离子液体中Co掺杂介孔TiO2可见光催化剂的制备及性能研究

doi:10.15541/jim20130586

无机材料学报 ›› 2014, Vol. 29 ›› Issue (8): 801-806.DOI: 10.15541/jim20130586

离子液体中Co掺杂介孔TiO₂可见光催化剂的制备及性能研究

张丽娟¹, 底兰波¹, 李燕春¹, 张秀玲^1,2

(大连大学 1. 物理科学与技术学院; 2. 辽宁省生物有机化学重点实验室, 大连 116622)

收稿日期:2013-11-12 修回日期:2013-12-24 出版日期:2014-08-20 网络出版日期:2014-07-15
作者简介:张丽娟(1988–), 女, 硕士研究生. E-mail: lijuanzhang818@126.com
基金资助:
国家自然科学基金(21173028);辽宁省高等学校优秀科技人才支持计划(LR2012042)

Preparation and Properties of Co-doped TiO₂ with Assistance of Ionic Liquid

ZHANG Li-Juan¹, DI Lan-Bo¹, LI Yan-Chun¹, ZHANG Xiu-Ling^1,2

(1. College of Physical Science and Technology, Dalian University, Daiian116622, China; 2. Liaoning Province Key Laborato ry of Bioorganic Chemistry, Dalian University, Dalian 116622, China)

Received:2013-11-12 Revised:2013-12-24 Published:2014-08-20 Online:2014-07-15
About author:ZHANG Li-Juan. E-mail: lijuanzhang818@126.com
Supported by:
National Natural Science Foundation of China (21173028);Program for Liaoning Excellent Talents in University (LR2012042)

摘要/Abstract

摘要：

以离子液体([C₄MIM]BF₄)为模板剂, 采用溶胶-凝胶法制备了介孔TiO₂和Co掺杂的介孔TiO₂光催化剂。研究了Co掺杂对样品的比表面积、晶相、元素价态、吸光特性及可见光活性的影响。结果表明: 所制备的Co/TiO₂光催化剂为介孔结构的具有较大比表面积的锐钛矿相纳米颗粒; XPS分析表明: Co以Co²⁺取代Ti⁴⁺进入TiO₂晶格形成杂质能级, 降低了TiO₂带隙能, 有效拓展了TiO₂的光响应范围。以亚甲基蓝水溶液为降解对象, 在可见光 (λ>420 nm)下考察制备样品的光催化活性, 结果表明: Co掺杂的TiO₂具有可见光活性, 且0.3%Co/TiO₂的活性最高。

关键词: 离子液体, 二氧化钛, 钴掺杂, 可见光活性

Abstract:

Co-doped mesoporous TiO₂ photocatalysts were prepared by an ionic liquid 1-butyl-3-methylimida-zolium tetrafluoroborate ([C₄MIM]BF₄) modified Sol-Gel method. The effects of Co doping on the surface area, crystalline phase, chemical binding states and compositions, and absorbance of the Co-doped mesoporous TiO₂ photocatalysts were studied by N₂ adsorption-desorption measurements (BET), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV-Vis diffuse reflectance absorption spectra (UV-Vis DRS). BET analysis showed that Co/TiO₂ photocatalyst was mesoporous structure with large surface area. XRD patterns indicated that the Co-doped mesoporous TiO₂ photocatalysts was anatase structure. XPS spectra indicated that the Co²⁺ replaced Ti⁴⁺and entered into TiO₂ lattice, which reduced the band gap of TiO₂and thereby extending the light response range to the visible region (UV-Vis spectra). Photocatalytic activity of the Co/TiO₂ mesoporous photocatalysts was evaluated by photodegradation of methylene blue (MB) under visible light (λ>420 nm). Co-doped TiO₂exhibited obvious visible light activity for MB photodegradation, and 0.3%Co/TiO₂ exhibited the highest photocatalytic activity.

