2 research outputs found
Observation of Olefin/Paraffin Selectivity in Azo Compound and Its Application into a Metal–Organic Framework
Olefin/paraffin separation
is an important and challenging issue
because the two molecules have similar physicochemical properties.
Although a couple of olefin adsorbents have been developed by introducing
inorganic nanoparticles into metal–organic frameworks (MOFs),
there has been no study on the development of an olefin adsorbent
by introducing a certain organic functional group into a MOF. In this
study, we posited that azo compounds could offer olefin/paraffin selectivity.
We have revealed using first-principles calculations that the simplest
aromatic azo compound (azobenzene, Azob) has an unusual propylene/propane
selectivity due to special electrostatic interactions between Azob
and propylene molecules. On the basis of this interesting discovery,
we have synthesized a novel propylene adsorbent, MIL-101Â(Cr)_DAA,
by grafting 4,4′-diaminoazobenzene (DAA) into open metal sites
in a mesoporous MIL-101Â(Cr). Remarkably, MIL-101Â(Cr)_DAA exhibited
enhanced propylene/propane selectivity as well as considerably higher
propylene heat of adsorption compared to pristine MIL-101Â(Cr) while
maintaining the high working capacity of MIL-101Â(Cr). This clearly
indicates that azo compounds when introduced into MOFs can provide
propylene selectivity. Moreover, MIL-101Â(Cr)_DAA showed good C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub> separation and easy
regeneration performances from packed-bed breakthrough experiments
and retained its propylene adsorption capacity even after exposure
to air for 12 h. As far as we know, this is the first study that improves
the olefin selectivity of MOF by postsynthetically introducing an
organic functional group
Synthesis of a Zr-Based Metal–Organic Framework with Spirobifluorenetetrabenzoic Acid for the Effective Removal of Nerve Agent Simulants
A new
microporous ZrÂ(IV)-based metal–organic framework (MOF) containing
4,4′,4″,4‴-(9,9′-spirobiÂ[fluorene]-2,2′,7,7′-tetrayl)Âtetrabenzoic
acid (Spirof-MOF) was synthesized, characterized, and size-controlled
for the adsorption and decomposition of a nerve agent simulant, dimethyl
4-nitrophenylphosphate (DMNP). Spirof-MOF showed a hydrolysis half-life
(<i>t</i><sub>1/2</sub>) of 7.5 min to DMNP, which was confirmed
by using in situ <sup>31</sup>P NMR spectroscopy. Additionally, size-controlled
Spirof-MOFb (∼1 μm) exhibited a half-life of 1.8 min
and 99% removal within 18 min for DMNP. The results show that Spirof-MOF
is a new active material in removing nerve agent simulants by adsorption
and hydrolytic decomposition