B和Ru共改性对TiO<sub>2</sub>纳米管阵列的结构和光催化性能的影响

doi:10.11901/1005.3093.2017.522

材料研究学报

2018, Vol. 32

Issue (9): 655-661 DOI: 10.11901/1005.3093.2017.522

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B和Ru共改性对TiO₂纳米管阵列的结构和光催化性能的影响

王竹梅, 朱晓玲, 李月明(

), 廖润华, 沈宗洋, 左建林

景德镇陶瓷大学中国轻工业功能陶瓷材料重点实验室江西省能量存储与转换陶瓷材料工程实验室景德镇 333403

Effect of B and Ru Co-modification on Structure and Photocatalytic Activity of TiO₂ Nanotubes

Zhumei WANG, Xiaoling ZHU, Yueming LI(

), Runhua LIAO, Zongyang SHEN, Jianlin ZUO

Energy Storage and Conversion Ceramic Materials Engineering Laboratory of Jiangxi Province; China National Light Industry Key Laboratory of Functional Ceramic Materials; Jingdezhen Ceramic Institute, Jingdezhen 333403, China

引用本文:

王竹梅, 朱晓玲, 李月明, 廖润华, 沈宗洋, 左建林. B和Ru共改性对TiO₂纳米管阵列的结构和光催化性能的影响[J]. 材料研究学报, 2018, 32(9): 655-661.
Zhumei WANG, Xiaoling ZHU, Yueming LI, Runhua LIAO, Zongyang SHEN, Jianlin ZUO. Effect of B and Ru Co-modification on Structure and Photocatalytic Activity of TiO₂ Nanotubes[J]. Chinese Journal of Materials Research, 2018, 32(9): 655-661.

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摘要:

采用阳极氧化法制备TiO₂纳米管(TNTs),在电解液中添加NaBF₄制备B改性的TiO₂纳米管(B/TNTs),用湿浸渍法在TNTs和B/TNTs表面进行Ru改性制备了Ru/TNTs和Ru/B/TNTs。使用扫描电镜(FE-SEM)、能谱仪(EDS)、X射线衍射(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)以及X射线光电子能谱(XPS)等手段对样品进行表征,以亚甲基蓝(MB)的光催化降解为目标反应评价样品的光催化活性。结果表明：掺入B/TNTs和Ru/B/TNTs样品中的B在TiO₂晶格中形成B-O-Ti键;Ru/TNTs样品中的Ru以RuO₂形式负载在TiO₂纳米管表面;Ru/B/TNTs样品中的Ru少量进入TiO₂晶格其余的负载在纳米管表面,大部分以Ru⁰形式存在,少量以RuO₂形式存在。B掺杂使B/TNTs纳米管表面的羟基量增加、光学带隙能减小、光吸收阈值红移,使其光催化活性大幅提高;Ru/TNTs表面负载的RuO₂并未增加TiO₂纳米管表面羟基数量但是使光学带隙能减小、光吸收阈值红移,因此其光催化活性也有很大的提高;Ru/B/TNTs表面大量的Ru⁰使Ru/B/TNTs表面的羟基量减少,带隙能升高,光吸收阈值蓝移,其光催化活性低于Ru/TNTs或B/TNTs,与纯纳米管的性能相当。

关键词 ：材料表面与界面, TiO₂纳米管阵列, 阳极氧化, B掺杂, 钌改性, 光催化活性

Abstract：

TiO₂ nanotube arrays (TNTs) and boron doped TiO₂ nanotube arrays (B/TNTs) on Ti-foil were prepared via anodic oxidation process in electrolyte composed of ethylene glycol, H₂O and NH₄F, without and with addition of NaBF₄ respectively. Then TNTs and B/TNTs were further impregnated in Ru²⁺ containing solution to fabricate Ru-modified TiO₂ nanotube arrays of Ru/TNTs and Ru/B/TNTs. The prepared products were characterized by multi-functional field-emission scanning electron microscope (FE-SEM), energy dispersive spectrometer (EDS), X-ray diffractometer (XRD), UV-visible diffuse-reflectance spectrum (UV-Vis DRS) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the products was examined via degradation test of methylene blue solution under visible light irradiation. Results show that B was incorporated into the TNTs lattice to form B-O-Ti bond and Ru was introduced to form RuO₂ on the surface of Ru/TNTs. However, the main part of Ru formed as RuO₂ deposited on the surface of B/TNTs. On the contrary, for Ru/B/TNTs there exist a large amount of Ru⁰ and small amount of RuO₂ in the surface deposits and whilst very little Ru incorporated into the TNTs lattice; B-doping could effectively raise the the number of hydroxyl groups on the surface of B/TNTs, decrease the band gap energy and make the red shifting of absorption edges of the B/TNTs, which induce the significant increasing of the photocatalytic activity of B/TNTs. For the Ru/TNTs, the deposit of RuO₂ could not lead to the increase of the number of hydroxyl groups on the surface of Ru/TNTs but would decrease the band gap energy and make the red-shifting of the absorption edges, eventually promoting the photocatalytic activity of Ru/TNTs to some extent. By comparison with B/TNTs, the surface of Ru/B/TNTs is rich in Ru⁰, which could increase the band-gap energy, thus induce the blue shifting of the absorption edges, which eventually induces a lower photocatalytic activity of Ru/B/TNTs (similar to pure TiO₂ nanotubes).

Key words： surface and interface in the materials TiO₂nanotubes arrays anodization B-doped ruthenium modified photocatalytic activity

收稿日期: 2017-09-05

ZTFLH:

O643

基金资助:国家自然科学基金(51462010)和景德镇市科技计划(2017GYZD019-06)

作者简介:

作者简介王竹梅,女,1971年生,副教授

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https://www.cjmr.org/CN/10.11901/1005.3093.2017.522 或 https://www.cjmr.org/CN/Y2018/V32/I9/655

图1 在不同条件下制备的样品的SEM照片和B0-R2、B6-R2样品的EDS谱线

图2 在不同条件下制备的样品的XRD图谱

图3 Ru/TNTs和Ru/B/TNTs样品表面C 1s和Ru 3d5/2的XPS能谱图

表1 Ru/TNTs和Ru/B/TNTs样品表面Ru3d5/2的XPS谱峰参数

表2 Ru/B/TNTs样品表面O 1s的XPS谱峰参数

图4 样品表面O 1s的XPS能谱图

图5 各样品的Kubelka-Munk转换谱线和UV-vis漫反射图谱

表3 Kubelka-Munk 计算的各样品光学带隙值和光吸收阈值

图6 在不同条件下制备的样品在可见光下的光催化活性

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