Key words: ionic liquid, titanium dioxide, Co doping, visible light activity

中图分类号:

O649

张丽娟, 底兰波, 李燕春, 张秀玲. 离子液体中Co掺杂介孔TiO₂可见光催化剂的制备及性能研究[J]. 无机材料学报, 2014, 29(8): 801-806.

ZHANG Li-Juan, DI Lan-Bo, LI Yan-Chun, ZHANG Xiu-Ling. Preparation and Properties of Co-doped TiO₂ with Assistance of Ionic Liquid[J]. Journal of Inorganic Materials, 2014, 29(8): 801-806.

图/表 8

图1 样品TiO2和Co/TiO2的吸附-脱附等温线(a)及孔径分布曲线(b)

Fig. 1 N2 adsorption-desorption isotherms (a) and pore size distribution curves (b) of TiO2 and Co/TiO2

图2 样品TiO2 (a)、0.1%Co/TiO2 (b)、0.3%Co/TiO2 (c)和0.5% Co/TiO2 (d)的XRD图谱

Fig. 2 XRD patterns of TiO2 (a), 0.1%Co/TiO2 (b), 0.3% Co/ TiO2 (c) and 0.5%Co/TiO2 (d)

表1 样品TiO2和Co/TiO2的结构参数

Table 1 Structural parameters of the TiO2 and Co/TiO2

Sample	Pore volume/<br/>(cm³·g^-1)	Pore radius/<br/>nm	Surface area/<br/>(m²·g^-1)
TiO₂	0.21	6.33	51.6
0.1%Co/TiO₂	0.21	6.31	57.4
0.3%Co/TiO₂	0.25	6.32	75.1
0.5%Co/TiO₂	0.23	6.33	63.9

图3 样品TiO2 (a)与0.3%Co/TiO2 (b)的TEM照片

Fig. 3 TEM images of TiO2 (a) and 0.3%Co/TiO2 (b)

图4 样品0.5%Co/TiO2的X射线光电子能谱

Fig. 4 High resolution XPS spectra of 0.5%Co/TiO2

图5 样品TiO2和Co/TiO2的紫外可见漫反射吸收光谱图

Fig. 5 UV-Vis DRS of TiO2 and Co/TiO2

表2 样品TiO2和Co/TiO2的带隙

Table 2 Band gap of the TiO2 and Co/TiO2

Sample	λ_g/nm	E_g/eV
TiO₂	387.5	3.20
0.1%Co/TiO₂	427.5	2.90
0.3%Co/TiO₂	463.4	2.68
0.5%Co/TiO₂	476.5	2.60

图6 掺杂量不同的Co/TiO2在可见光照下光催化曲线(a)与降解速率曲线(b)

Fig. 6 Photocatalytic activity (a) and the degradation rate curves (b) of Co/TiO2 with different contents of Co

