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Experimental and Density Functional Theory Studies on a Zinc(II) Coordination Polymer Constructed with 1,3,5-Benzenetricarboxylic Acid and the Derived Nanocomposites from Activated Carbon
journal contributionposted on 2021-10-21, 13:44 authored by Chinyere A. Anyama, Benedict I. Ita, Ayi A. Ayi, Hitler Louis, Emmanuel E. D. Okon, Joseph O. Ogar, Charles O. Oseghale
A coordination polymer with the composition C12H20O16Zn2 (ZnBTC) (BTC = benzene-1,3,5-tricarboxylate) was synthesized under hydrothermal conditions at 120 °C, and its crystal structure was determined using single-crystal X-ray crystallography. First-principles electronic structure investigation of the compound was carried out using the density functional theory computational approach. The highest occupied molecular orbital, the lowest unoccupied molecular orbital, the energy gap, and the global reactivity descriptors of ZnBTC were investigated in both the gas phase and the solvent phase using the implicit solvation model, while the donor–acceptor interactions were studied using natural bond orbital analyses. The results revealed that ZnBTC is more stable but less reactive in solvent medium. The larger stabilization energy E(2) indicates a greater interaction of ZnBTC in the solvent than in the gas phase. Orange peel activated carbon and banana peel activated carbon chemically treated with ZnCl2 and/or KOH were used to modify the synthesis of ZnBTC to obtain nanocomposites. ZnBTC and the nanocomposites were characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis, and Fourier transform infrared. The specific surface area (SBET) and the average pore diameter of the materials were determined by nitrogen sorption measurements using the Brunauer–Emmett–Teller (BET) method, while scanning electron microscopy and transmission electron microscopy were used to observe their morphology and particle size, respectively. The PXRD of all the activated carbon materials exhibited peaks at 2θ values of 12.7 and 13.9° corresponding to a d-spacing of 6.94 and 6.32 Å, respectively. The N2 adsorption–desorption isotherm of the materials are of type II with nanocomposites showing enhanced SBET compared to the pristine ZnBTC. The results also revealed that activated carbons from the banana peel and the derived nanocomposites exhibited better porous structure parameters than those obtained from orange peel. The degradation efficiency of methyl orange in aqueous solutions using ZnBTC as a photocatalyst was found to be 52 %, while that of the nanocomposites were enhanced up to 79 %.
transmission electron microscopyscanning electron microscopyimplicit solvation modelglobal reactivity descriptorsfourier transform infraredaverage pore diameter9 ° correspondinglarger stabilization energy120 ° c20 sub2 sub16 subresults also revealedcoordination polymer constructeddetermined using singlebet sub12 subnanocomposites showing enhancedsolvent phase usingresults revealedcoordination polymere >< subgas phaseenergy gapcomposition csolvent mediumray diffractionray crystallographypowder xparticle sizeorange peelobtain nanocompositesmethyl orangeless reactivehydrothermal conditionsgreater interactionderived nanocompositesdegradation efficiencycrystal xcrystal structurebenzenetricarboxylic acidbanana peelactivated carbonsactivated carbon>- spacing79 %.52 %,32 å2θ values