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第 36 卷第 7 期 精 细 化 工 Vol.36, No.7
201 9 年 7 月 FINE CHEMICALS July 2019

水处理技术与环境保护
铁-锌卟啉框架材料及其可见光催化降解罗丹明

1*
1
韩雅楠 ，张 宝 ，冯亚青 1,2
（1. 天津大学 化工学院，天津 300350；2. 天津化学化工协同创新中心，天津 300072）

摘要：以 5,10,15,20-四-（4-羧基苯基）锌卟啉（ZnTCPP）为配体，以金属 Fe 为节点构筑了具有三维网状结构
的铁-锌卟啉框架材料 PCN-600(Zn)，采用 PXRD、SEM、UV-Vis DRS 对所得材料进行了表征，并将其用于可见
光下罗丹明 B(RhB)的降解反应，考察了 H 2 O 2 浓度对 PCN-600(Zn)光催化性能的影响，并通过捕获实验确定了
光催化反应过程中的主要活性物种，对比了 PCN-600(Zn)与另一种锆-锌卟啉框架材料 PCN-222(Zn)的光催化性
能。结果表明:在 H 2 O 2 的协同作用下，PCN-600(Zn)对 RhB 的降解表现出显著的催化活性，可见光照射 90 min
后降解率可达 94.2%。在实验范围内，随着 H 2 O 2 浓度的增加，PCN-600(Zn)的催化活性不断提高，H 2 O 2 用量为
+ -
4 mL 时可最大程度上提升催化剂效率。实验证明，在催化过程中，空穴（h ）为主要活性中间体，·OH 和·O 2
也起到了一定的作用。此外，PCN-600(Zn)的光催化性能明显强于 PCN-222(Zn)，相同实验条件下，前者 RhB
的降解率可达 95.9%，后者仅为 67.6%。
关键词：金属有机框架材料; 金属卟啉框架材料; 光催化降解; 卟啉；水处理技术
中图分类号：0000 文献标识码：A 文章编号：1003-5214 (2019) 07-1428-07

Iron (III)-Zinc (II) Porphyrin Framework for Visible Light
Photocatalytic Degradation of Rhodamine B

1*
1,2
1
HAN Ya-nan , ZHANG Bao , FENG Ya-qing
（1. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China; 2. Tianjin Co-Innovation
Center of Chemical Science and Engineering, Tianjin 300072, China）
Abstract: A three-dimensional iron (III)-zinc (II) porphyrin framework, PCN-600 (Zn) was constructed
using 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin]-Zn (ZnTCPP) as ligand and Fe as nodes. The
resulting material was characterized by PXRD, SEM and UV-Vis DRS and used for the degradation of
rhodamine B (RhB) under visible light irradiation. The effect of H 2O 2 concentration on the photocatalytic
performance of PCN-600 (Zn) was investigated. The main reactive species during the photocatalytic
reaction were determined by capture experiments. In addition, the photocatalytic performance between
PCN-600 (Zn) and zirconium (IV)-zinc (II) porphyrin framework, PCN-222(Zn) was compared. The results
showed that PCN-600 (Zn) exhibited obvious catalytic performance for the degradation of RhB in the
presence of H 2O 2. The degradation rate of RhB reached 94.2% under visible light irradiation for 90 min.
With the increase of H 2O 2 concentration, the catalytic activity of PCN-600 (Zn) improved gradually. The
efficiency of catalyst was the greatest when the amount of H 2O 2 was 4 mL. Experiments proved that during
-
+
the catalytic process, holes (h ) were the main reactive species, and ·OH and ·O 2 also had a certain
contribution. More importantly, the photocatalytic performance of PCN-600 (Zn) was significantly better
than that of PCN-222 (Zn), and under the identical experimental conditions, the degradation rate of the
former for RhB was 95.9%, and that of the latter was only 67.6%.
Key words: metal organic frameworks; metal-porphyrin frameworks; photocatalytic degradation; porphyrin;
water treatment technology

收稿日期：2018-11-22; 定用日期：2019-02-14; DOI: 10.13550/j.jxhg.20180863
基金项目：国家重点研发计划-国际合作（2016YFE0114900）；国家自然基金国际（地区）合作与交流资助项目（21761132007）
作者简介：韩雅楠（1994—），女，硕士生，E-mail：1032693988@qq.com。联系人：张 宝（1976—），男，副教授，E-mail：
baozhang@tju.edu.cn。