蛋氨酸改性TiO<sub>2</sub>空心纳米盒高效可见光催化RhB分解和NO氧化

引用本文: 赵轩, 杜艳婷, 张成江, 田丽君, 黎小芳, 邓克俭, 陈连清, 段有雨, 吕康乐. 蛋氨酸改性TiO₂空心纳米盒高效可见光催化RhB分解和NO氧化[J]. 催化学报, 2018, 39(4): 736-746. doi: 10.1016/S1872-2067(18)63039-6 shu

Citation: Xuan Zhao, Yanting Du, Chengjiang Zhang, Lijun Tian, Xiaofang Li, Kejian Deng, Lianqing Chen, Youyu Duan, Kangle Lv. Enhanced visible photocatalytic activity of TiO₂ hollow boxes modified by methionine for RhB degradation and NO oxidation[J]. Chinese Journal of Catalysis, 2018, 39(4): 736-746. doi: 10.1016/S1872-2067(18)63039-6 shu

蛋氨酸改性TiO₂空心纳米盒高效可见光催化RhB分解和NO氧化

a 中南民族大学催化材料科学国家民委-教育部重点实验室, 湖北武汉 430074;
b 武汉科技大学化学化工学院, 湖北武汉 430081
基金项目:
国家自然科学基金（31402137，51672312，21373275）；湖北省杰出青年基金（2013CFA034）；湖北省英才计划（RCJH15001）；武汉市科技计划（2016010101010018）；中南民族大学中央高校基本科研业务费专项资金（CZP17077，CZP18016）.

摘要: 由高能面TiO₂纳米片（TiO₂-NSs）组装成的TiO₂空心纳米盒（TiO₂-HNBs）显示出比单独TiO₂-NSs更强的光催化性能，但是TiO₂-HNBs依然属于紫外光催化剂，无法充分利用太阳能.因此，开发具有可见光响应的由高能面TiO₂-NSs组装而成的TiO₂-HNBs具有重要意义.本文将立方体TiOF₂与含有N和S元素的生物分子蛋氨酸混合，通过一步焙烧制备了具有可见光响应活性的N和S元素共掺杂的TiO₂-HNBs（掺杂催化剂标记为TMx，未掺杂催化剂标记为Tx，x代表焙烧温度）.
由立方体TiOF₂到锐钛矿相TiO₂空心纳米盒的转变是一个自模板转化过程.氟离子的存在降低了TiO₂高能面（001）面的表面能，从而使得高能面TiO₂纳米片的形成变得可能.因此，热处理立方体TiOF₂可得到由高能面TiO₂纳米片组装的TiO₂空心纳米盒.
本文系统研究了焙烧温度（300-500℃）对所制TiO₂-HNBs结构与光催化性能的影响.结果发现，在350℃下焙烧，TiOF₂完全转化成锐钛矿相TiO₂-HNBs.但是焙烧蛋氨酸与TiOF₂的混合物，需400℃才能完全实现TiOF₂到锐钛矿相TiO₂-HNBs的转变.这说明蛋氨酸的加入阻碍了TiOF₂向锐钛矿相TiO₂-HNBs的转变.XPS结果显示，经过400℃焙烧的蛋氨酸改性样品（TM400），N和S元素成功掺入了TiO₂-HNBs晶格，使其产生可见光催化活性.
相对于400℃焙烧TiOF₂所得样品T400，蛋氨酸改性的TM400催化剂可见光降解罗丹明B染料（RhB）和NO氧化的性能分别提升了1.55倍和2.0倍，这与其更强的可见光吸收性能和光生载流子分离效率有关.400℃焙烧的蛋氨酸改性的TM400可见光催化活性稳定，连续5次可见光催化RhB降解后，其活性没有明显改变，显示了潜在的应用前景.

关键词:

English

Enhanced visible photocatalytic activity of TiO₂ hollow boxes modified by methionine for RhB degradation and NO oxidation

a Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education, Hubei Province, South-Central University for Nationalities, Wuhan 430074, Hubei, China;
b College of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China
Received Date: 07 December 2017
Revised Date: 15 January 2018
Fund Project:
This work was supported by the National Natural Science Foundation of China (31402137, 51672312, 21373275), Hubei Province Science Fund for Distinguished Yong Scholars (2013CFA034), the Program for Excellent Talents in Hubei Province (RCJH15001), the Science and Technology Program of Wuhan (2016010101010018), and the Fundamental Research Funds for the Central University, South-Central University for Nationalities (CZP17077, CZP18016).

Abstract: Hierarchical TiO₂ hollow nanoboxes (TiO₂-HNBs) assembled from TiO₂ nanosheets (TiO₂-NSs) show improved photoreactivity when compared with the building blocks of discrete TiO₂-NSs. However, TiO₂-HNBs can only be excited by ultraviolet light. In this paper, visible-light-responsive N and S co-doped TiO₂-HNBs were prepared by calcining the mixture of cubic TiOF₂ and methionine (C₅H₁₁NO₂S), a N-and S-containing biomacromolecule. The effect of calcination temperature on the structure and performance of the TiO₂-HNBs was systematically studied. It was found that methionine can prevent TiOF₂-to-anatase TiO₂ phase transformation. Both N and S elements are doped into the lattice of TiO₂-HNBs when the mixture of TiOF₂ and methionine undergoes calcination at 400℃, which is responsible for the visible-light response. When compared with that of pure 400℃-calcined TiO₂-HNBs (T400), the photoreactivity of 400℃-calcined methionine-modified TiO₂-HNBs (TM400) improves 1.53 times in photocatalytic degradation of rhodamine-B dye under visible irradiation (λ > 420 nm). The enhanced visible photoreactivity of methionine-modified TiO₂-HNBs is also confirmed by photocatalytic oxidation of NO. The successful doping of N and S elements into the lattice of TiO₂-HNBs, resulting in the improved light-harvesting ability and efficient separation of photo-generated electron-hole pairs, is responsible for the enhanced visible photocatalytic activity of methionine-modified TiO₂-HNBs. The photoreactivity of methionine modified TiO₂-HNBs remains nearly unchanged even after being recycled five times, indicating its promising use in practical applications.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

蛋氨酸改性TiO₂空心纳米盒高效可见光催化RhB分解和NO氧化

English

Enhanced visible photocatalytic activity of TiO₂ hollow boxes modified by methionine for RhB degradation and NO oxidation

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中国化学会秘书处

蛋氨酸改性TiO2空心纳米盒高效可见光催化RhB分解和NO氧化

English

Enhanced visible photocatalytic activity of TiO2 hollow boxes modified by methionine for RhB degradation and NO oxidation

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

蛋氨酸改性TiO₂空心纳米盒高效可见光催化RhB分解和NO氧化

Enhanced visible photocatalytic activity of TiO₂ hollow boxes modified by methionine for RhB degradation and NO oxidation

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs