基于水滑石前驱体制备ZnCr<sub>2</sub>O<sub>4</sub>-ZnO复合光催化剂及产氢性能

张丽; 戴超华; 粱青满; 阎建辉; 周民杰

基于水滑石前驱体制备ZnCr₂O₄-ZnO复合光催化剂及产氢性能

湖南理工学院化学化工学院, 湖南岳阳 414006

基金项目:

国家自然科学基金 51372080

湖南省自然科学基金面上项目 2017JJ2108

湖南省教育厅重点项目 15A076

详细信息

通讯作者:
周民杰, Tel:18773039728, E-mail:zmj0104@163.com

中图分类号: O614.24
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- 文章访问数: 153
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- 被引次数: 0
出版历程
- 收稿日期: 2017-06-26
- 修回日期: 2017-08-13
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-10-10

Preparation of ZnCr₂O₄-ZnO composite photocatalyst based on the hydrotalcite precursor and its performance in hydrogen production

College of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang 414006, China

Funds:

The project was supported by the National Natural Science Foundation of China 51372080

the Natural Science Foundation of Hunan Provincial of China 2017JJ2108

Scientific Research Foundation of Hunan Provincial Education Department of China 15A076

摘要

摘要: 以研磨水热法合成ZnCr₂O₄-ZnO异质结型光催化剂，对所得样品进行了TG-DTA、XRD、SEM、HRTEM、DRS和N₂吸附-脱附表征分析；在模拟太阳光下，以草酸为牺牲剂对样品的光催化产氢活性进行评价，并分别与共沉淀法、尿素回流法和尿素水热法制备的ZnCr₂O₄-ZnO样品进行比较，探讨了异质结型ZnCr₂O₄-ZnO复合光催化剂的产氢机理。结果表明，四种方法制备的Zn-Cr前驱体都具有一定的水滑石结构，经500℃焙烧后，均为球形纳米粒子，但团聚情况各异，比表面积和孔结构参数有较大差别。其中，研磨水热法所得样品ZnCr₂O₄-ZnO粒子均匀，光电流响应强度最大，产氢效率最高，为0.956 mmol/（h·g_cat），分别是共沉淀法、尿素回流法和尿素水热法制备样品产氢量的2.3、1.5和3.0倍。
- 研磨水热法 /
- ZnCr₂O₄-ZnO /
- 异质结 /
- 光催化产氢
Abstract: ZnCr₂O₄-ZnO composite photocatalyst with heterogeneous structure was synthesized by grinding hydrothermal method and characterized by TG-DTA, XRD, SEM, HRTEM, DRS, and N₂ absorption; its photocatalytic activity in H₂ production was evaluated by using oxalic acid as the sacrificial agent under simulated sunlight irradiation and compared with those of the ZnCr₂O₄-ZnO samples prepared by coprecipitation, urea reflux and urea hydrothermal methods. The results indicate that Zn-Cr precursors prepared by four methods show a certain hydrotalcite structure; the catalyst samples prepared at 500℃ are spherical nanoparticles, but different in agglomeration status, specific surface area and pore structure parameters. The ZnCr₂O₄-ZnO nanoparticles prepared by a grinding hydrothermal method exhibits the optimized photocurrent response and photocatalytic activity; the yield of hydrogen production is 0.956 mmol/(h·g_cat), which is 2.3, 1.5 and 3.0 times higher than that of the catalyst samples prepared by coprecipitation, urea reflux and urea hydrothermal methods, respectively. On the basis of these results, a possible mechanism for the hydrogen production over ZnCr₂O₄-ZnO composite photocatalyst with heterogeneous structure was then proposed.
- grinding hydrothermal method /
- ZnCr₂O₄-ZnO /
- heterojunction /
- photocatalytic hydrogen production

HTML全文

图 1 四种方法所得Zn-Cr-LDHs的TG-DTA曲线

Figure 1 TG-DTA curves of Zn-Cr-LDHs obtained by four methods

a: CP-LDHs; b: UR-LDHs; c: MP-LDHs; d: UH-LDHs

下载: 全尺寸图片幻灯片

图 2 四种方法所得Zn-Cr水滑石(a)及其0500℃焙烧后样品(b)的XRD谱图

Figure 2 XRD patterns of Zn-Cr-LDHs (a) and Zn-Cr-LDHs calcined at 500℃(b) prepared by four methods

下载: 全尺寸图片幻灯片

图 3 四种方法所得Zn-Cr-LDHs在500℃焙烧后样品的SEM照片

Figure 3 SEM images of Zn-Cr-LDHs calcined at 500℃

(a): CP-500; (b): UR-500; (c): MP-500; (d): UH-500

下载: 全尺寸图片幻灯片

图 4 MP-500样品的HRTEM照片和EDS谱图

Figure 4 HRTEM images ((a), (b)) and EDS spectra (c) of the MP-500 sample

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图 5 四种方法所得Zn-Cr-LDHs在500℃焙烧后样品的氮气吸附-脱附等温线(a)和孔径分布曲线(b)

Figure 5 Nitrogen adsorption-desorption isotherms (a) and pore size distribution curves (b) of Zn-Cr-LDHs calcined at 500℃

a: CP-500; b: UR-500; c: MP-500; d: UH-500

下载: 全尺寸图片幻灯片

图 6 四种方法所得Zn-Cr-LDHs在500℃焙烧后样品的紫外-可见漫反射光谱图

Figure 6 UV-vis diffuse reflectance spectra of Zn-Cr-LDHs calcined at 500℃

a: CP-500; b: UR-500; c: MP-500; d: UH-500

下载: 全尺寸图片幻灯片

图 7 制备方法对光催化产氢活性的影响

Figure 7 Effect of the preparation method on the photocatalytic performance in hydrogen production

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图 8 MP-500样品的光催化产氢稳定性

Figure 8 Stability of the MP-500 photocatalysts in hydrogen production

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图 9 四种方法所得样品在模拟太阳光下的光电流响应

Figure 9 Photocurrent response of the samples prepared by four methods under simulated sunlight irradiation

a: CP-500; b: UR-500; c: MP-500; d: UH-500

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图 10 ZnCr₂O₄-ZnO电荷分离与光催化产氢机理示意图

Figure 10 Schematic diagram of the charge separation and mechanism of photocatalytic H₂ evolution over ZnCr₂O₄-ZnO

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表 1 四种方法所得Zn-Cr-LDHs在500℃焙烧样品的比表面积和孔结构

Table 1 Specific surface area and pore-structure data of the samples prepared by four methods after calcinations at 500℃

Sample A_BET / (m²·g^-1) Average pore width d/nm Pore volume v/ (cm³·g^-1)

CP-500 81.3 18.6 0.38

UR-500 57.3 15.9 0.23

MP-500 53.3 22.8 0.31

UH-500 49.8 17.0 0.21

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