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

doi:10.7503/cjcu20150707

Abstract

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

CLC Number:

O641

TrendMD:

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

Figures/Tables 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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