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

Chinyere A Anyama; Benedict I Ita; Ayi A Ayi; Hitler Louis; Emmanuel E D Okon; Joseph O Ogar; Charles O Oseghale

doi:10.1021/acsomega.1c04037

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

ACS Omega. 2021 Oct 21;6(43):28967-28982. doi: 10.1021/acsomega.1c04037. eCollection 2021 Nov 2.

Authors

Chinyere A Anyama¹, Benedict I Ita², Ayi A Ayi¹, Hitler Louis³, Emmanuel E D Okon¹, Joseph O Ogar^{1

4}, Charles O Oseghale⁵

Affiliations

¹ Inorganic Materials Research Laboratory, Department of Pure and Applied Chemistry, University of Calabar, 540242 Calabar, Nigeria.
² Department of Pure and Applied Chemistry, University of Calabar, 540242 Calabar, Nigeria.
³ Computational and Bio-Simulation Research Group, University of Calabar, 540242 Calabar, Nigeria.
⁴ School of Chemistry, Nottingham University, NG7 2RD Nottingham, U.K.
⁵ Department of Chemistry, Federal University of Lafia, 950101 Lafia, Nigeria.

Abstract

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 (S _BET) 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 S _BET 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 %.