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用于刚果红可见光驱动光催化的超分子结构铜(II)/胍功能化二硅氧烷配合物

Cu(II)/Guanidine Functionalized Disiloxane Complex of Supramolecular Structures for Visible Light-Driven Photocatalysis of Congo Red.

作者信息

Fortună Maria E, Pricop Lucia, Zaltariov Mirela, Popovici Dumitru, Ignat Maria, Harabagiu Valeria, Simionescu Bogdan C

机构信息

"Petru Poni" Institute of Macromolecular Chemistry, 41A Grigore Ghica Voda Alley, 700487 Iasi, Romania.

Faculty of Chemistry, "Alexandru Ioan Cuza" University of Iaşi, 11 Bd. Carol I, 700506 Iaşi, Romania.

出版信息

Polymers (Basel). 2022 Feb 20;14(4):817. doi: 10.3390/polym14040817.

Abstract

The present study focuses on the synthesis of a new guanidine-functionalized disiloxane used as a ligand to obtain copper(II) complexes linked through hydrogen bonding into supramolecular structures. A two-step procedure was used to prepare the guanidine functionalized disiloxane ligand. Firstly, the hydrosilylation reaction between the siloxane precursor, namely 1,1,3,3-tetramethyldisiloxane (DS), and the allyl glycidyl ether (AGE) was performed in the presence of a platinum catalyst resulting in glycidoxypropyldisiloxane (DS-PMO) intermediary compound. In the second step, DS-PMO derivative was modified with 1,1,3,3-tetramethyl guanidine (TMGu) to obtain the guanidine-functionalized disiloxane ligand (bGu-DS) that was further used for the coordination of copper(II) acetate hydrate. The structures of the ligand and of its Cu(II) complex were confirmed by spectral methods (IR, UV-Vis, NMR, XRF) and correlated with theoretical calculations using semi-empirical PM6 and DFT methods. The copper(II) complex was found to exhibit low optical band gap energy (2.9 eV) and good photocatalytic activity under visible light irradiation in the decomposition of Congo Red (CR). A dye removal efficiency higher than 97% at the catalyst and CR concentrations of 1 and, respectively, 200 mg/L was obtained.

摘要

本研究聚焦于一种新型胍基官能化二硅氧烷的合成,该二硅氧烷用作配体以获得通过氢键连接成超分子结构的铜(II)配合物。采用两步法制备胍基官能化二硅氧烷配体。首先,在铂催化剂存在下,使硅氧烷前体,即1,1,3,3 - 四甲基二硅氧烷(DS)与烯丙基缩水甘油醚(AGE)发生硅氢加成反应,生成缩水甘油氧基丙基二硅氧烷(DS - PMO)中间化合物。第二步,用1,1,3,3 - 四甲基胍(TMGu)对DS - PMO衍生物进行修饰,得到胍基官能化二硅氧烷配体(bGu - DS),该配体进一步用于与水合醋酸铜(II)配位。通过光谱方法(红外光谱、紫外可见光谱、核磁共振光谱、X射线荧光光谱)确认了配体及其铜(II)配合物的结构,并与使用半经验PM6和密度泛函理论(DFT)方法的理论计算结果相关联。发现该铜(II)配合物在可见光照射下分解刚果红(CR)时表现出低光学带隙能量(2.9 eV)和良好的光催化活性。在催化剂和CR浓度分别为1和200 mg/L时,染料去除效率高于97%。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c53/8963006/5fa2995eafe6/polymers-14-00817-sch001.jpg

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