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Zr 和戊二醛交联聚乙烯亚胺功能化壳聚糖复合材料的制备、表征、Cr(VI)吸附性能、机制及再生。

Zr and glutaraldehyde cross-linked polyethyleneimine functionalized chitosan composite: Synthesis, characterization, Cr(VI) adsorption performance, mechanism and regeneration.

机构信息

School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054, China.

School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054, China.

出版信息

Int J Biol Macromol. 2023 Jun 1;239:124266. doi: 10.1016/j.ijbiomac.2023.124266. Epub 2023 Mar 30.

DOI:10.1016/j.ijbiomac.2023.124266
PMID:37003391
Abstract

In order to improve the stability, electrostatic interaction and ion exchange ability of chitosan for Cr (VI) removal, it is an effective strategy to introduce polyvalent metal ions and polymers into chitosan molecular chain through crosslinking. In this paper, Zr and glutaraldehyde crosslinked polyethyleneimine functionalized chitosan (CGPZ) composite was successfully synthesized and characterized by XRD, SEM, FTIR, BET, and XPS. The results showed that polyethyleneimine was successfully grafted onto chitosan by Schiff base reaction, while the appearance of ZrO and ZrN bonds verified the successful preparation of CGPZ. The monolayer maximum adsorption capacity of Cr(VI) by CGPZ was 593.72 mg g at 298 K and t = 210 min. The removal efficiency of 100 mg L Cr(VI) reached 95.7 %. The thermodynamic, isotherm and kinetic results show that the adsorption process of Cr (VI) by CGPZ is a spontaneous endothermic process controlled by entropy, which accords with Freundlich model and pseudo-second-order kinetic model. The regeneration experiments show that both HCl and NaOH can effectively desorb Cr(III) and Cr(VI) from the adsorbent surface, and the adsorbent has good acid-base resistance and regeneration performance. The removal of Cr(VI) mainly involves electrostatic attraction, ion exchange, reduction and complexation. CGPZ can synergistically adsorb Cr(VI) by electrostatic interaction of -NH/-C=N and ion exchange of Cl ion in the center of Zr, then reduce Cr(VI) to Cr(III) (45.4 % at pH = 2.0) by the -OH group on its surface, and chelate Cr(III) through COO- and -NH- groups.

摘要

为了提高壳聚糖对 Cr(VI)的去除稳定性、静电相互作用和离子交换能力,通过交联将多价金属离子和聚合物引入壳聚糖分子链是一种有效的策略。本文成功合成并通过 XRD、SEM、FTIR、BET 和 XPS 对 Zr 和戊二醛交联聚乙烯亚胺功能化壳聚糖(CGPZ)复合材料进行了表征。结果表明,壳聚糖通过希夫碱反应成功接枝了聚乙烯亚胺,而 ZrO 和 ZrN 键的出现验证了 CGPZ 的成功制备。CGPZ 在 298 K 和 t=210 min 时对 Cr(VI)的单层最大吸附容量为 593.72 mg g。100 mg L Cr(VI)的去除效率达到 95.7%。热力学、等温线和动力学结果表明,CGPZ 对 Cr(VI)的吸附过程是一个自发的吸热过程,由熵控制,符合 Freundlich 模型和准二级动力学模型。再生实验表明,HCl 和 NaOH 均可有效从吸附剂表面解吸 Cr(III)和 Cr(VI),且吸附剂具有良好的酸碱稳定性和再生性能。Cr(VI)的去除主要涉及静电吸引、离子交换、还原和络合。CGPZ 可以通过-NH/-C=N 的静电相互作用和中心 Zr 上 Cl 离子的离子交换协同吸附 Cr(VI),然后通过表面上的-OH 基团将 Cr(VI)还原为 Cr(III)(在 pH=2.0 时为 45.4%),并通过 COO-和-NH-基团螯合 Cr(III)。

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