基于表面优先型相变过程构建TiO2(B)/锐钛矿异相结纳米纤维及其光催化性能

doi:10.1016/S1872-2067(18)63096-7

催化学报 ›› 2018, Vol. 39 ›› Issue (9): 1500-1510.DOI: 10.1016/S1872-2067(18)63096-7

基于表面优先型相变过程构建TiO₂(B)/锐钛矿异相结纳米纤维及其光催化性能

王奕岚, 张婉, 王子豪, 曹祎萌, 冯佳米, 王增林, 马艺

陕西师范大学化学化工学院, 应用表面与胶体化学教育部重点实验室, 陕西西安 710119

收稿日期:2018-03-05 修回日期:2018-04-29 出版日期:2018-09-18 发布日期:2018-07-19
通讯作者: 马艺
基金资助:
国家自然科学基金（21603134）；陕西省高校科协青年人才托举计划项目（20150104）；陕西省自然科学基金（2016JQ2023）；中央高校基本科研业务费专项资金项目（GK201603032）.

Fabrication of TiO₂(B)/anatase heterophase junctions in nanowires via a surface-preferred phase transformation process for enhanced photocatalytic activity

Yilan Wang, Wan Zhang, Zihao Wang, Yimeng Cao, Jiami Feng, Zenglin Wang, Yi Ma

Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, Shaanxi, China

Received:2018-03-05 Revised:2018-04-29 Online:2018-09-18 Published:2018-07-19
Contact: 10.1016/S1872-2067(18)63096-7
Supported by:
This work was supported by the National Natural Science Foundation of China (21603134), Young Talent Fund of University Association for Science and Technology in Shaanxi, China (20150104), Natural Science Basic Research Plan in Shaanxi Province of China (2016JQ2023) and the Fundamental Research Funds for the Central Universities (GK201603032).

摘要/Abstract

摘要：

近年来，随着光催化研究的逐渐深入，人们发现有效的电荷分离往往是提高半导体光催化材料活性的关键步骤.其中，在多晶相半导体材料中构建异相结结构是提高其活性的最有效途径之一.在TiO₂四种稳定晶相中，TiO₂（B）是发现最晚且研究较少的，并且目前对它的研究主要集中于锂离子电池方面，而在光催化领域中研究较少.然而，该材料特殊的晶相结构带来的各向异性和较大的比表面积都表明其在光催化领域同样具有潜在应用前景.本文通过三步合成法，包括水热过程、离子交换、退火过程，研究了TiO₂（B）向锐钛矿转变的相变过程，同时构建了具有TiO₂（B）/锐钛矿异相结结构的纳米线.在材料退火过程中，通过X射线衍射（XRD）和表面灵敏的紫外拉曼光谱（UV-Raman）分别监测了样品体相和表面相的晶相结构变化过程.发现了XRD与UV-Raman结果的不同步性.同时，通过对样品扫描电镜和透射电镜的形貌表征可知，TiO₂（B）纳米线在退火过程中部分结构发生坍塌，且逐渐转化成锐钛矿相，而相变过程很可能首先发生在坍塌结构处.高分辨电镜结果表明，纳米线中同时存在着TiO₂（B）结构和锐钛矿结构，并形成很好的异相结.根据相结构变化和形貌观察结果，我们推测TiO₂（B）向锐钛矿转变过程为表面优先型的相变过程，即材料表面相先于体相先发生相变过程，由此得到的材料表面相含有较多的锐钛矿，而体相中含有较多的TiO₂（B）.为了验证构建的异相结材料的光催化活性，采用光催化产氢和降解污染物双重反应对样品进行了表征.结果发现，单独的TiO₂（B）材料活性较锐钛矿材料相差较多，但其混相结构能较大幅度地提高光催化活性.其中，通过逐渐退火过程形成的体相为24%的TiO₂（B）、表面为100%的锐钛矿相的催化剂活性最高，其产氢活性可达4.82mmol/（h·g），降解污染物反应速率常数为0.0402min^-1.采用光电流测试、电化学阻抗和荧光光谱表征了材料在光催化过程中的载流子动力学行为.结果表明，最优活性的催化剂中体相的异相结结构对光生电荷的分离、传输都起到良好地促进作用，而表面的锐钛矿相主要负责高活性的表面反应，二者共同对高活性的光催化反应起到推动作用.

关键词: TiO₂(B)/锐钛矿, 异相结, 表面优先, 光催化, 相变

Abstract:

Heterojunction fabrication is one of the most effective strategies for enhancing the photocatalytic performance of semiconductor photocatalysts. Here, TiO₂(B)/anatase nanowires with interfacial heterostructures were prepared through a three-step synthesis method, including hydrothermal treatment, H⁺ exchange, and annealing. The phase structures of the nanowires in the bulk and on the surface during the annealing process were monitored by XRD and UV-Raman spectroscopy, respectively. SEM and TEM results indicate that the TiO₂(B) nanowires partially collapse and transform into anatase during the annealing process and the heterophase junction structure is formed simultaneously. On the basis of the phase structure together with morphology data, a phase-transformation mechanism was proposed. Photocatalytic activity was evaluated by hydrogen production and pollutant-degradation assays. The optimized structure of the photocatalyst contains 24% TiO₂(B) in the bulk and 100% anatase on the surface. The charge-carrier behavior during the photocatalytic process was investigated by photocurrent, electrochemical impedance spectroscopy (EIS), and photoluminescence (PL) spectroscopy, which revealed that the heterophase-junction structure in the bulk was responsible for the highly efficient charge separation and transportation, etc.; the anatase on the surface took control of the high surface-reaction activity.

Key words: TiO₂(B)/anatase, Heterophase junction, Surface-preferred, Photocatalysis, Phase transformation

王奕岚, 张婉, 王子豪, 曹祎萌, 冯佳米, 王增林, 马艺. 基于表面优先型相变过程构建TiO₂(B)/锐钛矿异相结纳米纤维及其光催化性能[J]. 催化学报, 2018, 39(9): 1500-1510.

Yilan Wang, Wan Zhang, Zihao Wang, Yimeng Cao, Jiami Feng, Zenglin Wang, Yi Ma. Fabrication of TiO₂(B)/anatase heterophase junctions in nanowires via a surface-preferred phase transformation process for enhanced photocatalytic activity[J]. Chinese Journal of Catalysis, 2018, 39(9): 1500-1510.

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基于表面优先型相变过程构建TiO₂(B)/锐钛矿异相结纳米纤维及其光催化性能

Fabrication of TiO₂(B)/anatase heterophase junctions in nanowires via a surface-preferred phase transformation process for enhanced photocatalytic activity

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