Preparation of TiO2 Mesocrystals by Topochemical Conversion and Their Performance

doi:10.12422/j.issn.1672-6952.2023.01.005

Journal of Liaoning Petrochemical University ›› 2023, Vol. 43 ›› Issue (1): 27-31.DOI: 10.12422/j.issn.1672-6952.2023.01.005

• Material Science and New Energy • Previous Articles Next Articles

Preparation of TiO₂ Mesocrystals by Topochemical Conversion and Their Performance

Shuaikang Chang(), Chuang Liu, Kunchen Li, Bo Li, Fangfang Wang, Caiyun Lu, Changdong Chen()

School of Petrochemical Engineering，Liaoning Petrochemical University，Fushun Liaoning 113001，China

Received:2021-09-18 Revised:2022-03-18 Online:2023-02-25 Published:2023-03-13
Contact: Changdong Chen

介观TiO₂晶体材料的拓扑转变合成及其性能

常帅康(), 刘闯, 李坤宸, 李波, 王芳芳, 陆彩云, 陈常东()

辽宁石油化工大学石油化工学院，辽宁抚顺 113001

通讯作者: 陈常东
作者简介:常帅康（1999⁃），男，本科生，无机非金属材料工程专业，从事无机非金属材料方面的研究；E⁃mail：473623923@qq.com。
基金资助:
教育部“春晖计划”合作科研项目(2020703?8);国家留学基金委公派访学学者面上项目(CSC202008210025);辽宁省教育厅科学技术研究项目(L2019036);辽宁石油化工大学科研启动基金项目(2016xJJ?075);辽宁省大学生创新创业训练计划项目(2020101480002)

Abstract

Abstract:

In this work, the rutile mesocrystals TiO₂ were synthesized by hydrothermal method using layered titanate HTO (H₄_x_/3Ti_2-_x_/3□ _x_/3O₄?nH₂O) as the precursor. By means of X?ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and other testing methods, the effect of reaction temperature on the synthesis of rutile?type mesoscopic TiO₂ crystal material by means of topological structure transformation was studied. The results reveal that rutile TiO₂ can be obtained under the condition of pH 0.5 of the reaction system, and with the gradual increase of the reaction temperature, the rutile?type mesoscopic TiO₂ crystal material is formed at 120 ℃. Taking Rhodamine B (RhB) as the pollutant model for degradation experiments, the photocatalytic activity of rutile mesocrystals TiO₂ is significantly higher than that of other samples. Experiments on dye?sensitized solar cells (DSSCs) show that the mesocrystals structure formed at 120 ℃ is conducive to the rapid migration of photogenerated carriers, thus obtaining high cell characteristics.

Key words: Mesocrystals, Hydrothermal, Topotactic phase transformation, Photo(electric) catalysis

摘要：

以层状结构的钛酸盐HTO（H₄_x_/3Ti_2-_x_/3□ _x_/3O₄?nH₂O）为原料，采用水热的方法合成了金红石型介观TiO₂晶体。通过X射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）等测试手段，研究了反应温度对利用拓扑结构转变方式合成的金红石型介观TiO₂晶体材料的影响。结果表明，金红石型TiO₂晶体材料可以在反应体系pH为0.5的条件下得到，当反应温度升高到120 ℃时，形成了金红石型介观TiO₂晶体材料。以罗丹明B（RhB）为污染物模型进行了降解实验。结果表明，120 ℃时金红石型介观TiO₂晶体材料的光催化活性明显高于其他样品，主要是由于介观晶体具有较为特殊的电子传导特性，有助于电子与空穴的分离。染料敏化太阳能电池（DSSCs）实验结果表明，120 ℃时所形成的介观晶体结构有助于光生载流子的快速迁移，从而获得较高的电池特性。

关键词: 介观晶体, 水热, 拓扑相变, 光（电）催化

CLC Number:

TE09

Shuaikang Chang, Chuang Liu, Kunchen Li, Bo Li, Fangfang Wang, Caiyun Lu, Changdong Chen. Preparation of TiO₂ Mesocrystals by Topochemical Conversion and Their Performance[J]. Journal of Liaoning Petrochemical University, 2023, 43(1): 27-31.

常帅康, 刘闯, 李坤宸, 李波, 王芳芳, 陆彩云, 陈常东. 介观TiO₂晶体材料的拓扑转变合成及其性能[J]. 辽宁石油化工大学学报, 2023, 43(1): 27-31.

