Zn2GeO4微米球的一步合成及其光催化制氢活性

doi:10.15541/jim20160290

无机材料学报 ›› 2017, Vol. 32 ›› Issue (2): 141-147.DOI: 10.15541/jim20160290 CSTR: 32189.14.10.15541/jim20160290

Zn₂GeO₄微米球的一步合成及其光催化制氢活性

杨敏^1,2, 贾晓鹏³, 李秉轲¹, 邓国伟¹, 王琪慧¹, 刘晓旸²

(1. 成都师范学院化学与生命科学学院, 成都611130; 2.吉林大学无机合成与制备化学国家重点实验室, 长春130012; 3. 吉林大学超硬材料国家重点实验室, 长春130012)

收稿日期:2016-05-03 修回日期:2016-06-29 出版日期:2017-02-20 网络出版日期:2017-01-13
作者简介:杨敏(1982–), 女, 博士, 副教授. E-mail：yangmin820525@126.com
基金资助:
国家自然科学基金(21271082);中国博士后第56批面上资助项目(801141080411);四川省教育厅项目(15ZA0328);成都师范学院高层次引进人才专项科研项目(YJRC2015-5)

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

YANG Min^1,2, JIA Xiao-Peng³, LI Bing-Ke¹, DENG Guo-Wei¹, WANG Qi-Hui¹, LIU Xiao-Yang²

(1. Department of Chemistry and Bioscience,Chengdu Normal University, Chengdu 611130, China; 2. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of Chemistry, Jilin University Changchun 130012, China; 3. National Lab of Superhard Materials, Jilin University, Changchun 130012, China)

Received:2016-05-03 Revised:2016-06-29 Published:2017-02-20 Online:2017-01-13
About author:YANG Min. E-mail：yangmin820525@126.com
Supported by:
National Natural Sciences Foundation of China (21271082);China Postdoctoral Science Foundation (801141080411);Sichuan Province Project Education Fund (15ZA0328);Special Project for Introduced Talents of Chengdu Normal University(YJRC2015-5)

摘要/Abstract

摘要：

采用微波辅助水热法一步合成尺寸约为5 μm的Zn₂GeO₄微米球。实验研究了微波水热的反应温度、反应时间、乙酸锌与氧化锗的摩尔比等因素对合成Zn₂GeO₄微米球的影响。采用FE-SEM、TEM、XRD和UV-Vis对合成的微米球进行表征。结果表明, 当乙酸锌：氧化锗为6:2, 微波辐射温度为170℃, 反应时间10 min, 尿素用量3.604 g, 制备的Zn₂GeO₄微米球具有良好的光催化效果。实验测试Zn₂GeO₄微米球比表面积为13 m²/g, 在紫外光辐射下, 在甲醇体系中的光解水产氢速率可达到3.76 mmol/(h·g)。该方法缩短反应时间, 增强了光催化活性。

关键词: Zn2GeO4, 微波水热法, 光催化剂, 微米球

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

中图分类号:

TQ174

杨敏, 贾晓鹏, 李秉轲, 邓国伟, 王琪慧, 刘晓旸. Zn₂GeO₄微米球的一步合成及其光催化制氢活性[J]. 无机材料学报, 2017, 32(2): 141-147.

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.

图/表 11

图1 不同温度反应得到的Zn2GeO4微米球的XRD图谱

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

图2 不同温度反应合成样品的扫描电镜照片

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

图3 在170℃下反应不同时间得到的Zn2GeO4微米球的XRD图谱

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

图4 在170℃下反应不同时间获得的Zn2GeO4微米球的SEM照片

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

图5 不同Zn(CH3COOH)2•H2O和GeO2反应摩尔比合成微米球的SEM照片

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

图6 Zn2GeO4微米球的紫外-可见吸收光谱图

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

图7 Zn2GeO4微米球材料吸附脱附等温线及孔径分布图

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

图8 (a)紫外光照下样品的光催化产氢量和(b)在水溶液和甲醇体系中产氢的速率

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

图9 Zn2GeO4光催化产氢的循环实验

Fig. 9 Photocatalytic hydrogen evolution cycling tests of Zn2GeO4

表1 近期报道的Zn2GeO4光催化材料在甲醇-水体系中紫外灯光照下的分解水产氢速率

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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Zn₂GeO₄微米球的一步合成及其光催化制氢活性

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

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