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新型纳米玫瑰状铈(III)掺杂和未掺杂的铜(II)-联苯-4,4-二羧酸(Cu(II)-BPDCA)金属有机骨架作为可见光光催化剂:合成、表征、有毒染料的光降解及优化

Novel nanorose-like Ce(III)-doped and undoped Cu(II)-biphenyl-4,4-dicarboxylic acid (Cu(II)-BPDCA) MOSs as visible light photocatalysts: synthesis, characterization, photodegradation of toxic dyes and optimization.

作者信息

Mousavinia S E, Hajati S, Ghaedi M, Dashtian K

机构信息

Department of Physics, Yasouj University, Yasouj, 75918-74831, Iran.

Chemistry Department, Yasouj University, Yasouj, 75918-74831, Iran.

出版信息

Phys Chem Chem Phys. 2016 Apr 28;18(16):11278-87. doi: 10.1039/c6cp00910g.

Abstract

A novel nanorose-like metal organic system (MOS) based on Cu(II) and biphenyl-4,4-dicarboxylic acid (Cu-BPDCA) was hydrothermally synthesized and characterized via EDS, FE-SEM, XRD, DRS and FT-IR analysis. This novel nanomaterial was found to be of narrow energy band gap (1.24 eV) and thus it was applied as a photocatalyst driven by visible light for the degradation of the rose bengal (RB) and eosin Y (EY) dyes. For further improvement in the photocatalytic performance of Cu-BPDCA, it was doped with a trace amount of Ce(III) in a simple way followed by characterization. The achieved improvement is due to the formation of a large number of O2⁻˙ and ˙OH radicals compared to the case of undoped Cu-BPDCA. The influence of important variables such as initial dye concentration, photocatalyst dosage and time of irradiation on the photocatalytic degradation efficiency was studied and optimized using central composite design. The optimum condition for the photodegradation of RB was found to be 40 min, 4.0 mg L(-1) and 0.015 g, corresponding to the irradiation time, RB concentration and photocatalyst mass, respectively. The photodegradation of EY was optimized at 4.0, 76 min, 5.9 mg L(-1) and 0.015 g corresponding to the pH, irradiation time, EY concentration and photocatalyst mass, respectively. At these optimum conditions, the photocatalytic degradation percentages of RB and EY with a desirability of 0.95 and 1.0 were found to be 78.90% and 67.63%, respectively. Kinetics study showed that the Langmuir-Hinshelwood kinetics model suitably fits the experimental data. From the Langmuir-Hinshelwood kinetics model, a significantly high photodegradation to surface adsorption ratio was obtained which is the great advantage of this work in addition to applying visible light.

摘要

通过水热法合成了一种基于铜(II)和联苯 - 4,4 - 二羧酸(Cu - BPDCA)的新型纳米玫瑰状金属有机体系(MOS),并通过能谱分析(EDS)、场发射扫描电子显微镜(FE - SEM)、X射线衍射(XRD)、漫反射光谱(DRS)和傅里叶变换红外光谱(FT - IR)分析对其进行了表征。发现这种新型纳米材料具有窄带隙(1.24 eV),因此被用作可见光驱动的光催化剂,用于降解孟加拉玫瑰红(RB)和曙红Y(EY)染料。为了进一步提高Cu - BPDCA的光催化性能,以简单的方式对其进行了微量Ce(III)掺杂,随后进行了表征。与未掺杂的Cu - BPDCA相比,实现的性能提升归因于大量超氧阴离子自由基(O2⁻˙)和羟基自由基(˙OH)的形成。使用中心复合设计研究并优化了初始染料浓度、光催化剂用量和照射时间等重要变量对光催化降解效率的影响。发现RB光降解的最佳条件分别为40分钟、4.0 mg L⁻¹和0.015 g,对应于照射时间、RB浓度和光催化剂质量。EY的光降解在pH为4.0、照射时间为76分钟、EY浓度为5.9 mg L⁻¹和光催化剂质量为0.015 g时达到最佳。在这些最佳条件下,RB和EY的光催化降解率分别为78.90%和67.63%,可取性分别为0.95和1.0。动力学研究表明,朗缪尔 - 欣谢尔伍德动力学模型适合该实验数据。从朗缪尔 - 欣谢尔伍德动力学模型中,获得了显著高的光降解与表面吸附比,这是这项工作除了应用可见光之外的一大优势。

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