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Two novel Zn (II)-based metal–organic frameworks for rapidly selective adsorption and efficient photocatalytic degradation of hazardous aromatic dyes in aqueous phase
Two novel Zn-MOFs constructed from 5-hydroxy-2-nitroisophthalic acid (H 2 DIPA) and 5-(4-carboxy-2-nitrophenoxy)-2-nitroisophthalic acid (H 3 BPPA), namely: {[Zn 2 (DIPA) 2 (bimp) 5 ]·DMF·2H 2 O} n ( Zn-MOF 1 ), {[Zn 2 (HBPPA) 2 (bibp) 2 ]·2H 2 O} n ( Zn-MOF 2 ) (bimp = 1,4-di(1H-imidazol-1-yl)butane, bibp = 4,4′-bis(imidazolyl) biphenyl), have been synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction, elemental analysis, IR spectra, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TG). The single-crystal X-ray diffraction analysis indicates that Zn-MOF 1 exhibits an uncommon 3-nodal framework with a (4·6·8)(4·6 3 ·8 2 )(6 6 ) topology, whereas Zn-MOF 1 exhibits an uninodal 4-connected framework with a (4 4 ·6 2 ) topology. Moreover, both of the two Zn-MOFs exhibit exceptional dye adsorption capacities towards the organic dyes with high adsorption rates and excellent adsorption amounts. Particularly, Zn-MOF 1 can selectively adsorb the cationic dye malachite green (MG) whereas Zn-MOF 2 adsorb the anionic dye methyl orange (MO) when there exists another kind of dye in the system. The adsorption process can be illustrated by pseudo-second order kinetic and Langmuir isotherm, and the feasible adsorption mechanism could be the electrostatical interactions, hydrogen bonding between the MOFs and the dyes. Meanwhile, the two Zn-MOFs also show good photocatalytic degradation capabilities toward MB/MV dyes under UV irradiation, and the mechanism studies demonstrate that the main active species are ·OH radicals. Therefore, this functional MOF materials can be treated as a convenient and cost-efficient solution for the sewage handling and environmental protection.