拓扑相变制备具有拓宽可见光响应范围的Ti3+自掺杂3D空盒状TiO2

doi:10.1016/S1872-2067(18)63106-7

催化学报 ›› 2018, Vol. 39 ›› Issue (8): 1373-1383.DOI: 10.1016/S1872-2067(18)63106-7

拓扑相变制备具有拓宽可见光响应范围的Ti³⁺自掺杂3D空盒状TiO₂

张成江^a, 田丽君^a, 陈连清^a, 黎小芳^b, 吕康乐^a, 邓克俭^a

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

收稿日期:2017-12-11 修回日期:2018-05-13 出版日期:2018-08-18 发布日期:2018-07-04
通讯作者: 陈连清
基金资助:
国家自然科学基金（20702064，21177161，31402137）；湖北省杰出青年基金（2013CFA034）；湖北省青年英才开发计划（RCJH15001）；绿色催化四川省高校重点实验室开放课题基金（LYZ1107）；中南民族大学中央高校专项基金（CZP17077）.

One-pot topotactic synthesis of Ti³⁺ self-doped 3D TiO₂ hollow nanoboxes with enhanced visible light response

Chengjiang Zhang^a, Lijun Tian^a, Lianqin Chen^a, Xiaofang Li^b, Kangle Lv^a, Kejian Deng^a

a Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education, 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:2017-12-11 Revised:2018-05-13 Online:2018-08-18 Published:2018-07-04
Contact: 10.1016/S1872-2067(18)63106-7
Supported by:
The work was supported by the National Natural Science Foundation of China (20702064, 21177161, 31402137), Hubei Province Science Fund for Distinguished Yong Scholars (2013CFA034) and the Program for Excellent Talents in Hubei Province (RCJH15001), the Opening Project of Key Laboratory of Green Catalysis of Sichuan Institutes of High Education (LYZ1107), and the Fundamental Research Funds for the Central University, South-Central University for Nationalities (CZP17077).

摘要/Abstract

摘要：

TiO₂广泛用作半导体光催化材料，但由于自身对光利用率低（只吸收紫外光）、禁带宽度较大、光生载流子复合率极高，限制了它在相关领域的应用.为此，设计了Ti³⁺离子自掺杂来克服TiO₂半导体材料的上述缺点，进而提高其光催化活性.在不引入其他元素的情况下，以TiOF₂为原料，Zn粉为还原剂，在水热条件下采用拓扑相变法原位制备了具有可见光响应的Ti³⁺自掺杂空盒状TiO₂（记为Ti³⁺/TiO₂）催化剂材料.掺杂金属离子可以改变半导体TiO₂的结晶度和产生晶格缺陷，形成电子或空穴的捕获中心，影响电子-空穴对的复合；同时，掺杂金属离子产生的晶格缺陷有利于Ti³⁺和氧空位的形成，有利于提高TiO₂的量子效率.Ti³⁺掺杂是一种既清洁又未引入其他金属离子的掺杂改性方法，它能有效保持催化剂的结构和形貌不受其他金属离子的影响.总之，金属离子掺杂有效拓展了TiO₂的光吸收范围，并极大地提高了TiO₂的光催化活性.
本文研究了不同量的还原剂对催化剂空盒状TiO₂结构形貌影响，以及在可见光下光催化降解罗丹明B反应性能，发现Ti³⁺/TiO₂催化剂均拥有非常好的光催化活性，其中R0.25催化剂在可见光下120min，RhB降解率达到96%，是TiO₂的4倍多.且可循环使用5次的光催化循环降解实验后，表现出较高的稳定性.催化剂经过Ti³⁺自掺杂后，对催化剂自身的空盒状结构形貌并无很大的影响，随着还原剂Zn粉的量增加，Ti⁴⁺还原形成Ti³⁺数量增加，导致形成更多的氧空位.皆为锐钛矿型TiO₂，与未掺杂Ti³⁺的TiO₂比较发现，自掺杂Ti³⁺的TiO₂的（105）XRD衍射峰越来越尖锐，（004）衍射峰越来越宽.随着还原剂Zn粉质量的逐渐增加，催化剂的光响应范围拓宽到可见光区，且逐渐增强.这说明Ti³⁺的掺杂不仅提高了TiO₂在可见光的响应能力，也提高了TiO₂在紫外光范围的响应能力.另外，掺杂后的TiO₂禁带宽度的减小，使其价带上的电子更容易被可见光激发，产生更多的电子-空穴对参与光催化反应，从而提高TiO₂的光催化效率.

关键词: Ti³⁺自掺杂, 拓扑相变, 3维空盒子, 可见光响应, 光催化活性

Abstract:

Ti³⁺ self-doped anatase three-dimensional (3D) TiO₂ hollow nanoboxes were synthesized via a topological transformation process involving template participation by a facile one-pot hydrothermal treatment with an ethanol solution of zinc powder and TiOF₂. It is worth noting that the 3D TiO₂ hollow nanoboxes are assembled from six single-crystal nanosheets and have dominant exposure of the {001} facets. It is found from EPR spectra that adding zinc powder is an environment-friendly and effective strategy to introduce Ti³⁺ and oxygen vacancy (O_v) into the bulk of 3D hollow nanoboxes rather than the surface, which is responsible for their enhanced visible photocatalytic properties. The photocatalytic activity was evaluated by measuring the formation rate of hydroxide free radicals using 7-hydroxycoumarin as a probe. The sample prepared with zinc/TiOF₂ mass ratio of 0.25 exhibited the highest RhB photodegradation activity under visible-light irradiation with a degradation rate of 96%, which is 4.0-times higher than that of pure TiO₂. The results suggest a novel approach to construct in-situ 3D hierarchical TiO₂ hollow nanoboxes doped with Ti³⁺ and O_v without introducing any impurity elements for superior visible-light photocatalytic activity.

Key words: Ti³⁺ self-doped, Topological transformation, Three-dimensional hollow nanoboxes, Visible light response, Photocatalytic activity

张成江, 田丽君, 陈连清, 黎小芳, 吕康乐, 邓克俭. 拓扑相变制备具有拓宽可见光响应范围的Ti³⁺自掺杂3D空盒状TiO₂[J]. 催化学报, 2018, 39(8): 1373-1383.

Chengjiang Zhang, Lijun Tian, Lianqin Chen, Xiaofang Li, Kangle Lv, Kejian Deng. One-pot topotactic synthesis of Ti³⁺ self-doped 3D TiO₂ hollow nanoboxes with enhanced visible light response[J]. Chinese Journal of Catalysis, 2018, 39(8): 1373-1383.

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拓扑相变制备具有拓宽可见光响应范围的Ti³⁺自掺杂3D空盒状TiO₂

One-pot topotactic synthesis of Ti³⁺ self-doped 3D TiO₂ hollow nanoboxes with enhanced visible light response

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