ZIF-8/g-C<sub>3</sub>N<sub>4</sub>复合材料光催化深度氧化NO性能的研究

尹晓荷; 庞吉胜; 娄晨思; 史雨翰; 朱鹏飞; 王传义

doi:10.19906/j.cnki.JFCT.2022046

ZIF-8/g-C₃N₄复合材料光催化深度氧化NO性能的研究

doi: 10.19906/j.cnki.JFCT.2022046

陕西科技大学环境科学与工程学院, 陕西西安 710021

基金项目: 国家自然科学基金（22006097）和陕西省重点研发计划（2022SF-250）资助

详细信息

通讯作者:
Tel：18392586563, E-mail: zhupengfei@sust.edu.cn

中图分类号: TQ034
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出版历程
- 收稿日期: 2022-04-22
- 修回日期: 2022-05-31
- 录用日期: 2022-06-01
- 网络出版日期: 2022-06-23
- 刊出日期: 2022-12-28

Photocatalytic performance of ZIF-8/g-C₃N₄ composite for deep oxidation of NO

School of Environmental Science and Engineering, Shaanxi University of Science and Technology, Xi’an 710021, China

Funds: The project was supported by National Natural Science Foundation of China (22006097) and the Key Research and Program of Shaanxi Province(2022SF-250)

摘要

摘要: 采用热聚合法和原位沉积法分别制备g-C₃N₄、ZIF-8及不同质量比的ZIF-8/g-C₃N₄复合光催化材料，通过X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）等表征手段对其结构性质进行表征。表征结果表明，合成的ZIF-8/g-C₃N₄复合材料没有破坏ZIF-8与g-C₃N₄原始的晶体结构与形貌，且ZIF-8与g-C₃N₄形成了异质结，ZIF-8/g-C₃N₄复合材料的BET比表面积比g-C₃N₄提高了30多倍。光催化氧化去除NO结果表明，12.5%-ZIF-8/g-C₃N₄的NO氧化去除效率最佳，且不生成有毒中间产物NO₂，具有最优异的光催化活性，对于NO的氧化去除率可达55.1%。机理研究表明，基于g-C₃N₄的异质结构不仅抑制了光生载流子的复合，而且由于g-C₃N₄与ZIF-8之间的协同作用，促进了可见光的吸收以及反应物分子NO的吸附，从而提高了复合材料对NO的光催化氧化性能。
- 光催化 /
- 金属有机框架材料 /
- 复合光催化剂 /
- 一氧化氮
Abstract: g-C₃N₄, ZIF-8 and ZIF-8/g-C₃N₄ composite photocatalysts with different mass ratios were prepared by thermal polymerization method and in-situ deposition method, respectively. The structural properties of prepared samples were characterized by using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), and X-ray photoelectron spectroscopy (XPS), etc. The results showed that the ZIF-8/g-C₃N₄ composite did not destroy the original crystal structure and morphology of ZIF-8 and g-C₃N₄, and ZIF-8 formed a heterojunction with g-C₃N₄. The BET specific surface area of ZIF-8/g-C₃N₄ was improved more than 30 times compared with g-C₃N₄. The results of photocatalytic oxidation of NO showed that 12.5%-ZIF-8/g-C₃N₄ exhibited the best removal efficiency of NO and no toxic intermediate NO₂ production, and it had the most excellent photocatalytic activity with the nitric oxide removal efficiency of 55.1%. The mechanism study showed that the formed heterostructure not only inhibited the recombination of photogenerated charge carriers, but also promoted the absorption of visible light and the adsorption of reactant molecular NO due to the synergy between ZIF-8 and g-C₃N₄, thus improving the photocatalytic oxidation performance of NO.
- photocatalysis /
- MOFs /
- composite photocatalyst /
- NO

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FIG. 2032. FIG. 2032.

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图 1 ZIF-8、g-C₃N₄和ZIF-8/g-C₃N₄的XRD谱图

Figure 1 XRD patterns of ZIF-8, g-C₃N₄ and ZIF-8/g-C₃N₄

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图 2 ZIF-8、g-C₃N₄和ZIF-8/g-C₃N₄的傅里叶红外光谱谱图

Figure 2 FT-IR spectra of ZIF-8, g-C₃N₄ and ZIF-8/g-C₃N₄

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图 3 ZIF-8、g-C₃N₄和ZIF-8/g-C₃N₄的紫外-可见漫反射光谱谱图

