基于表面金属有机化学方法的硅胶表面氧化钛的制备及表征

doi:10.7503/cjcu20150707

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (5): 956.doi: 10.7503/cjcu20150707

基于表面金属有机化学方法的硅胶表面氧化钛的制备及表征

李金灵^1,², 高子伟²()

1. 西安石油大学化学化工学院, 西安 710065
2. 陕西师范大学化学化工学院, 西安 710119

收稿日期:2015-09-11 出版日期:2016-05-10 发布日期:2016-04-07
作者简介:联系人简介: 高子伟, 男, 博士, 教授, 博士生导师, 主要从事金属有机化学方面的研究. E-mail:zwgao@snnu.edu.cn
基金资助:
国家自然科学基金(批准号: 21271124, 20771071)、陕西省自然科学基础研究计划项目(批准号: 2014JQ2056)和陕西省教育厅重点实验室科研计划项目(批准号: 14JS086)资助

Preparation and Characterization of Ti—O Units Anchored on Silica by Surface Organometallic Chemistry Method^†

LI Jinling^1,², GAO Ziwei^2,^*()

1. College of Chemistry and Chemical Engineering, Xi’an Shiyou University, Xi’an 710065, China
2. School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China

Received:2015-09-11 Online:2016-05-10 Published:2016-04-07
Contact: GAO Ziwei E-mail:zwgao@snnu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21271124, 20771071), the Natural Science Basic Research Plan of Shaanxi Province, China (No.2014JQ2056) and the Key Laboratory Scientific Research Program of Shaanxi Provincial Education Department, China(No.14JS086)

摘要/Abstract

摘要：

以普通硅胶为载体, 采用表面金属有机化学合成技术, 通过“一锅”反应制备了硅胶表面金属有机钛化合物, 然后经高温煅烧获得了硅胶表面氧化钛. 采用傅里叶变换红外光谱(FTIR)、 X射线光电子能谱(XPS)、热重分析(TG-DTA)及原子力显微镜(AFM)对硅胶表面金属有机钛化合物和表面氧化钛进行了结构表征. 结果表明, 高温煅烧过程中, 硅胶表面金属有机钛化合物不仅脱除了有机配体, 并且通氧使其表面“再生”羟基, 确保了钛的四配位形式不变; 氧化钛通过Si—O—Ti键锚定在硅胶表面, 呈分散、孤立状态分布. 高温煅烧后, 硅胶的骨架结构保持完好.

关键词: 表面金属有机化学方法, 表面金属有机钛化合物, 硅胶表面氧化钛, 表面结构

Abstract:

Based on the surface organometallic chemistry method, four surface organtitanium complexes anchored on silica were obtained by the reaction of spacer ligand (phenol, benzoic acid, 1-naphthol and 1-naphthol acid as spacer ligand, respectively), Ti(NMe₂)₄ and silica in one pot reaction system. Then, the four products were calcined respectively to obtain the titanum oxide anchored on silica. The surface organtitanium complexes and surface titanum oxides were characterized by Fourier transform infrared spectrum(FTIR), thermogravimetry analysis(TG-DTA), X-ray photoelectron spectrometry(XPS) and atomic force microscopy(AFM). The results showed that after calcination of surface organtitanium complexes at high temperature in O₂, not only were the organic ligands removed, but also the surface hydroxy was regenerated, which ensured that the four coordination forms of Ti were not changed. Meanwhile, titanium oxides anchored on silica surface by Si—O—Ti bonds, and existed as isolated, dispersed and ordered form. In addition, the skeleton structure of the silica was kept well after calcination of surface organtitanium complexes.

Key words: Surface organometallic chemistry, Surface organtitanium complex, Surface titanium oxide, Surface structure

中图分类号:

O641

TrendMD:

李金灵, 高子伟. 基于表面金属有机化学方法的硅胶表面氧化钛的制备及表征. 高等学校化学学报, 2016, 37(5): 956.

LI Jinling, GAO Ziwei. Preparation and Characterization of Ti—O Units Anchored on Silica by Surface Organometallic Chemistry Method^†. Chem. J. Chinese Universities, 2016, 37(5): 956.

图/表 9

Fig.1 Synthetic routes of surface organtitanium complexes and surface titanium oxide

Fig.2 FTIR spectra of surface organtitanium complexes and surface titanium oxide within 3500—4000 cm-1(A) a. SiO2-550, b. Ti/SiO2(1), c. TiO2/SiO2(1); (B) a. SiO2-550, b. Ti/SiO2(2), c. TiO2/SiO2(2);(C) a. SiO2-550, b. Ti/SiO2(3), c. TiO2/SiO2(3); (D) a. SiO2-550, b. Ti/SiO2(4), c. TiO2/SiO2(4).

Fig.3 FTIR spectra of surface organtitanium complexes and surface titanium oxide within 400—1200 cm-1(A)a. SiO2-550, b. Ti/SiO2(1), c. TiO2/SiO2(1); (B) a. SiO2-550, b. Ti/SiO2(2), c. TiO2/SiO2(2);(C) a. SiO2-550, b. Ti/SiO2(3), c. TiO2/SiO2(3); (D) a. SiO2-550, b. Ti/SiO2(4), c. TiO2/SiO2(4).

Fig.4 TG-DTA curves of surface organtitanium complexes(A) Ti/SiO2(1); (B) Ti/SiO2(2); (C) Ti/SiO2(3); (D) Ti/SiO2(4).

Fig.5 XPS survery spectra for surface organtitanium complexes(A) Ti/SiO2(1); (B) Ti/SiO2(2); (C) Ti/SiO2(3); (D) Ti/SiO2(4).

Fig.6 Ti2p peak fitting results of surface organtitanium complexes(A) Ti/SiO2(1); (B) Ti/SiO2(2); (C) Ti/SiO2(3); (D) Ti/SiO2(4).

Fig.7 N1s peak fitting result of surface organtitanium complexes(A) Ti/SiO2(1); (B) Ti/SiO2(2); (C) Ti/SiO2(3); (D) Ti/SiO2(4).

Fig.8 AFM images of SiO2-550 and surface titanium oxide(A) SiO2-550; (B) TiO2/SiO2(1); (C) TiO2/SiO2(2); (D) Ti/SiO2(3); (E) TiO2/SiO2(4).

Fig.9 Grafting of Ti(Ⅳ)-centred active sites on silica

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基于表面金属有机化学方法的硅胶表面氧化钛的制备及表征

Preparation and Characterization of Ti—O Units Anchored on Silica by Surface Organometallic Chemistry Method^†

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基于表面金属有机化学方法的硅胶表面氧化钛的制备及表征

Preparation and Characterization of Ti—O Units Anchored on Silica by Surface Organometallic Chemistry Method†

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Preparation and Characterization of Ti—O Units Anchored on Silica by Surface Organometallic Chemistry Method^†