Design of amino-functionalized chelated macroporous copolymer [poly(GMA-EDGMA)] for the sorption of Cu (II) ions

Abstract

Polymer-based, highly porous nanocomposites with functionalized ligands attached to the core structure are extremely efficient in the detection, removal and recovery of metals through the process of sorption. Quantumchemical models could be helpful for sorption process analyses. The sorption of Cu(II) ions by amino-functionalized chelating macroporous copolymers poly(GMA-co-EGDMA)-amine and sorption selectivity of the subject copolymers, ethylenediamine (en), diethylenetriamine (dien) and triethylenetetramine (trien), were successfully modelled by quantum chemical calculations. Considering the crystal structures from CSD and experimental conditions during the formation of metal complexes, the most frequent mononuclear complexes are those with the tetradentate teta ligand, while binuclear complexes are formed when the metal ion is in large excess. Although the en-copolymer was the most effective functionalized one, higher maximum sorption capacities (Qmax) were observed for the dien- and trien-copolymers, due to their abilities to form binuclear complexes. The enthalpy term has the greatest contribution to the total Gibbs energy change of reaction for the formation of mononuclear Cu(II) complexes (?Gaq), while the solvation energy of the reaction has the greatest contribution in the formation of binuclear complexes. The results of the study indicate that small amines with the ability to form binuclear complex are the best choice for functionalization of the considered copolymer. [Projects of the Serbian Ministry of Education, Science and Technological Development, Grant no. OI 172043, Grant no. 172023 and Grant no. III 43009]

Speciation of Hexavalent Chromium in Aqueous Solutions Using a Magnetic Silica-Coated Amino-Modified Glycidyl Methacrylate Polymer Nanocomposite

“…Our previous works demonstrated that calculating the coordination bond energy for the chemisorption of metal ions on the polymer gives excellent agreement with the experimentally determined maximum sorption capacities [ 27 , 67 ]. Quantum chemical modeling of physisorption and calculation of the energy of non-covalent binding proved to help explain the binding mechanism of oxyanions to the polymer and the affinity of individual oxyanions for the polymer [ 21 ].…”

“…Cr(III) oxyanion, which is less toxic than Cr(VI), binds to N atoms directly by forming covalent bonds [ 66 ]. The sorption of Cu(II), Co(II), Cd(II), and Ni(II) ions by amino-functionalized chelating macroporous copolymers poly(GMA- co -EGDMA)-amine and sorption selectivity of the subject copolymers were successfully quantified experimentally and modeled by quantum chemical calculations [ 27 , 31 , 67 ]. According to these results, coordination of the diethylenetriamine group from Fe 3 O 4 @APTMS/PGME-deta to the Cr(III) ion can be expected.…”

Fast Gold Recovery from Aqueous Solutions and Assessment of Antimicrobial Activities of Novel Gold Composite

“…The presence of porous channels, their large surface area, and their unique chemical characteristics have led to the numerous potential applications of these porous materials [11][12][13][14][15][16][17]. Among them, the chelating polymer ligands based on glycidyl methacrylate (GMA) are very attractive, due to the presence of oxirane rings that can easily be transformed into various functional groups [18]. These materials have found applications in very diverse areas such as drug delivery [19], support for enzymes [20], and wastewater treatment [21], as well as catalysis [22].…”

Recovery of Vanadium (V) Oxyanions by a Magnetic Macroporous Copolymer Nanocomposite Sorbent

“…Several studies showed that amino-functionalized GM-based copolymers possess a significant affinity for the sorption metal ions [7,8]. Moreover, these polymers are characterized by thermal and chemical stability [9,10].…”