Figure 3 UV-Vis DRS of ZIF-8, g-C₃N₄ and ZIF-8/g-C₃N₄

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图 4 g-C₃N₄和ZIF-8/g-C₃N₄的光电流响应图（a）与电化学阻抗谱图（b）

Figure 4 Photocurrent responses (a) and EIS (b) of g-C₃N₄ and ZIF-8/g-C₃N₄

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图 5 g-C₃N₄和ZIF-8/g-C₃N₄的光催化活性：NO去除率（（a）,（c））；NO₂的生成量（b）；ZIF-8/g-C₃N₄光催化去除NO的循环活性图（d）

Figure 5 ((a), (c)) Photocatalytic performance of different photocatalyst samples for removal of NO under visible light irradiation; (b) Corresponding amount of NO₂ generated over different photocatalyst samples; (d) Cyclic experiment of ZIF-8/g-C₃N₄ photocatalytic removal of NO

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图 6 g-C₃N₄（（a）, （e））、ZIF-8（（b）, （f））、12.5%-ZIF-8/g-C₃N₄（（c）, （g））和PM-12.5%-ZIF-8/g-C₃N₄（（d）, （h））的SEM图像（（a）−（d））与TEM图像（（e）−（h））和12.5%-ZIF-8/g-C₃N₄的EDS元素分布图（（i）−（l））

Figure 6 SEM ((a)−(d)) and TEM ((e)−(h)) images of g-C₃N₄((a), (e)), ZIF-8((b), (f)), 12.5%-ZIF-8/g-C₃N₄((c), (g)) and PM-12.5%-ZIF-8/g-C₃N₄((d), (h)); Elements mappings ((i)−(l)) of 12.5%-ZIF-8/g-C₃N₄

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图 7 ZIF-8、g-C₃N₄和12.5%-ZIF-8/g- C₃N₄的N₂吸附-脱附曲线（a）和BJH孔径分布（b）

Figure 7 N₂ adsorption-desorption curves (a) and BJH pore size distributions (b) of ZIF-8, g-C₃N₄ and 12.5%-ZIF-8/g- C₃N₄

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图 8 ZIF-8、g-C₃N₄和12.5%-ZIF-8/g-C₃N₄的XPS全谱（a）及高分辨Zn 2p（b）、C 1s（c）和N 1s（d）谱图

Figure 8 XPS profiles of ZIF-8, g-C₃N₄ and 12.5%-ZIF-8/g-C₃N₄ (a) Full scan, (b) Zn 2p, (c) C 1s, (d) N 1s

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图 9 g-C₃N₄、12.5%-ZIF-8/g-C₃N₄和PM-12.5%-ZIF-8/g-C₃N₄的荧光光谱谱图

Figure 9 PL spectra of g-C₃N₄, 12.5%-ZIF-8/g-C₃N₄ and PM-12.5%-ZIF-8/g-C₃N₄

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图 10 ZIF-8和g-C₃N₄的禁带宽度图（a）、莫特-肖特基图（b）及ZIF-8/g-C₃N₄光催化去除NO机理图（c）

Figure 10 (a) Band gaps and (b) Mott-schottky plots of ZIF-8 and g-C C₃N₄, (c) Possible mechanism of photocatalytic NO removal over ZIF-8/g-C₃N₄

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表 1 制备ZIF-8/g-C₃N₄纳米复合材料的原料配比

Table 1 Raw material ratio for preparing ZIF-8/g-C₃N₄ nanocomposite

Zinc acetate	2-methylimidazole	Name
0.5 mmol	2 mmol	6.25%-ZIF-8/g-C₃N₄
1 mmol	4 mmol	12.5%-ZIF-8/g-C₃N₄
2 mmol	8 mmol	25%-ZIF-8/g-C₃N₄
3 mmol	12 mmol	37.5%-ZIF-8/g-C₃N₄
4 mmol	16 mmol	50%-ZIF-8/g-C₃N₄

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表 2 ZIF-8-g-C₃N₄和12.5%-ZIF-8/g-C₃N₄纳米复合材料的比表面积、孔体积和孔径

Table 2 Specific surface areas, pore volumes and pore sizes of g-C₃N₄, ZIF-8 and 12.5%-g-C₃N₄/ZIF-8

Sample	BET specific surface area /(m²·g⁻¹)	Pore volume /(cm³·g⁻¹)	Pore size /nm
ZIF-8	1244.20	0.0573	2.301
g-C₃N₄	8.07	0.0479	28.8231
ZIF-8/g-C₃N₄	260.25	0.0488	2.7986

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