In2O3/ZrO2-TiO2空心球复合材料的制备与光解水制氢性能

doi:10.7503/cjcu20160544

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (2): 238.doi: 10.7503/cjcu20160544

In₂O₃/ZrO₂-TiO₂空心球复合材料的制备与光解水制氢性能

张晶晶^1,², 李莉^1,^2,³(), 郝玉婷², 孙雷雷², 张鑫悦²

1. 齐齐哈尔大学材料科学与工程学院
2. 化学与化学工程学院
3. 黑龙江省高校精细化工重点实验室, 齐齐哈尔 161006

收稿日期:2016-07-28 出版日期:2017-02-10 发布日期:2017-01-17
作者简介:联系人简介: 李莉, 女, 博士, 教授, 主要从事纳米复合材料的设计、制备与光催化性能研究. E-mail: qqhrll@163.com
基金资助:
国家自然科学基金(批准号: 21376126)、黑龙江省自然科学基金(批准号: B201106)、黑龙江省教育厅科学技术研究项目(批准号: 12511592)、黑龙江省政府博士后资助经费(批准号: LBH-Z11108)、黑龙江省政府博士后科研启动经费(批准号: LBH-Q13172)和齐齐哈尔大学研究生创新计划项目(批准号: YJSCX2015-ZD03)资助

Preparation and Photocatalytic Hydrogen Evolution Performance of In₂O₃/ZrO₂-TiO₂ Hollow Spheres^†

ZHANG Jingjing^1,², LI Li^1,^2,^3,^*(), HAO Yuting², SUN Leilei², ZHANG Xinyue²

1. College of Materials Science and Engineering
2. College of Chemistry and Chemical Engineering
3. Key Laboratory of Fine Chemicals of Heilongjiang Province, Qiqihar University, Qiqihar 161006, China

Received:2016-07-28 Online:2017-02-10 Published:2017-01-17
Contact: LI Li E-mail:qqhrll@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(No.21376126), the Natural Science Foundation of Heilongjiang Province, China(No.B201106), the Scientific Research Foundation of Educaton Department of Heilongjiang Province, China(No.12511592), the Postdoctoral Grants of Government of Heilongjiang Province, China(No.LBH-Z11108), the Initiation Grant Project for Postdoctoral Researchers in Heilongjiang Province, China(No.LBH-Q13172) and the Innovation Project of Qiqihar University Graduate Education, China(No.YJSCX2015-ZD03)

摘要/Abstract

摘要：

以聚苯乙烯(PS)胶球为模板, 通过一步法结合煅烧后处理制备了空心球复合材料In₂O₃/ZrO₂-TiO₂. 采用X射线衍射(XRD)、 X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、紫外-可见漫反射吸收光谱(UV-Vis DRS)和氮气吸附-脱附等测试手段对复合材料的结构、组成和形貌进行了表征. 结果表明, In₂O₃/ZrO₂-TiO₂复合材料的晶型结构以锐钛矿型TiO₂为主, 同时存在少量含有Ti—O—Zr键的混合氧化物. 该复合材料经聚苯乙烯模板处理后呈现空心球状结构, 球壁由纳米粒子堆积而成. In₂O₃/ZrO₂-TiO₂空心球复合材料的比表面积较大(66.92 m²/g), 且In₂O₃与ZrO₂-TiO₂复合后光吸收发生了红移. 对该复合材料光解水制氢性能的研究结果表明, 空心球状In₂O₃/ZrO₂-TiO₂具有较好的产氢效果(56.7 μmol/g, 8 h), 明显高于P25、 ZrO₂、空心球状ZrO₂-TiO₂及粉末状In₂O₃/ZrO₂-TiO₂.

关键词: 聚苯乙烯, 空心球, In₂O₃/ZrO₂-TiO₂, 一步法, 光解水制氢

Abstract:

Using polystyrene spheres(PS) latex as the template, In₂O₃/ZrO₂-TiO₂ hollow spheres were prepared by one-step method combined with calcination treatment. The structure, composition and morphology of the composite were characterized by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), ultraviolet-visible diffuse reflectance spectroscopy(UV-Vis DRS), scanning electron microscopy(SEM) and N₂ absorption-desorption measurements. The results showed that In₂O₃/ZrO₂-TiO₂ hollow sphere was mainly anatase TiO₂ and its optical absorption red-shifted slightly. In₂O₃/ZrO₂-TiO₂ hollow spheres also showed higher activity for hydrogen production, its hydrogen production was higher than that of P25, ZrO₂, hollow sphere ZrO₂-TiO₂ and powder In₂O₃/ZrO₂-TiO₂.

