Zn掺杂CuO/CuAl2O4复合空心球的制备及光催化性能

doi:10.15541/jim20140008

摘要/Abstract

摘要：

以葡萄糖为模板, 硝酸锌、硝酸铜和硝酸铝为原料, 采用水热法制备高比表面Zn-CuO/CuAl₂O₄复合空心球。采用XRD、SEM、HRTEM、BET、DRS和PL等手段对样品进行表征, 结果表明: 在600℃下焙烧的Zn-CuO/CuAl₂O₄复合物呈空心球状, 球体直径约为2 μm, 比表面积高达214.97 m²/g。引入Zn有助于提高样品对紫外和可见光的吸收能力, 减少光生电子空穴对的复合, 光催化活性显著提高。在模拟太阳光照下, 以甲基橙溶液为目标降解物, 考察样品的煅烧温度和Zn加入量对光催化活性的影响。当Zn加入量为0.5wt%, 煅烧温度为600℃时, 样品的光催化活性最佳。光照60 min, 0.5 g/L光催化剂用量对25 mg/L甲基橙溶液的脱色率高达97%。

关键词: Zn-CuO/CuAl2O4, 空心球, 水热法, 光催化, 降解

Abstract:

Zn-doped CuO/CuAl₂O₄composite hollow spheres with high specific surface area were synthesized by hydrothermal method, using glucose as template and Zn(NO₃)₂·6H₂O, Cu(NO₃)₂·3H₂O, Al(NO₃)₃·9H₂O as raw materials. The samples were characterized by XRD, SEM, HRTEM, BET, DRS and PL spectra. The results showed that Zn- doped CuO/CuAl₂O₄ composites possessed hollow microspheres shape with specific surface area up to 214.97 m²/g and diameter of about 2 μm after calcined at 600℃. The Zn doped photocatalysts exhibited enhanced absorption intensity, decreased electron-hole recombination. Further photocatalytic activities of the samples were greatly increased. The influences of calcination temperature and Zn doping content on photocatalytic activities of the samples were investigated by measuring the degradation rate of methyl orange (MO) under simulated sunlight irradiation. The sample doped with 0.5wt% Zn which was calcined at 600℃ showed the highest efficiency. Under visible light irradiation for 60 min, the decolorizing efficiency of 25 mg/L MO by 0.5 g/L photocatalyst reached 97%.

Key words: Zn-CuO/CuAl2O4, hollow sphere, hydrothermal process, photocatalysis, degradation

中图分类号:

O614

李小艳, 阎建辉, 张丽, 周民杰, 刘又年. Zn掺杂CuO/CuAl₂O₄复合空心球的制备及光催化性能[J]. 无机材料学报, 2014, 29(10): 1055-1060.

LI Xiao-Yan, YAN Jian-Hui, ZHANG Li, ZHOU Ming-Jie, LIU You-Nian. Preparation and Photocatalytic Properties of Hollow Spheres-like Zn-doped CuO/CuAl₂O₄ Composite Photocatalysts[J]. Journal of Inorganic Materials, 2014, 29(10): 1055-1060.

图/表 10

图1 不同温度煅烧0.5wt% Zn-CuO/CuAl2O4样品的XRD图谱

Fig. 1 XRD patterns of 0.5wt% Zn-CuO/CuAl2O4 samples calcined at different temperatures

图2 600℃煅烧Zn掺杂CuO/CuAl2O4样品的XRD图谱

Fig. 2 XRD patterns of Zn-doped CuO/CuAl2O4 samples calcined at 600℃ (a) 0wt% Zn-CuO/CuAl2O4; (b) 0.5wt% Zn-CuO/CuAl2O4; (c) 1wt% Zn- CuO/CuAl2O4; (d) 2wt% Zn-CuO/CuAl2O4

表1 1wt% Zn-CuO/CuAl2O4样品的EDS分析结果

Table 1 EDS analyses of 1wt% Zn-CuO/CuAl2O4 samples

Element	Area 1		Area 2
Element	wt%	at%	wt%	at%
O	32.00	52.78	30.99	51.06
Al	33.76	33.01	36.15	35.32
Cu	33.30	13.83	32.03	13.29
Zn	0.94	0.38	0.83	0.34

图3 Zn微球(a, b), 500℃煅烧Zn微球(c)和0.5wt% Zn-CuO/CuAl2O4样品(d, e)的SEM照片, 0.5wt% Zn-CuO/CuAl2O4样品(f)的HRTEM照片

Fig. 3 SEM images of Zn microspheres (a, b), Zn microspheres calcined at 500℃(c), 0.5wt% Zn-CuO/CuAl2O4 samples (d, e) and HRTEM images of 0.5wt% Zn-CuO/CuAl2O4 samples (f)

图4 Zn掺杂CuO/CuAl2O4样品的(a)N2吸附-脱附等温线和(b)孔径分布图

Fig. 4 (A) N2 adsorption-desorption isotherms and (B) pore size distribution curves of Zn-doped CuO/CuAl2O4 samples (a) 0wt% Zn-CuO/CuAl2O4; (b) 0.5wt% Zn-CuO/CuAl2O4; (c) 1wt% Zn-CuO/CuAl2O4; (d) 2wt% Zn-CuO/CuAl2O4

图5 Zn掺杂CuO/CuAl2O4样品的UV-Vis DRS图谱

Fig. 5 UV-Vis DRS spectra of Zn-doped CuO/CuAl2O4 samples (a) 0wt% Zn-CuO/CuAl2O4; (b) 0.5wt% Zn-CuO/CuAl2O4; (c) 1wt% Zn-CuO/CuAl2O4 calcined at 600℃

表2 Zn掺杂CuO/CuAl2O4样品的物理性质

Table 2 Physical property of Zn-doped CuO/CuAl2O4 samples

Sample	S_BET/(m²·g^-1)	Adsorption average pore width / nm	Pore volume /(cm³·g^-1)
0.3wt% Zn-CuO/CuAl₂O₄	208.25	7.7	0.59
0.5wt% Zn-CuO/CuAl₂O₄	214.97	9.2	0.71
1wt% Zn-CuO/CuAl₂O₄	182.92	7.0	0.45
2wt% Zn-CuO/CuAl₂O₄	171.42	6.5	0.37

图6 0wt% Zn-CuO/CuAl2O4和0.5wt% Zn-CuO/CuAl2O4样品的光致发光图谱

Fig. 6 PL spectra of 0wt% Zn-CuO/CuAl2O4 and 0.5wt% Zn- CuO/CuAl2O4 samples

图7 煅烧温度对0.5wt% Zn-CuO/CuAl2O4样品降解甲基橙的影响

Fig. 7 Effect of calcination temperatures on methyl orange degradation of 0.5wt% Zn-CuO/CuAl2O4 samples (a) 500℃; (b) 600℃; (c) 700℃; (d) 800℃; (e) 900℃

图 8 Zn加入量对CuO/CuAl2O4样品降解甲基橙的影响

Fig. 8 Effect of Zn doped content on methyl orange degradation of Zn-CuO/CuAl2O4 samples (a) 0wt% Zn-CuO/CuAl2O4; (b) 0.3wt% Zn-CuO/CuAl2O4; (c) 0.5wt% Zn-CuO/CuAl2O4; (d) 1wt% Zn-CuO/CuAl2O4; (e) 2wt% Zn-CuO/ CuAl2O4 calcined at 600℃

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Zn掺杂CuO/CuAl₂O₄复合空心球的制备及光催化性能

Preparation and Photocatalytic Properties of Hollow Spheres-like Zn-doped CuO/CuAl₂O₄ Composite Photocatalysts

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