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

doi:10.15541/jim20140008

Abstract

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

CLC Number:

O614

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.

Figures/Tables 10

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

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

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

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)

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

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℃

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

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

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℃

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℃

References 21

[1]	LI F H, LIN H, LI J F, et al. Influence of LiF on the infrared transmissivity of magnesia alumina spinel transparent ceramics. Journal of Inorganic Materials, 2012, 27(4): 417-421.
[2]	TORKIAN L, AMINI M M, BAHRAMI Z. Synthesis of nano crystalline MgAl2O4 spinel powder by microwave assisted combustion. Journal of Inorganic Materials, 2011, 26(5): 550-554.
[3]	BAYAL N, JEEVANANDAM P. Synthesis of metal aluminate nanoparticles by Sol-Gel method and studies on their reactivity. J. Alloys Compd., 2012, 516: 27-32.
[4]	NADERI M, SHAMIRIAN A, EDRISI M. Synthesis, characterization and photocatalytic properties of nanoparticles CuAl2O4 by pechini method using taguchi statistical design. J. Sol-Gel Sci. Technol., 2011, 58(2): 557-563.
[5]	EDRISI M, TAJIK S, SOLEYMANI M. Synthesis of CuAl2O4 nanoparticles by mixed chelates thermolysis and homogeneous precipitation using solubility difference reactions; taguchi optimization and photocatalytic application. Journal of Materials Science: Materials in Electronics, 2013, 24(10): 3914-3920.
[6]	LIANG C X, LI X Y, QU Z P, et al. The role of copper species on Cu/γ-Al2O3 catalysts for NH3-SCO reaction. Applied Surface Science, 2012, 258(8): 3738-3743.
[7]	SHANG H X, TIAN Y, WANG X T, et al. Photocatalytic H2 evolution from glycerol solution over Bi3+-doped TiO2 nanoparti-cles. Journal of Inorganic Materials, 2012, 27(12): 1283-1288.
[8]	YIN J, ZANG Y S, YUE C, et al. Ag nanoparticle/ZnO hollow nanosphere arrays: large scale synthesis and surface plasmon resonance effect induced Raman scattering enhancement. J. Mater. Chem., 2012, 22(16): 7902-7909.
[9]	ZHAO G, LIU S W, LU Q F. Synthesis of TiO2/Bi2WO6 nanofibers with electrospinning technique for photocatalytic methyl blue degradation. J. Sol-Gel Sci. Technol., 2013, 66(3): 406-412.
[10]	LI Z Q, CHEN X T, XUE Z L. Microwave-assisted synthesis and photocatalytic properties of flower-like Bi2WO6 and Bi2O3-Bi2WO6 composite. J. Colloid Interface sci., 2013, 394: 69-77.
[11]	TIAN G H, CHEN Y J, MENG X Y, et al. Hierarchical composite of Ag/AgBr nanoparticles supported on Bi2MoO6 hollow spheres for enhanced visible-light photocatalytic performance. ChemPlusChem, 2013, 78(1): 117-123.
[12]	BAO Y, YANG Y Q, MA J Z. Research progress of hollow structural materials prepared via templating method. Journal of Inorganic Materials, 2013, 28(5): 459-468.
[13]	ZHAO B, LIN L, CHEN C, et al. Research progress on crystal growth mechanism of titania/titanate nano-powder materials. Journal of Inorganic Materials, 2013, 28(7): 683-690.
[14]	MENG H X, WANG B B, LIU S, et al. Hydrothermal preparation, characterization and photocatalytic activity of TiO2/Fe-TiO2 composite catalysts. Ceram. Int., 2013, 39(5): 5785-5793.
[15]	YIN B, WANG J T, XU W, et al. Preparation of TiO2/mesoporous carbon composites and their photocatalytic performance for methyl orange degradation. New Carbon Materials, 2013, 28(1): 47-54.
[16]	ZHANG L, YAN J H, ZHOU M J, et al. Fabrication and photocatalytic properties of spheres-in-spheres ZnO/ZnAl2O4 composite hollow microspheres. Appl. Surf. Sci., 2013, 268: 237-245.
[17]	ZHANG L, YAN J H, ZHOU M J, et al. Preparation and photocatalytic property of hollow sphere-like ZnO/ZnAl2O4 composite photocatalysts with high specific surface area. Journal of Inorganic Chemistry, 2012, 28(9): 1827-1834.
[18]	LV K, YU J, DENG K, et al. Synergistic effects of hollow structure and surface fluorination on the photocatalytic activity of titania. Journal of Hazardous Materials, 2010, 173(1): 539-543.
[19]	ZHANG Y J, XU Y, LI T, et al. Preparation of ternary Cr2O3-SiC-TiO2 composites for the photocatalytic production of hydrogen. Particuology, 2012, 10(1): 46-50.
[20]	DONG F, SUN Y J, FU M, et al. Room temperature synthesis and highly enhanced visible light photocatalytic activity of porous BiOI/BiOCl composites nanoplates microflowers. Journal of Hazardous Materials, 2012, 219: 26-34.
[21]	LEE S S, BAI H W, LIU Z Y, et al. Novel-structured electrospun TiO2/CuO composite nanofibers for high efficient photocatalytic cogeneration of clean water and energy from dye wastewater. Water Research, 2013, 47(12): 4059-4073.

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

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