Synthesis and Characterization of Titanium-containing Periodic Mesoporous Organosilicas†

doi:10.7503/cjcu20150035

Abstract

Abstract:

Titanium-containing periodic mesoporous organosilicas(Ti-PMO) were hydrothermally synthesized using triblock copolymer P123 as the template, 1,2-bis(trimethoxysilyl)ethane as the silica precursor and titanocene dichloride as the titanium precursor. The crystal and textural properties of Ti-PMO were characterized by X-ray diffraction(XRD), transmission electron microscope(TEM) and N₂ physisorption. The influence of different titanium precursors, prehydrolysis time of titanium precursor, acid concentration and molar ratio of Si/Ti on the form of titanium in PMO were investigated by means of diffuse reflectance UV-Vis spectroscopy. It was revealed that Ti atoms could be incorporated into the framework of PMO materials in the form of tetrahedral coordination by finely controlling the synthesis condition. The hydrolysis rate of titanium and silica precursors should be precisely balanced to bring the oligomer titanium species and oligomer silica species, which are the hydrolysis intermediates of titanium precursor and silica precursor, into intimate contact and then co-condensate to form Ti—O—Si structure. Tetrahedral-coordinated Ti-containing PMO with good thermal and hydrothermal stability can be successfully obtained using titanocene dichloride as the titanium precursor at the ratio of n(Si)/n(Ti)>20 and prehydrolyzed for 6 h at acid concentration of 0.18 mol/L.

Key words: Periodic mesoporous organosilica, Tetrahedrally-coordinated Ti, Doping, Hydrolysis rate, Hydrothermal synthesis

CLC Number:

O614.4

TrendMD:

WANG Donglong, ZHOU Jinghong, SUI Zhijun, ZHOU Xinggui, SCOTT L. Susannah. Synthesis and Characterization of Titanium-containing Periodic Mesoporous Organosilicas^†[J]. Chem. J. Chinese Universities, 2015, 36(6): 1042.

Figures/Tables 17

Table 1 Synthetic conditions for Ti-PMO preparation

Sample(abbr.)	Ti precursor	Si/Ti molar ratio	Ti precursor prehydrolysis time/h	c_HCl/(mol·L^-1)
TB-0-0.18-50(TB)	TBOT	50	0	0.18
TT-0-0.18-50(TT)	TiCl₃	50	0	0.18
TD-0-0.18-50(TD1)	Cl₂TiCp₂	50	0	0.18
TD-3-0.18-50(TD2)	Cl₂TiCp₂	50	3	0.18
TD-6-0.18-50(TD3)	Cl₂TiCp₂	50	6	0.18
TD-9-0.18-50(TD4)	Cl₂TiCp₂	50	9	0.18
TD-6-0.033-50(TD5)	Cl₂TiCp₂	50	6	0.033
TD-6-0.5-50(TD6)	Cl₂TiCp₂	50	6	0.5
TD-6-1.5-50(TD7)	Cl₂TiCp₂	50	6	1.5
TD-6-0.18-100(TD8)	Cl₂TiCp₂	100	6	0.18
TD-6-0.18-20(TD9)	Cl₂TiCp₂	20	6	0.18
TD-6-0.18-10(TD10)	Cl₂TiCp₂	10	6	0.18

Fig.1 XRD patterns of Ti-PMO samples prepared with different Ti precursorsa. PMO; b. TB; c. TT; d. TD1.

Fig.2 N2 adsorption-desorption isotherms(A) and pore size distributions(B) of Ti-PMO samples prepared with different Ti precursorsa. PMO; b. TB; c. TT; d. TD1.

Fig.3 TEM images of Ti-PMO samples prepared under different conditions (A) TD1; (B) TD4; (C) TD7; (D) TD10.

Fig.4 Diffuse reflectance UV-Vis spectra of Ti-PMO samples prepared with different Ti precursors a. TB; b. TT; c. TD1; d. TiO2

Fig.5 XRD patterns(A) and N2 adsorption-desorption isotherms(B) of Ti-PMO samples prepared at different Cl2TiCp2 prehydrolysis timea. TD1; b. TD2; c. TD3; d. TD4.

Fig.6 Diffuse reflectance UV-Vis spectra of Ti-PMO samples prepared at different Cl2TiCp2 prehydrolysis timea. TD1; b. TD2; c. TD3; d. TD4.

Fig.7 XRD patterns of Ti-PMO samples prepared with different HCl concentrationsa. TD5; b. TD3; c. TD6; d. TD7.

Fig.8 N2 adsorption-desorption isotherms(A) and pore size distributions(B) of Ti-PMO samples prepared with different HCl concentrations a. TD5; b. TD3; c. TD6; d. TD7.

Fig.9 Diffuse reflectance UV-Vis spectra of Ti-PMO samples prepared with different HCl concentrationsa. TD5; b. TD3; c. TD6; d. TD7.

Fig.10 XRD patterns of Ti-PMO samples with different Ti contentsa. TD8; b. TD3; c. TD9; d. TD10.

Fig.11 Diffuse reflectance UV-Vis spectra of Ti-PMO samples with different Ti contentsa. TD8; b. TD3; c. TD9; d. TD10.

Scheme 1 Mechanism for the incorporation of Ti into the pore wall of PMO

Fig.12 Diffuse reflectance UV-Vis spectra of Ti-PMO samples obtained after coordinating the hydrolysis processTitanium precursor: a. TBOT; b. TiCl3.

Fig.13 TGA curves of PMO, Ti-PMO and SBA-15 under air(A) and nitrogen(B) atmospherea. PMO; b. TD3; c. SBA-15.

Fig.14 XRD patterns of TD3 before(a) and after(b) hydrothermal treatment

Fig.15 TEM images of TD3 before(A) and after(B) hydrothermal treatment

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