Mg掺杂TiO2纳米晶光氧化还原染料的可逆颜色转变研究

doi:10.15541/jim20180070

无机材料学报 ›› 2018, Vol. 33 ›› Issue (10): 1124-1130.DOI: 10.15541/jim20180070

Mg掺杂TiO₂纳米晶光氧化还原染料的可逆颜色转变研究

赵海兵^1,2, 徐海峰^1,2, 杨克伟^1,2, 林辰学^1,2, 冯苗^1,2, 于岩^1,2

福州大学 1.材料科学与工程学院;2 生态环境材料先进技术福建省高等学校重点实验室, 福州 350116

收稿日期:2018-02-06 修回日期:2018-03-30 出版日期:2018-10-20 网络出版日期:2018-09-25
作者简介:赵海兵(1991-), 男, 硕士研究生. E-mail: 1913686245@qq.com
基金资助:
国家自然科学基金(51402051, 51102047);福建省高校杰出青年科研人才计划(2016);福州大学贵重仪器设备开放测试基金(2018T005)

Enhanced Photoreversible Color Switching of Methylene Blue Catalyzed by Magnesium-doped TiO₂ Nanocrystals

ZHAO Hai-Bing^1,2, XU Hai-Feng^1,2, YANG Ke-Wei^1,2, LIN Chen-Xue^1,2, FENG Miao^1,2, YU Yan^1,2

1.College of Materials Science and Engineering, Fuzhou University, Fuzhou 350116 China;2. Key Laboratory of Eco-Materials Advanced Technology, Fuzhou University, Fuzhou 350116, China

Received:2018-02-06 Revised:2018-03-30 Published:2018-10-20 Online:2018-09-25
About author:ZHAO Hai-Bing. E-mail: 1913686245@qq.com
Supported by:
National Natural Science Foundation of China (51402051, 51102047);Fujian Provincial Outstanding Young Scientists Program (2016);Fuzhou University, Expensive Equipment Open-end Test Fund (2018T005)

摘要/Abstract

摘要：

由于非直接接触、远程控制、高效及快捷的优点, 光可逆颜色转换材料在信息存储、显示器件、传感器等领域有着重要应用。复合无机材料和有机材料, 实现协同增效, 是新型光驱动可逆颜色转换材料的研究热点之一。本研究采用一步液相合成法制备粒径约为5 nm的锐钛矿型Mg²⁺掺杂TiO₂纳米晶, 通过X射线衍射、透射电子显微镜、X射线光电子能谱、红外光谱和拉曼光谱等表征手段确认材料的组成结构, 并对比研究了Mg²⁺掺杂TiO₂对亚甲基蓝(MB)光可逆颜色转换性能的增强效应。结果表明, 掺杂Mg²⁺在TiO₂晶格中能产生杂质能级, 有效抑制了光生载流子的复合, 提高了TiO₂光氧化还原MB的活性; 另一方面, 掺杂Mg²⁺降低了TiO₂纳米晶的吸收波长, 在可见光照射下能够有效地抑制MB向还原态LMB的转变, 提高系统着色速率。这种基于碱金属掺杂TiO₂纳米晶的光可逆颜色转换材料在许多光电子器件领域具有潜在的应用价值。

关键词: TiO₂纳米晶, 碱金属掺杂, 氧化还原, 亚甲基蓝

Abstract:

Because the advantages of non-direct contact, remote control, high efficiency and fastness, light-driven reversible color switching materials (LDRCSMs) have important applications in information storage, display devices, sensors, and other fields. The combination of inorganic materials and organic materials to achieve synergies is one of the research hotspots of new LDRCSMs. A one-step liquid-phase synthesis method was used to prepare Mg-doped TiO₂ nanocrystals (Mg-TiO₂ NCs) with a particle size of ~5 nm. The reversible light-responsive color switching of methylene blue (MB) by using Mg-TiO₂ NCs was investigated. The results show that Mg²⁺ doping generates impurity levels in the TiO₂ lattice, effectively inhibiting the recombination of photogenerated carriers and increasing the activity of TiO₂ photooxidation-reduced MB. On the other hand, Mg²⁺doping can decrease the absorption wavelength of TiO₂ NCs, which effectively represses the partial reduction of MB to reduced LMB under visible light irradiation, leading to a higher recoloration rate. Such LDRCSMs based on alkali metal-doped TiO₂ NCs may have potential application in many optoelectronic device fields.