参考文献 22

[1]	SAMUEL V, MUTHUKUMAR P, GAIKWAD S P, et al. Synthesis of mesoporous rutile TiO2. Mater. Lett.,2004, 58: 2514-2518.
[2]	CROSSLAND E J W, NOEL N, SIVARAM V, et al. Mesoporous TiO2 single crystals delivering enhanced mobility and optoelectronic device performance. Nature, 2013, 495: 215-219.
[3]	ZHENG Q, ZHOU B X, BAI J, et al. Self-organized TiO2 nanotube array sensor for the determination of chemical oxygen demand. Adv. Mater., 2008, 20(5): 1044-1049.
[4]	BISWAS S K, PATHAK A, PRAMANIK N K, et al. Codoped Cr and W rutile nanosized powders obtained by pyrolysis of triethanolamine complexes. Ceram. Int., 2008, 34(8): 1875-1883.
[5]	WAN B, CHEN M B, ZHOU X Y, et al. Photoclectrocatalytic performance of Ag/TiO2-xNx nanotube. J. Inorg. Mater., 2010, 25(3): 285-288.
[6]	DENG L X,WANG S R,LIU D Y, et al. Synthesis, characterization of Fe-doped TiO2 Nanotubes with high photocatalytic activity. Catal. Lett., 2009, 129(3/4): 513-518.
[7]	NAKASHIMA T, KIMIZUKA N. Interfacial synthesis of hollow TiO2 microspheres in ionic liquids. J. Am. Chem. Soc., 2003, 125(21): 6386-6387.
[8]	ZHOU Y, ANTONIETTI M. Synthesis of very small TiO2 nanocrystals in a room-temperature ionic liquid and their self- assembly toward mesoporous spherical aggregates. J. Am. Chem. Soc., 2003, 125(49): 14960-14961.
[9]	ZHENG W J, LIU X D, YAN Z Y, et al. Ionic liquid-assisted synthesis of large-scale TiO2 nanoparticles with controllable phase by hydrolysis of TiCl4. ACS Nano, 2009, 3(1): 115-122.
[10]	HAN Y D, WANG K, XU Z J, et al. Preparation of mesoporous TiO2 by ionic liquid modified Sol-Gel method .J. Chin. Ceram. Soc., 2012, 40(9): 1289-1293.
[11]	KANDIEL T A, ISMAIL A A, BAHNEMANN D W. Mesoporous TiO2 nanostructures: a route to minimize Pt loading on titania photocatalysts for hydrogen production. Phys. Chem. Chem. Phys., 2011, 13(45): 20155-20161.
[12]	ZHOU Y, SCHATTKAJ H, ANTONIETTI M. Room-temperature ionic liquids as template to monolithic mesoporous silica with wormlike pores via a Sol-Gel nanocasting technique. Nano Lett., 2004, 4(3): 477-481.
[13]	EUN H C, SUK-IN H, DONG J M. Preparation of thermally stable mesostructured nano-sized TiO2 particles by modified Sol-Gel method using ionic liquid. Catal. Lett., 2008, 123(1-2): 84-89.
[14]	SONG H B, ZHOU G W, WANG C F, et al. Synthesis and photocatalytic activity of nanocrystalline TiO2 co-doped with nitrogen and cobalt(II). Res. Chem. Intermed., 2013, 39(2): 747-758.
[15]	KIRIT S, DIMPLE S. Characterization of nanocrystalline cobalt doped TiO2 Sol-Gel material. J.Cryst. Growth, 2012, 352(11): 224-228.
[16]	SANG H X, TIAN Y, WANG X T, et al. Photocatalytic H2 evolution from glycerol solution over Bi3+-doped TiO2 nanoparticles. J. Inorg. Mater., 2012, 27(12): 1283-1288.
[17]	SUN J, LIU S X. Preparation of lanthanum-doped TiO2 film and its application for gaseous toluene removal.J. Inorg. Mater., 2010, 25(9): 928-934.
[18]	LI J G, ROBERT B, MASAAKI I, et al. Cobalt-doped TiO2 nanocrystallites: Radio-Frequency thermal plasma processing, phase structure, and magnetic properties. Phys. Chem. C, 2009, 113(19): 8009-8015.
[19]	WU Y Q, LU G X, LI S B. The preparation, optimization and photocatalytic properties of CoOx-modified TiO2 photocatalysts for hydrogen generation from photocatalytic water splitting. Chin. J. Inorg. Chem., 2005, 3(21): 309-314.
[20]	LEE A C, LIN R H, YANG C Y, et al. Preparations and characterization of novel photocatalysts with mesoporous titanium dioxide (TiO2) via a Sol-Gel method. Mater. Chem. Phys., 2008, 109(2/3): 275-280.
[21]	TANG S Q, HE J P, ZHANG Z. Synthesis and photocatalytic activity of Fe-doped mesoporous TiO2 powder. J. Chin. Ceram. Soc., 2012, 40(7): 950-956.
[22]	CHEN J B, WANG C W, MA B H, et al. Field emission from the structure of well-aligned TiO2/Ti nanotube arrays. Thin Soild Films, 2009, 517(15): 4390-4393.

离子液体中Co掺杂介孔TiO₂可见光催化剂的制备及性能研究

Preparation and Properties of Co-doped TiO₂ with Assistance of Ionic Liquid

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