席夫碱钴卟啉-TiO<sub>2</sub>复合光催化剂的制备及其光催化性能研究*

doi:10.11901/1005.3093.2016.174

材料研究学报

2016, Vol. 30

Issue (12): 947-954 DOI: 10.11901/1005.3093.2016.174

本期目录 | 过刊浏览

席夫碱钴卟啉-TiO₂复合光催化剂的制备及其光催化性能研究*

钮金芬¹(

),韩广超²,戴佩璇¹,姚秉华¹,刘存瑞¹,王钰¹

1. 西安理工大学应用化学系西安 710048
2. 辽宁大学有机化学系沈阳 110036

Preparation and Photocatalytic Activity of Schiff Base Cobalt Porphyrin-TiO₂ Composites

Jinfen NIU^1,^*(

),Guangchao HAN²,Peixuan DAI¹,Binghua YAO¹,Cunrui LIU¹,Yu WANG¹

1. Department of Applied Chemistry, Xi'an University of Technology, Xi'an 710048, China
2. Department of Organic Chemistry, Liaoning University, Shenyang 110036, China

引用本文:

钮金芬,韩广超,戴佩璇,姚秉华,刘存瑞,王钰. 席夫碱钴卟啉-TiO₂复合光催化剂的制备及其光催化性能研究*[J]. 材料研究学报, 2016, 30(12): 947-954.
Jinfen NIU, Guangchao HAN, Peixuan DAI, Binghua YAO, Cunrui LIU, Yu WANG. Preparation and Photocatalytic Activity of Schiff Base Cobalt Porphyrin-TiO₂ Composites[J]. Chinese Journal of Materials Research, 2016, 30(12): 947-954.

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摘要:

采用Alder法合成的5-对硝基苯基-10, 15, 20-三苯基钴卟啉, 通过浓盐酸/SnCl₂还原得5-对氨基苯基-10, 15, 20-三苯基钴卟啉, 再与对硝基苯甲醛反应生成席夫碱钴卟啉, 以希夫碱钴卟啉为敏化剂, 并与纯锐钛矿型TiO₂作用, 得到相应的金属卟啉敏化TiO₂复合光催化剂XFJ-Co-TPP-TiO₂。利用红外、紫外-可见漫反射光谱、XRD和SEM对所得金属卟啉以及XFJ-Co-TPP-TiO₂复合光催化剂进行了表征和分析。分析结果表明, 所合成的金属卟啉均为目标化合物, 金属卟啉成功负载于TiO₂表面。以亚甲基蓝和罗丹明B为模型反应物, 研究XFJ-Co-TPP-TiO₂复合催化剂的可见光光催化性能, 与纯TiO₂的光催化效果相比, 用席夫碱钴卟啉敏化后的TiO₂对亚甲基蓝和罗丹明B的光催化效果有了明显的提高。可见光条件照射下, 各种清除剂对光催化降解反应的影响表明, 空穴(h⁺)是催化剂XFJ-Co-TPP-TiO₂-1光降解罗丹明B反应体系中的主要活性物种。

关键词 ：无机非金属材料, 席夫碱卟啉, TiO2, 敏化, 光催化

Abstract：

A Schiff base cobalt porphyrin, namely N-(5-p-phenyl) -10, 15, 20-triphenyl porphyrin-nitrophenyl azomethine, denoted as XFJ-Co-TPP, was prepared by chemical synthetic method. Using XFJ-Co-TPP as sensitizer, anatase TiO₂ samples were impregnated with metal porphyrin to form XFJ-Co-TPP-TiO₂ composite photocatalysts. The photocatalysts were characterized by FT-IR, UV-Vis DRS, XRD and SEM. The results showed that the as-synthesised Schiff base cobalt porphyrins were target compound, which were successfully depositedon the surface of TiO₂. The photocatalytic activity of XFJ-Co-TPP-TiO₂ composite photocatalysts was investigated throughthe photocatalysts assisted degradation of methylene blue(MB) and Rhodamine B (RhB) under visible light irradiation. It was found that XFJ-Co-TPP-TiO₂ composite exhibited much higher photodegradation efficiency than the bare TiO₂ catalysts. The effect of various radical scavengers on the degradation of RhB with XFJ-Co-TPP-TiO₂-1 as catalyst showed thath⁺was likely to be major active specie responsible for the dye degradation under visible light.

Key words： inorganic non-metallic materials Schiff base porphyrin TiO2 sensitize photocatalytic

收稿日期: 2016-04-01

基金资助:* 陕西省教育厅科研计划项目16JK1546、2015年陕西省大学生创新创业训练计划项目306-251051570、西安理工大学高学历人才博士启动项目108-211309、西安理工大学优秀青年创新团队计划项目108-00T1402资助

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https://www.cjmr.org/CN/10.11901/1005.3093.2016.174 或 https://www.cjmr.org/CN/Y2016/V30/I12/947

图1 席夫碱钴卟啉结构式图

图2 希夫碱钴卟啉(XFJ-Co-TPP)合成路线

图3 TiO2, XFJ-Co-TPP与XFJ-Co-TPP -TiO2的红外光谱

图4 不同光催化剂的漫反射图

图5 不同光催化剂的XRD谱图

图6 不同光催化剂的SEM图(a) TiO2; (b)XFJ-Co-TPP-TiO2; (c) Ti, O, N和Co的元素面扫描图

图7 可见光下不同光催化剂对亚甲基蓝的降解率曲线和ln(C0/C)随时间变化曲线

图8 可见光下不同光催化剂对罗丹明B的降解率曲线(a); ln(C0/C)随时间变化曲线(b); XFJ-Co-TPP-TiO2-1光降解过程RhB过程中UV-vis图谱变化曲线(c); XFJ-Co-TPP-TiO2-1循环使用特性(d)

图9 亚甲基蓝和罗丹明B的结构式

图10 催化剂自由基捕获实验

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