School of Chemistry and Materials Science, Ludong University, Yantai, 264025, China.
Environ Sci Pollut Res Int. 2019 Jun;26(18):18098-18112. doi: 10.1007/s11356-019-05220-z. Epub 2019 Apr 29.
Water pollution caused by Cr(III) is a serious environmental problem which bring adverse effect to environmental protection and public safety. Efficient removal of Cr(III) from aqueous solution is important for the remediation of Cr(III) pollution. Herein, a series of silica-gel/polyamidoamine (PAMAM) dendrimer hybrid materials (SG-G0~SG-G4.0) were used for the removal of Cr(III) from aqueous solution. The factors that affect the adsorption were extensively studied and the adsorption mechanism was demonstrated based on the experimental results and density functional theory (DFT) calculation. Result demonstrates the adsorption capacity of ester-terminated silica-gel/PAMAM dendrimers follow the order of SG-G2.5 > SG-G3.5 > SG-G1.5 > SG-G0.5, while that of amino-terminated ones decrease in the order of SG-G2.0 > SG-G4.0 > SG-G3.0 > SG-G1.0 > SG-G0. The highest adsorption is achieved at pH 4.0 for both ester- and amino-terminated materials. Adsorption kinetic indicates the adsorption equilibrium can be reached at about 240 and 180 min for amino- and ester-terminated hybrids, respectively. Adsorption kinetic can be well fitted by pseudo-second-order kinetic model with film diffusion process as the rate-limiting step. Adsorption isotherm follows Langmuir model with monolayer adsorption behavior. Fourier transform infrared spectra (FTIR) indicate the adsorption of Cr(III) by PAMAM dendrimer mainly involve the participation of N-H and C=O groups. DFT calculation demonstrates the uptake of Cr(III) by ester-terminated adsorbents mainly involves carbonyl oxygen and secondary amine nitrogen atoms to form tetra-coordinated chelate, while that of amino-terminated one tends to form hexa-coordinated chelates by carbonyl oxygen, primary and secondary amine nitrogen atoms.
三价铬造成的水污染是一个严重的环境问题,对环境保护和公共安全造成了不利影响。高效去除水溶液中的三价铬对于修复三价铬污染至关重要。在此,我们使用一系列硅胶/聚酰胺胺(PAMAM)树枝状大分子杂化材料(SG-G0~SG-G4.0)来去除水溶液中的三价铬。广泛研究了影响吸附的因素,并根据实验结果和密度泛函理论(DFT)计算证明了吸附机理。结果表明,酯基封端的硅胶/PAMAM 树枝状大分子的吸附容量顺序为 SG-G2.5>SG-G3.5>SG-G1.5>SG-G0.5,而氨基封端的则顺序为 SG-G2.0>SG-G4.0>SG-G3.0>SG-G1.0>SG-G0.0。对于酯基和氨基封端的材料,吸附的最佳 pH 值均为 4.0。吸附动力学表明,氨基和酯基封端的杂化材料的吸附平衡分别在约 240 和 180 min 时达到。吸附动力学可以很好地拟合准二级动力学模型,其中膜扩散过程为限速步骤。吸附等温线遵循 Langmuir 模型,表现出单层吸附行为。傅里叶变换红外光谱(FTIR)表明,PAMAM 树枝状大分子对 Cr(III)的吸附主要涉及 N-H 和 C=O 基团的参与。DFT 计算表明,酯基封端吸附剂对 Cr(III)的摄取主要涉及羰基氧和仲胺氮原子形成四配位螯合物,而氨基封端的则倾向于通过羰基氧、伯胺和仲胺氮原子形成六配位螯合物。