL-101(Cr)-4F(1%). As a result of the functionalisation the acidity of the metal centres for MIL-101(Cr)-4F(1%) was enhanced, which was measured by cyclic voltammetry. The resulting adsorption properties of the new material were explored and compared to those of MIL-101(Cr). H2O sorption experiments demonstrated an augmented hydrophobicity of the material due to the incorporation of fluorine atoms. CO2 adsorption experiments exhibited an augmented CO2 interaction energy (DH) for MIL-101(Cr)-4F(1%). The diffusion time constant (D-M=r(c)(2)) for CO2 showed a higher CO2 mobility inside the pores of MIL-101(Cr) than in MIL-101(Cr)-4F(1%), which was also associated with a higher selectivity (a) of MIL-101(Cr)-4F(1%) towards CO2. O-2 sorption isotherms of MIL-101(Cr)-4F(1%), at a high pressure (up to 90 bar), demonstrated O-2 uptakes among the highest values reported for a MOF material. H-2 adsorption isotherms exhibited, at low pressures, higher H-2 uptakes for the fluorine functionalised material. This was attributed to dipolar interactions of H-2 molecules with the fluorine atoms and corroborated by the calculation of Delta H for H-2. Xe-129 NMR experiments were used to investigate the atypical pore-surface electron density of MIL-101(Cr)-4F(1%), demonstrating a huge effect of the polarising power of the fluorine atoms on the highly polarisable Xe atoms. Finally, the capture of I-2 and H2S on MIL-101(Cr)-4F(1%) showed considerably higher values in comparison to MIL-101(Cr). This was attributed to the high dipolarity and polarisability of the fluorinated pores.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available