RESUMEN
Desulfurization of oragnosulfur-containing fuels signify a great importance in improving the quality of fuel and is also beneficial to the environment. In this work, we report two new composites, namely, MOF-5@γ-Al2O3 and IRMOF-3@γ-Al2O3, synthesized by loading iso-structural MOF-5 and amino bearing IRMOR-3 onto the γ-Al2O3 beads (the loading amount of MOF-5 and IRMOF-3 are 13.4 wt% and 16.3 wt%, respectively). The composites are fully characterized by IR spectroscopy, XRD, SEM, BET and XRF. These iso-structural MOFs and their composites exhibit substantially high adsorptive desulfurization capacities for benzothiophene (BT), 3-methylthiophene (3-MT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT). The adsorption capacities of amino bearing IR-MOF-3 and IRMOF-3@γ-Al2O3 are significantly greater than those of MOF-5 and MOF-5@γ-Al2O3, e.g., the adsorption capacities for DBT of IRMOF-3@γ-Al2O3, IRMOF-3, MOF-5@γ-Al2O3 and MOF-5 are 54.9, 45.1, 31.4 and 24.1 mg S g-1 MOFs, respectively, under optimal conditions (time 60 min, temperature 30 °C, MOFs@γ-Al2O3/Moil = 1/40). The adsorption results revealed the predominant role of hydrogen bonding between the Lewis basic S atoms of the organo sulfurs and -NH2 groups in IR-MOF-3 and also the π-π interactions that works well in MOF-5. The enhancement in the desulfurization capability of MOFs@γ-Al2O3versus the corresponding pristine MOFs shall be attributed to the advantage of the confinement effect of the γ-Al2O3 pores that results in larger specific surface area, much more exposed active sites, and shorter diffusion channels of the MOFs. The kinetics and thermodynamic parameters indicate that the adsorption process is spontaneous and endothermic, and the increase in entropy is the primary driving force for the desulfurization. In addition, it is found that the composites possess good reusability and can be regenerated by simple washing due to enhanced mechanical strength.
RESUMEN
Composite films derived from the water-soluble Keplerate-type polyoxometalate (NH4)42[Mo132O372(CH3COO)30(H2O)72]·ca. 300H2O·ca. 10CH3COONH4 (denoted (NH4)42{Mo132}) and chloroform-soluble tetraphenylporphyrin perchlorate [H2TPP](ClO4)2 are successfully fabricated by a layer-by-layer self-assembly method and characterized by UV-vis spectroscopy and X-ray photoelectron spectroscopy (XPS). The structure of the {Mo132} and [H2TPP](2+) in the films remain intact in light of the results of UV-vis spectroscopy and XPS. UV-vis spectra measurements reveal that the amounts of deposition of {Mo132} and [H2TPP](2+) remain constant in every adsorption cycle in the composite films assembly process. Nonlinear optical properties of the composite films have been investigated by using the Z-scan technique at a wavelength of 532 nm and pulse width of 7 ns. The results show that the composite films have notable nonlinear saturated absorption and self-defocusing effects. The combination of {Mo132} with [H2TPP](2+) can result in composite films with remarkably enhanced optical nonlinearities. The interfacial charge transfer induced by laser from porphyrin to POM in the films is thought to play a key role in the enhancement of NLO response. The third-order NLO susceptibility χ((3)) of the composite films increases with the increase of film thickness.