Key words: TiO₂ nanocrystals, alkali metal doping, redox, methylene blue

中图分类号:

TK511

赵海兵, 徐海峰, 杨克伟, 林辰学, 冯苗, 于岩. Mg掺杂TiO₂纳米晶光氧化还原染料的可逆颜色转变研究[J]. 无机材料学报, 2018, 33(10): 1124-1130.

ZHAO Hai-Bing, XU Hai-Feng, YANG Ke-Wei, LIN Chen-Xue, FENG Miao, YU Yan. Enhanced Photoreversible Color Switching of Methylene Blue Catalyzed by Magnesium-doped TiO₂ Nanocrystals[J]. Journal of Inorganic Materials, 2018, 33(10): 1124-1130.

图/表 8

图1 纯TiO2和Mg-TiO2的XRD(a)和Raman(b)图谱

Fig. 1 XRD patterns (a) and Raman spectra (b) of pure TiO2 and Mg-TiO2 NC

表1 纯TiO2和Mg-TiO2的XRD分析结果

Table 1 XRD analysis results of pure TiO2 and Mg-TiO2

Sample	Particle size D/nm	Interplanar spacing, d/nm	Cell parameters a=b/nm	2θ/(°)
TiO₂	5.21	0.35238	0.038052	25.253
Mg-TiO₂	4.54	0.35173	0.037950	25.273

图2 Mg-TiO2(a)~(b)和TiO2(c)~(d)不同放大倍数的TEM照片

Fig. 2 TEM images at different magnifications of (a, b) Mg-TiO2 and (c, d) TiO2

图3 纯TiO2和Mg-TiO2的Ti2p XPS图谱(a); Mg-TiO2样的Mg1s XPS图谱(b)

Fig. 3 Ti2p XPS spectra (a) of pure TiO2 and Mg-TiO2, and (b) Mg1s XPS spectrum (b) of Mg-TiO2

图4 TiO2和Mg-TiO2的FT-IR谱图(a)和UV-Vis谱图(样品浓度均为10 mg/mL)(b)

Fig. 4 FT-IR spectra (a) and UV-Vis absorption spectra (b) of pure TiO2 and Mg-TiO2Inset: Mott-Schottky plots and pictures of pure TiO2 and Mg-TiO2

图5 紫外光照射下MB褪色过程的UV-Vis吸收光谱图((a)TiO2, (c)Mg-TiO2); 可见光照射下着色过程的UV-Vis吸收光谱图((b)TiO2, (d)Mg-TiO2)

Fig. 5 UV-Vis spectra showing the decoloration process of MB under UV irradiation ((a) TiO2, (c) Mg-TiO2); UV-Vis spectra showing the recoloration process of MB under visible light irradiation ((b)TiO2, (d) Mg-TiO2)Inset: the pictures of the reaction system solutions changing with the illumination time

图6 纯TiO2和Mg-TiO2纳米晶的PL图(a)和i-t图(b)

Fig. 5 Fluorescence spectra (a) and photocurrent intensity (b) of pure TiO2 and Mg-TiO2

图7 纯TiO2和Mg-TiO2 NCs的Zeta电位测试结果

Fig. 7 Zeta-potential of pure TiO2 and Mg-TiO2 NCs

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Mg掺杂TiO₂纳米晶光氧化还原染料的可逆颜色转变研究

Enhanced Photoreversible Color Switching of Methylene Blue Catalyzed by Magnesium-doped TiO₂ Nanocrystals

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