One-pot Synthesis and Photocatalytic Hydrogen Evolution Properties of Zn2GeO4 Microspheres

doi:10.15541/jim20160290

Abstract

Abstract:

Zn₂GeO₄ microspheres were synthesized via a one-pot microwave-hydrothermal route, Zn₂GeO₄particles with the diameter of about 5 μm can be obtained．The synthesis conditions were investigated by a series of controled experiments, revealing that reaction temperature, reaction time and molar ratio of Zn(CH₃COOH)₂•H₂O to GeO₂ were crucial factors controlling formation and morphology of Zn₂GeO₄ microspheres. The products were characterized by various techniques including field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis). The results showed that Zn₂GeO₄ synthesized at conditions when n(Zn(CH₃COOH)₂·H₂O )/n(GeO₂)=6:2, 3.604 g urea, microwave heating at 170℃ for 10 min exhibited best photo-degradation activity. With specific surface area being 13 m²/g, the Zn₂GeO₄ microspheres showed a stable H₂ evolution rate of 3.76 mmol/(h·g) under UV light irradiation. Data from this study suggest that this method greatly reduces the reaction time and enhances the photocatalytic activity.

Key words: Zn2GeO4, microwave-hydrothermal, photocatalyst, microsphere

CLC Number:

TQ174

YANG Min, JIA Xiao-Peng, LI Bing-Ke, DENG Guo-Wei, WANG Qi-Hui, LIU Xiao-Yang. One-pot Synthesis and Photocatalytic Hydrogen Evolution Properties of Zn₂GeO₄ Microspheres[J]. Journal of Inorganic Materials, 2017, 32(2): 141-147.

Figures/Tables 11

Fig. 1 XRD patterns of Zn2GeO4 microspheres reacted at different temperatures

Fig. 2 SEM images of the products at different reaction temperatures(a) 100℃; (b) 120℃; (c) 140℃; (d)170℃; (e) FESEM image of Zn2GeO4 microspheres constructed of randomly packed nanosheets, and (f) TEM and HRTEM images of the individual Zn2GeO4 microspheres

Fig. 3 XRD patterns of Zn2GeO4 microspheres reacted at 170℃ for different time

Fig. 4 SEM images of Zn2GeO4 microspheres reacted at170℃ for different time (a) 1 min; (b) 5 min; (c) 10 min

Fig. 5 SEM images of the microspheres with molar ratios of Zn(CH3COOH)2 to GeO2

Scheme 1 Schematic illustration of the possible formation process of hierarchical Zn2GeO4 microspheres

Fig. 6 UV-visabsorption spectra of the Zn2GeO4 microspheres (Inset is for the calculation of Eg)

Fig. 7 N2 adsorption-desorption isotherms of Zn2GeO4 microspheres and the corresponding pore size distribution derived from the desorption isotherm

Fig. 8 (a) Photocatalytic hydrogen evolution and (b) hydrogen evolution rate from an aqueous methanol solution over various photocatalysts under exposure to UV lightCatalyst amount：0.075 g; H2O volume：75 mL; CH3OH volume：5 mL

Fig. 9 Photocatalytic hydrogen evolution cycling tests of Zn2GeO4

Table 1 Hydrogen evolution rate of some recently-reported methanol-water solutions under exposure to UV light

Material	Prepare method	Energy gap /eV	photosourc (UV-irradiation)	H₂ evolution rate (mmol·g^-1·h^-1)	Reference
Zn₂GeO₄ microspheres	Micrwave-hydrothermal,urea	4.45	125 W Hg	3.76	In this work
Zn₂GeO₄ nanobundles	Hydrothermal,triethanolamine	4.67	300 W Xe	4.90	[1]
Zn₂GeO₄ nanorods	Microwave-hydrothermal	4.26	125 W Hg	6.24	[1]
Zn₂GeO₄ hollow spheres	Hydrothermal, triethanolamine, Sodium hydrate	4.59	500 W Xe	6.23	[28]
Zn₂GeO₄ nanopowder	Hydrothermal	4.77	150 W Hg	0.43	[29]

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One-pot Synthesis and Photocatalytic Hydrogen Evolution Properties of Zn₂GeO₄ Microspheres

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