Figures/Tables 6

References 16

1	Fujishima A， Honda K. Electrochemical photolysis of water at a semiconductor electrode［J］. Nature， 1972， 238： 37⁃38.
2	Fujishima A， Kobayakawa K， Honda K. Hydrogen production under sunlight with an electrochemical photocell［J］. Journal of the Electrochemical Society， 1975， 122： 1487⁃1489.
3	O'Regan B， Grätzel M. A low ⁃ cost， high ⁃ efficiency solar cell based on dye ⁃ sensitized colloidal TiO₂ films［J］. Nature， 1991， 353： 737⁃740.
4	Nam S H， Shim H S， Kim Y S， et al. Ag or Au nanoparticle⁃embedded one⁃dimensional composite TiO₂ nanofibers prepared via electrospinning for use in lithium⁃ion batteries［J］. ACS Applied Materials & Interfaces， 2010， 2： 2046⁃2052.
5	Fujishima A， Rao T N， Tryk D A. Titanium dioxide photocatalysis［J］. Journal of Photochemistry and Photobiology C， 2000， 1： 1⁃21.
6	Grätzel M. Dye⁃sensitized solar cells［J］. Journal of Photochemistry and Photobiology C， 2003， 4： 145⁃153.
7	Chen X， Mao S S. Titanium dioxide nanomaterials： Synthesis， properties， modifications， and applications［J］. Chemical Reviews， 2007， 107： 2891⁃2959.
8	Cölfen H， Antonietti M. Mesocrystals： Inorganic superstructures made by highly parallel crystallization and controlled alignment［J］. Angewandte Chemie International Edition， 2005， 44： 5576⁃5591.
9	Wu J， Liao W， Yoshimura M. Soft processing of hierarchical oxide nanostructures for dye⁃sensitized solar cell applications［J］. Nano Energy， 2013， 2： 1354⁃1372.
10	王鑫，张静. CdS 异相结的固相法制备及其光催化性能［J］. 辽宁石油化工大学学报， 2019， 39（3）： 30⁃34.
11	Sun Y Y， Zong Z M， Li Z K， et al. Hydrothermal synthesis of TiO₂ nanotubes from one⁃dimensional TiO₂ nanowires on flexible non⁃metallic substrate［J］. Ceramics International， 2018， 44： 3501⁃3504.
12	Yan X， Feng L， Jia J， et al. Controllable synthesis of anatase TiO₂ crystals for high⁃performance dye⁃sensitized solar cells［J］. Journal of Materials Chemistry A， 2013， 1： 5347⁃535.
13	Gong J， Liang J， Sumathy K. Review on dye⁃sensitized solar cells （DSSCs）： Fundamental concepts and novel materials［J］. Renewable and Sustainable Energy Reviews， 2012， 16： 5848⁃5860.
14	Chen C， Xu L， Sewvandi G A， et al. Microwave⁃assisted topochemical conversion of layered titanate nanosheets to ｛010｝⁃faceted anatase nanocrystals for high performance photocatalysts and dye⁃sensitized solar cells［J］. Crystal Growth & Design， 2014， 14： 5801⁃5811.
15	Du Y， Feng Q， Chen C， et al. Photocatalytic and dye⁃sensitized solar cell performances of ｛010｝⁃faceted and ［111］⁃faceted anatase TiO₂ nanocrystals synthesized from tetratitanate nanoribbons［J］. ACS Applied Materials & Interfaces， 2014， 6： 16007⁃16019.
16	Chen C， Ikeuchi Y， Xu L， et al. Synthesis of ［111］⁃ and ｛010｝⁃faceted anatase TiO₂ nanocrystals from tri⁃titanate nanosheets and their photocatalytic and DSSC performances［J］. Nanoscale， 2015， 7： 7980⁃7991.

反应温度/℃	晶型	电流密度/(mA·cm^-2)	电压/V	填充因子/%	转化效率/%	膜厚度/μm
120	金红石	13.2	0.69	62.5	5.7	12.1
140	金红石	8.8	0.63	65.5	3.6	11.8

反应温度/℃	晶型	电流密度/(mA·cm^-2)	电压/V	填充因子/%	转化效率/%	膜厚度/μm
120	金红石	13.2	0.69	62.5	5.7	12.1
140	金红石	8.8	0.63	65.5	3.6	11.8

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