A dye-sensitized metal-organic framework, TMU-5S, was synthesized based on introducing the laser dye Rhodamine B into the porous framework TMU-5. TMU-5S was investigated as a ratiometric fluorescent sensor for the detection of explosive nitro aromatic compounds and showed four times greater selectivity to picric acid than any state-of-the-art luminescent-based sensor. Moreover, it can selectively discriminate picric acid concentrations in the presence of other nitro aromatics and volatile organic compounds. Our findings indicate that using this sensor in two dimensions leads to a greatly reduced environmental interference response and thus creates exceptional sensitivity toward explosive molecules with a fast response.
Two new porous cobalt-based metal-organic frameworks, [Co6(oba)5(OH)2(H2O)2(DMF)4]n · 5DMF (TMU-10) and [Co3(oba)3(O) (Py)0.5] n · 4DMF · Py (TMU-12) have been synthesized by solvothermal method using a nonlinear dicarboxylate ligand. Under mild reaction conditions, these compounds exhibited good catalytic activity and reusability in oxidative desulfurization (ODS) reaction of model oil which was prepared by dissolving dibenzothiophene (DBT) in n-hexane. FT-IR and Mass analysis showed that the main product of DBT oxidation is its corresponding sulfone, which was adsorbed on the surfaces of catalysts. The activation energy was obtained as 13.4 kJ/mol.
Photo-oxidative
desulfurization (PODS) properties of MoO3–metal–organic
framework composite photocatalysts were investigated by introducing
the proper weight percent of MoO3 into a Zn(II)-based MOF,
[Zn(oba)(4-bpdh)0.5]
n
·1.5DMF
(TMU-5), for the mineralization of dibenzothiophene from model oil.
The addition of 3 wt % of MoO3 into a TMU-5 host acting
as a crystal growth inhibitor was confirmed by PXRD and BET results.
For the first time, under mild and green reaction conditions, 5 wt
% MoO3–TMU-5 composite (MT-5) exhibited good photocatalytic
activity in the model oil PODS reaction, which has no limitations
in the current oxidative desulfurization catalytic systems. Only 3%
of the total amount of MoO3 content in the MT catalyst
is leached during the reaction. In addition, the rate of PODS of MT-5
obeys a pseudo-first-order equation with an apparent rate constant
of 0.0305 min–1 and half-life t
1/2 of 22.7 min. Radical scavenger experiments and terephthalic
acid fluorescence techniques confirmed that OH
•
and O2
•–
are
the main reactive species in the dibenzothiophene photocatalytic degradation.
The synergic effects of the active surface of TMU-5 (organic linkers
as antennas) together with the active sites of MoO3 may
lead to the further enhancement of the PODS activity of the MT-5 photocatalyst.
Moreover, a possible photocatalytic desulfurization mechanism was
proposed in the presence of MoO3–TMU-5 composites.
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