ZIF-8/TiO2复合介观晶体的制备及光催化活性

doi:10.15541/jim20240043

无机材料学报 ›› 2024, Vol. 39 ›› Issue (8): 937-944.DOI: 10.15541/jim20240043

ZIF-8/TiO₂复合介观晶体的制备及光催化活性

马彬彬¹(), 钟婉菱², 韩涧¹, 陈椋煜¹, 孙婧婧¹, 雷彩霞¹^,²()

1.厦门理工学院材料科学与工程学院，福建省功能材料及应用重点实验室，厦门 361024
2.广西大学资源环境与材料学院，南宁 530004

收稿日期:2024-01-22 修回日期:2024-03-13 出版日期:2024-08-20 网络出版日期:2024-03-30
通讯作者: 雷彩霞, 副研究员. E-mail: leicx@xmut.edu.cn
作者简介:马彬彬(1997-), 男, 硕士研究生. E-mail: 949843122@qq.com
基金资助:
福建省自然科学基金项目(2022J011265);厦门理工学院科学技术研究项目(303021002)

ZIF-8/TiO₂ Composite Mesocrystals: Preparation and Photocatalytic Activity

MA Binbin¹(), ZHONG Wanling², HAN Jian¹, CHEN Liangyu¹, SUN Jingjing¹, LEI Caixia¹^,²()

1. School of Materials Science and Engineering, Xiamen University of Technology, Xiamen 361024, China
2. School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China

Received:2024-01-22 Revised:2024-03-13 Published:2024-08-20 Online:2024-03-30
Contact: LEI Caixia, associate professor. E-mail: leicx@xmut.edu.cn
About author:MA Binbin (1997-), male, Master candidate. E-mail: 949843122@qq.com
Supported by:
Natural Science Foundation of Fujian Porvince(2022J011265);Sci & Tech Research Foundation of Xiamen University of Technology(303021002)

摘要/Abstract

摘要：

TiO₂的微观形貌、颗粒尺寸及比表面积是影响其光催化活性的重要因素, 介观晶体是一类由无机纳米粒子沿着相同的结晶轴方向有序排列的超结构材料, 在光催化领域具有重要的研究价值。本工作分别以六氟钛酸铵和硼酸为钛源和氟离子捕获剂, 以无水乙醇和去离子水的混合溶液为溶剂, 采用简单绿色的方法制备了NH₄TiOF₃介观晶体前驱体, 然后用硼酸溶液酸洗, 使NH₄TiOF₃介观晶体通过拓扑转变形成TiO₂介观晶体。最后采用沸石咪唑骨架材料ZIF-8纳米粒子对TiO₂介观晶体进行修饰, 制备了ZIF-8/TiO₂复合介观晶体材料, 并研究了其光催化降解亚甲基蓝的活性。实验结果表明, ZIF-8纳米粒子能够均匀生长在TiO₂介观晶体表面, 形成比较致密的包覆层。ZIF-8/TiO₂复合介观晶体光催化剂具有较高的比表面积和较窄的禁带宽度, 其光生电子和空穴的分离效率得到一定程度的提高。其中, 样品M-TiZIF-2(加入4 mmol硝酸锌的复合介观晶体)展现出最高的光催化活性, 其一级反应速率是TiO₂介观晶体的42倍, 是ZIF-8单元材料的16倍。总之, 在ZIF-8纳米粒子和TiO₂介观晶体的协同作用下, ZIF-8/TiO₂复合介观晶体材料显示出更优异的光催化性能。

关键词: TiO₂介观晶体, ZIF-8纳米粒子, 光催化, 复合介观晶体

Abstract:

Microstructure, particle size and specific surface area of TiO₂ are crucial factors influencing its photocatalytic activity. Mesocrystals represent a type of superstructural material formed by inorganic nanoparticles aligned along a common crystallographic axis, holding significant research potential in the field of photocatalysis. This study employed ammonium hexafluorotitanate and boric acid as titanium precursor and fluorine ion scavenger, respectively, and used a blend of anhydrous ethanol and deionized water as reaction medium. NH₄TiOF₃ mesocrystals precursors were prepared by a facile green method. Subsequently, washing with boric acid solution enabled the transformation of NH₄TiOF₃ mesocrystals into TiO₂ mesocrysals through topotaxial conversion. Ultimately, the TiO₂ mesocrystals were functionalized with ZIF-8 nanoparticles, and the photocatalytic degradation activity of the obtained ZIF-8/TiO₂ composite mesocrystals was studied. The experimental results shows that ZIF-8 nanoparticles can uniformly nucleate on the surface of TiO₂ mesocrystals, resulting in a relatively dense coating layer. ZIF-8/TiO₂ composite photocatalyst exhibits a higher specific surface area and a narrower band gap. Meanwhile, the separation efficiency of photogenerated electrons and holes is also improved to a certain extent. Notably, the sample M-TiZIF-2 (with addition of 4 mmol Zn(NO₃)₂) demonstrated superior photocatalytic activity, and achieved a first-order reaction rate of 42-fold that of TiO₂mesocrystals and 16-fold that of pristine ZIF-8 nanoparticles. In conclusion, the synergistic effect of ZIF-8 nanoparticles and TiO₂ mesocrystals significantly augments the photocatalytic performance of the ZIF-8/TiO₂ composite mesocrystal materials.

Key words: TiO₂ mesocrystal, ZIF-8 nanoparticle, photocatalysis, composite mesocrystal

中图分类号:

TB332

马彬彬, 钟婉菱, 韩涧, 陈椋煜, 孙婧婧, 雷彩霞. ZIF-8/TiO₂复合介观晶体的制备及光催化活性[J]. 无机材料学报, 2024, 39(8): 937-944.

MA Binbin, ZHONG Wanling, HAN Jian, CHEN Liangyu, SUN Jingjing, LEI Caixia. ZIF-8/TiO₂ Composite Mesocrystals: Preparation and Photocatalytic Activity[J]. Journal of Inorganic Materials, 2024, 39(8): 937-944.

图/表 10

图1 样品的XRD图谱

Fig. 1 XRD patterns of the samples

图2 样品的SEM微观形貌

Fig. 2 SEM morphologies of the samples (a) M-TiO2; (b) ZIF-8; (c) M-TiZIF-1; (d) M-TiZIF-2; (e) M-TiZIF-3; (f) M-TiZIF-4

图3 样品的TEM照片

Fig. 3 TEM images of the samples (a, b) M-TiO2; (c, d) M-TiZIF-2

图4 样品的氮气吸附-脱附曲线(a)、孔径分布图(b)、比表面积(c)和孔体积(d)

Fig. 4 (a) Nitrogen adsorption-desorption curves, (b) pore size distributions, (c) specific surface areas, and (d) pore volumes of the samples Colorful figures are available on website

图5 样品的(a)固体紫外-可见漫反射光谱图和(b)带隙能(αhν)1/2与能带(hν)的关系曲线

Fig. 5 (a) UV-Vis diffuse reflectance spectra and (b) relationship between band gap energy (αhν)1/2 and energy (hν) of the samples Colorful figures are available on website

图6 亚甲基蓝溶液被不同光催化剂样品降解后的紫外-可见吸收光谱图(a~f), 降解率随时间的变化曲线(g)和降解曲线拟合图(h)

Fig. 6 (a-f) UV-Vis spectra of methylene blue solution degraded by different catalysts under illumination, (g, h) changes of (g) degradation rate and (h) fitted plots of ln(Ct/C0) with time Colorful figures are available on website

图7 M-TiO2、ZIF-8和M-TiZIF-2的光电流-时间曲线(a)和电化学交流阻抗Nyquist曲线(b)

Fig. 7 (a) Photocurrent-time curves and (b) Nyquist curves of M-TiO2, ZIF-8 and M-TiZIF-2

图8 M-TiO2、ZIF-8和M-TiZIF-2的PL图谱

Fig. 8 PL spectra for M-TiO2, ZIF-8 and M-TiZIF-2 Colorful figure is available on website

图9 M-TiZIF-2四次循环光催化降解亚甲基蓝的降解率曲线

Fig. 9 Degradation rate curves of methylene blue by four- cycle photocatalytic degradation of sample M-TiZIF-2

图10 M-TiZIF-2光催化剂在循环降解亚甲基蓝(a, b)前(c, d)后的SEM照片

Fig. 10 SEM images of M-TiZIF-2 photocatalyst (a, b) before and (c, d) after cyclic degradation of methylene blue

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ZIF-8/TiO₂复合介观晶体的制备及光催化活性

ZIF-8/TiO₂ Composite Mesocrystals: Preparation and Photocatalytic Activity

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