Key words: Polystyrene, Hollow sphere, In₂O₃/ZrO₂-TiO₂, One-step method, Photocatalytic hydrogen evolution

中图分类号:

O644

TrendMD:

张晶晶, 李莉, 郝玉婷, 孙雷雷, 张鑫悦. In₂O₃/ZrO₂-TiO₂空心球复合材料的制备与光解水制氢性能. 高等学校化学学报, 2017, 38(2): 238.

ZHANG Jingjing, LI Li, HAO Yuting, SUN Leilei, ZHANG Xinyue. Preparation and Photocatalytic Hydrogen Evolution Performance of In₂O₃/ZrO₂-TiO₂ Hollow Spheres^†. Chem. J. Chinese Universities, 2017, 38(2): 238.

图/表 9

Fig.1 XRD patterns of In2O3/ZrO2-TiO2-H(a), In2O3/ZrO2-TiO2(b), ZrO2-TiO2-H(c), TiO2(d), ZrO2(e) and In2O3(JCPDS No. 22-0336)(f)

Table 1 BET surface areas(SBET), average pore diameters(D), pore volumes(Vtotal ), crystallite size(D), band-gap energy(Eg) and cell parameters of In2O3/ZrO2-TiO2 and In2O3/ZrO2-TiO2-H

Sample	S_BET/(m²·g^-1)	D/nm	V_total/(cm³·g^-1)	D/nm	E_g/eV	Crystal parameter/nm
Sample	S_BET/(m²·g^-1)	D/nm	V_total/(cm³·g^-1)	D/nm	E_g/eV	a	c
In₂O₃/ZrO₂-TiO₂	57.45	10.78	0.155	19.16	3.09	0.3822	0.9735
In₂O₃/ZrO₂-TiO₂-H	66.92	11.24	0.188	24.10	3.15	0.3802	0.9661

Fig.2 Full scan XPS spectrum(A) and O1s(B), Ti2p(C), Zr3d(D) and In3d(E) XPS spectra of In2O3/ZrO2-TiO2-H

Fig.3 SEM images of PS(A) and In2O3/ZrO2-TiO2-H(B)

Fig.4 UV-Vis DRS spectra(A) and Kubelka-Munk energy curve plots(B) of ZrO2(a), TiO2(b), In2O3(c), ZrO2-TiO2-H(d), In2O3/ZrO2-TiO2(e) and In2O3/ZrO2-TiO2-H(f)

Table 2 Absolute electronegativity(X/eV), energy band gaps(Eg/eV), conduction band potential(ECB/eV) and valence band potential(EVB/eV) of In2O3, ZrO2 and TiO2

Semiconductor	X/eV	E_g/eV	E_CB/eV	E_VB/eV
In₂O₃	5.28	2.53	-0.48	2.05
ZrO₂	5.91	3.75	-0.46	3.30
TiO₂	5.81	3.22	-0.30	2.92

Fig.5 N2 adsorption-desorption isotherms of In2O3/ZrO2-TiO2-H(A) and In2O3/ZrO2-TiO2(B) The insets show the BJH pore size distribution of the corresponding samples.

Fig.6 Hydrogen production amount of different photocatalysts(t=8 h)(A) and capture test results for UV photocatalytic degradation of MO using In2O3/ZrO2-TiO2-H(B) (A) a. P25; b. ZrO2; c. ZrO2-TiO2-H; d. In2O3/ZrO2-TiO2; e. In2O3/ZrO2-TiO2-H. (B) a. Benzoquinone; b. triethanolamine; c. tert-butanol; d. In2O3/ZrO2-TiO2-H.

Fig.7 Possible photocatalytic reaction mechanism of In2O3/ZrO2-TiO2-H

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In₂O₃/ZrO₂-TiO₂空心球复合材料的制备与光解水制氢性能

Preparation and Photocatalytic Hydrogen Evolution Performance of In₂O₃/ZrO₂-TiO₂ Hollow Spheres^†

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