Adsorption of 1,2-dichlorobenzene and 1,2,4-trichlorobenzene in nano- and microsized crystals of MIL-101(Cr): static and dynamic gravimetric studies.

This work aims to highlight the promising adsorption capacity and kinetic of (poly)chlorobenzene pollutants in the hybrid MIL-101(Cr) type material for technological uses in industrial waste exhaust decontamination. The influence of the MIL-101(Cr) crystal size (nano- and microcrystals) on the adsorption behavior was studied in static and dynamic modes. For this purpose, crystals of MIL-101(Cr) in nano- and micrometric sizes were synthesized and fully characterized. Their sorption properties regarding 1,2-dichlorobenzene were examined using gravimetric method in dynamic (p/p° = 0.5) and static (p/p° = 1) modes at room temperature. 1,2,4-trichlorobenzene adsorption was only performed under static mode because of its too low vapor pressure. 1,2-dichlorobenzene and 1,2,4-trichlorobenzene were used to mimic 2,3-dichlorodibenzo-p-dioxin and 1,2,3,4-tetrachlorodibenzo-p-dioxin, respectively, and more largely dioxin compounds. Adsorptions of these probes were successfully carried out in nano- and microcrystals of MIL-101(Cr). Indeed, in static mode (p/p° = 1) and at room temperature, nanocrystals adsorb 2266 molecules of 1,2-dichlorobenzene and 2093 molecules of 1,2,4-trichlorobenzene per unit cell, whereas microcrystals adsorb 1871 molecules of 1,2-dichlorobenzene and 1631 molecules of 1,2,4-trichlorobenzene per unit cell. In dynamic mode, the 1,2-dichlorobenzene adsorbed amounts are substantially similar to those obtained in static mode. However, the adsorption kinetics are different because of a different scheme of diffusivity of the adsorbate between the two modes. To the best of our knowledge, these adsorption capacities of MIL-101(Cr) as adsorbent for polychlorobenzenes trapping have never been referenced. MIL-101(Cr) appears as a promising material for technological uses in industrial waste exhaust decontamination.