MOF衍生的多孔ZnO/C、Ag/ZnO/C复合材料光催化性能研究

doi:10.15541/jim20150201

无机材料学报 ›› 2015, Vol. 30 ›› Issue (12): 1321-1326.DOI: 10.15541/jim20150201 CSTR: 32189.14.10.15541/jim20150201

MOF衍生的多孔ZnO/C、Ag/ZnO/C复合材料光催化性能研究

郭艳蓉¹, 常薇¹, 张雯², 汪辉³

(1. 西安工程大学环境与化学工程学院, 西安 710048; 2. 西安交通大学理学院, 西安 710049; 3. 西安交通大学能动学院, 西安 710049)

收稿日期:2015-04-24 修回日期:2015-06-26 出版日期:2015-12-20 网络出版日期:2015-11-24
作者简介:郭艳蓉(1991–), 女, 硕士研究生. E-mail: 1227225213@qq.com
基金资助:
中央高校基本科研业务费(08143053);西安碑林科技计划项目(JX1419);西安工程大学研究生创新基金(CX2014022)

Photocatalytic Properties of MOF-derived ZnO/C, Ag/ZnO/C Porous Composite Materials

GUO Yan-Rong¹, CHANG Wei¹, ZHANG Wen², WANG Hui³

(1. College of Environmental and Chemical Engineering, Xi’an Polytechnic University, Xi’an 710048, China; 2. School of Science, Xi’an Jiaotong University, Xi’an 710049, China; 3. School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an 710049, China)

Received:2015-04-24 Revised:2015-06-26 Published:2015-12-20 Online:2015-11-24
About author:GUO Yan-Rong. E-mail: 1227225213@qq.com

摘要/Abstract

摘要：

以金属有机骨架(MOF-5)为前驱体, 通过高温热处理和湿化学法获得ZnO/C和Ag/ZnO/C两种光催化复合材料。采用X 射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能谱(EDS)和紫外-可见分光漫反射(UV-Vis DRS)等方法对所得样品的晶体结构、形貌特征、组成及光谱特性进行了表征。结果显示, 高温热处理保留了MOF-5的原始结构。ZnO/C比表面积为390 m²/g, 载银后比表面积仍达232 m²/g, 负载的银颗粒尺寸约30 nm。光催化降解实验表明ZnO/C和Ag/ZnO/C复合材料对亚甲基蓝(MB)都具有很高的降解效率, 均优于商业TiO₂。Ag/ZnO/C的光催化性能更好, 且具有较好的重复利用和稳定性。因此, 适度的高温碳化和掺杂贵金属是获得优良光催化性能的根本原因。

关键词: 金属有机骨架, 掺杂, 氧化锌, 改性, 光催化

Abstract:

Two photocatalytic materials, ZnO/C and Ag/ZnO/C, were synthesized by high temperature heat-treatment and wet-chemical methods using a typical metal-organic framework (MOF-5) as precursor. The samples were characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM), X-ray energy dispersive spectroscope (EDS), and UV-Vis diffuse reflection spectroscope (UV-Vis DRS), respectively. After heat-treatment under nitrogen, the initial morphology of MOF-5 is mostly retained. As a result, relatively high surface area up to 390 m²/g of ZnO/C and 232 m²/g of Ag/ZnO/C are realized. The size of Ag particles loaded on Ag/ZnO/C is about 30 nm. The photocatalytic efficiencies of both ZnO/C and Ag/ZnO/C composites on photo-degradation of methylene blue (MB) are higher than that of commercial TiO₂ powder (Degussa P25). Ag/ZnO/C possesses even higher photocatalytic ability, repeatability and stability than does ZnO/C. The results strongly suggest that high temperature heat-treatment of the MOF properly followed by moderate silver doping is a facile way to improve the photocatalytic properties.

Key words: metal-organic framework, dopping, ZnO, modification, photocatalysis

中图分类号:

TQ132

郭艳蓉, 常薇, 张雯, 汪辉. MOF衍生的多孔ZnO/C、Ag/ZnO/C复合材料光催化性能研究[J]. 无机材料学报, 2015, 30(12): 1321-1326.

GUO Yan-Rong, CHANG Wei, ZHANG Wen, WANG Hui. Photocatalytic Properties of MOF-derived ZnO/C, Ag/ZnO/C Porous Composite Materials[J]. Journal of Inorganic Materials, 2015, 30(12): 1321-1326.

图/表 8

图1 (a) MOF-5及其衍生物MOF-5 (b) 的XRD图谱

Fig. 1 XRD patterns of (a) MOF-5 and (b) derivatives

图2 (a) ZnO/C, (b)AZC-1, (c) Ag/MOF-5和(d)AZC-2样品的SEM照片及EDS分析结果

Fig. 2 SEM images of samples (a) ZnO/C, (b) AZC-1, (c) Ag/MOF-5, (d) AZC-2, and corresponding EDS patterns for (b) and (d)

表1 样品的物理特性

Table 1 Physical property of the samples

Sample	MOF-5	ZnO/C	AZC-1	Ag/MOF-5	AZC-2
BET/(m²•g^-1)	766	390	232	21	21
Pore volume/(mL•g^-1)	0.477	0.599	0.568	0.145	0.076

图3 复合材料的紫外可见漫反射谱曲线

Fig. 3 UV-Vis diffuse reflection spectra of composite materials

图4 样品对亚甲基蓝(MB)的吸附曲线

Fig. 4 Absorption curves for different samples of methylene blue

图5 样品对亚甲基蓝(MB)的光催化降解曲线

Fig. 5 Photo-degradation curves of methylene blue for different samples

图6 样品重复使用光催化降解亚甲基蓝(MB)

Fig. 6 Recycling uses of the samples for Methylene Blue (MB)

图7 AZC-1光催化降解实验机理示意图[17]

Fig. 7 Scheme diagram of photodegradation mechanism of AZC-1[17]

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MOF衍生的多孔ZnO/C、Ag/ZnO/C复合材料光催化性能研究

Photocatalytic Properties of MOF-derived ZnO/C, Ag/ZnO/C Porous Composite Materials

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