锐钛矿相二氧化钛晶粒的形貌调控及其显微结构分析

锐钛矿相二氧化钛晶粒的形貌调控及其显微结构分析

丁晓坤，陈  芳，裘雅渔

（浙江大学化学系，浙江 杭州 310027）

摘  要  利用简单水热反应，通过在弱酸性条件下引入氟离子，促使晶体的生长方式发生改变，使得其形貌由十面体转化为块状立方体，主要暴露晶面由常规的（101）晶面转变为（001）晶面，最终形成两种尺寸均一，但形貌不同的锐钛矿相二氧化钛晶体颗粒。通过两者罗丹明B光降解实验比较可以发现主暴露面为（001）面的非常规块状立方体二氧化钛晶粒的光催化性能要高于主暴露面为（101）的十面体结构晶粒。这被归因于（001）晶面具有的较高表面能及其可能存在的缺陷结构和氧空位密度。

关键词  二氧化钛；晶面；羟联；降解

中图分类号：TB383；TN304；TG115.21  文献标识码：A    doi:10.3969/j.issn.1000-6281.2019.04.006

Synthesis and microstructure analysis of shape-tuned anatase TiO₂ particles

DING Xiao-kun，CHEN Fang，QIU Ya-yu

(Department of Chemistry, Zhejiang University, Hangzhou Zhejiang 310027，China)

Abstract  The anatase TiO₂ was synthesized by simple hydrothermal route in acid solution.The shape of samples transformed from decahedron into square-like cube because the mainly exposed facets changed from (101) into (001). For the high surface energy and abundant structural defects on (001) facet, square-like anatase nanoparticles showed improved photocatalytic activity for degradation of Rhodamine B than traditional octahedron nanoparticles.

Keywords  TiO₂；crystal facet；olation；degradation

全文下载请到同方知网，万方数据库或重庆维普等数据库中下载！

[1] 张浩，朱庆明. 工业废水处理中纳米TiO₂光催化技术的应用[J]. 工业水处理，2011，31（5）：17-20.

[2]GRATZEL M. Photoelectric chemical cells[J].  Nature，2001，414（6861）: 338-344.

[3] 谢裕兴，孙振亚，李涵，等. 石英基多层纳米TiO₂-FeOOH复合材料的制备和显微结构的表征[J], 电子显微学报，2017，36（3）: 207-213.

[4] 杨亮，刘钟馨，周琼，等. 纯钛表面纳米多孔TiO₂膜的孔径分布研究[J]. 电子显微学报，2012，31（1）：41-45.

[5] XIA Y N，XIONG Y J，LIM B，et al.Shape-controlled synthesis of metal nanocrystals: simple chemistry meets complex physics[J].  AngewChem Int Ed，2009，48: 60-103

[6] TIAN N，ZHOU Z Y，SUN S G，et al.  Electrochemical preparation of Pd nanorods with high-index facets[J]. Chem Comun，2009，12: 1502-1504.

[7] HAN X G，KUANG Q，JIN M S，et al.  Synthesis of titania nanosheets with high percentage of exposed (001) facets and related photocatalytic properties[J].  JACS，2009，131（9）：3152-3153.

[8] YANG H G，SUN C H，QIAO S Z，et al. Anatase TiO₂ single crystals with a large percentage of reactive facets[J].  Nature，2008，453: 638-642.

[9] LIN H C，De-OLIVEIRA PW，HUCH V，et al.  Hydroxometalates from anion exchange reaction in ionic liquids: formation of [M(OH)₆]^2- (M = Ti, Zr) and [Zr(OH)₅]^-[J].  Chem Mater，2010, 22: 6518-6523.

[10] GONG X Q, SELLONI A. Reactivity of anatase TiO₂ nanoparticles: The role of the minority (001) surface[J]. J Phys Chem B, 2005，109（4）: 19560-19562.

[11] CHEN Y，CHEN D，LI Z，et al. Symmetry-breaking for formation of rectangular CdSe two-dimensional nanocrystals in zinc-blende structure[J].  JACS，2017，139（29）: 10009-10019.

[12] 丁晓坤. 基于量子点的正方块状二氧化钛纳米晶的形成分析[J].  电子显微学报，2012，31（1）：17-21.

[13] TURNER M，GOLOVKO V B，VAUGHAN O P，et al. Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters[J].  Nature，2008，454（7207）：981-983

[14] YUAN W, JIANG Y, WANG Y, et al. In situ observation of facet-dependent oxidation of graphene on platinum in an environmental TEM[J].  ChemCommun， 2015，51：350-353.

[15] GUO S, ZHANG S, SUN S. Tuning nanoparticle catalysis for the oxygen reduction reaction[J]. Angew Chem Int Ed，2013，52: 2-21.

[16] ONG W，TAN L，CHAI S，et al.  Highly reactive {001} facets of TiO₂-based composites:synthesis, formation mechanism and characterization[J]. Nanoscale，2014，6: 1946-2008.

[17] ZHANG Y，DAI R，HU S. Study of the role of oxygen vacancies as active sites in reduced graphene oxide modified TiO₂[J]. PhysChem ChemPhys，2017，19: 7307-7315.

[18] UMA T，DAI R，HOWJ D，MOUNFIELD W P，et al.  Effect of surface structure of TiO₂ nanoparticles on CO₂ adsorption and SO₂ resistance[J].  ACS Sustainable Chem Eng，2017，5: 9295-9306.