Ag/AgCl/ZIF-8复合材料的制备及其对NO光催化氧化性能的研究

doi:10.6023/A22060266

摘要/Abstract

采用室温沉淀法合成菱形十二面体晶体结构ZIF-8(一种Zn金属有机框架材料), 然后通过光还原沉积法将Ag/AgCl纳米颗粒沉积于ZIF-8表面, 得到Ag/AgCl/ZIF-8复合光催化剂, 通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、比表面积测试法(BET)、紫外-可见漫反射吸收光谱(UV-Vis DRS)等一系列表征手段对其晶体结构、形貌、比表面积及吸光性能等进行了表征. 以低浓度NO作为目标去除污染物, 系统研究了Ag/AgCl/ZIF-8复合材料对NO的可见光催化氧化性能, 并对其反应机理进行了深入分析. 结果表明: (1) Ag/AgCl/ZIF-8复合材料中Ag⁰表面等离子体共振(SPR)效应增强了可见光的吸收; (2) ZIF-8具有大的比表面积, 使其能富集更多的氧分子和NO分子, 促进生成超氧自由基和NO光催化氧化; (3) 复合材料中光生空穴能够转移到AgCl的表面氧化Cl^-为Cl⁰, Cl⁰具有强氧化性, 一方面促进了NO光催化氧化, 另一方面有效抑制了光生电子-空穴的复合, 提高了催化剂的稳定性.

关键词: 氮氧化物, 光催化氧化, 金属有机框架材料, ZIF-8复合材料

ZIF-8, a subclass of metal-organic frameworks with Zn²⁺ and 2-methylimidazole, featuring high special surface area and easily adjustable structures have exhibit great application potential in photocatalytic reaction. However, ZIF-8 often suffers from short light harvesting range and rapid recombination of photogenerated carriers, resulting in poorer catalytic activity. Here, ZIF-8 was synthesized by a precipitation method, and then Ag/AgCl nanoparticles were deposited on the surface of ZIF-8 by photo-deposition to obtain Ag/AgCl/ZIF-8 composite. The typical synthesis procedure is as follows: 0.2 g of ZIF-8 powder was dispersed in 50 mL of methanol and sonicated for 30 min to make it uniformly dispersed, then 0.1699 g of AgNO₃ (1 mmol) and 0.045 g ZnCl₂were added to the above solution, which was placed on a magnetic stirrer and stirred in the dark for 30 min, followed irradiating it under light for 10 min. The obtained sample was washed several times with methanol and dried under a freeze-drying oven for 12 h. The crystal structure, morphology, specific surface area and light absorption properties were characterized by using X-ray diffractometer (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), specific surface area test method (BET) and UV-Vis diffuse reflection absorption spectra (UV-Vis DRS), respectively. Finally, the photocatalytic oxidation performance of Ag/AgCl/ZIF-8 for NO removal under visible light was systematically studied, and its reaction mechanism was further analyzed. Thus, the resulting Ag/AgCl/ZIF-8 composite showed enhanced NO photocatalytic removal performance, reaching the highest NO removal of 43.5% under 35 min visible light irradiation and better stability compared with the parent ZIF-8. The above results show that: (1) Ag⁰ surface plasmon resonance (SPR) effect in Ag/AgCl/ZIF-8 composite enhances the absorption of visible light; (2) ZIF-8 can enrich more oxygen molecules and NO molecules, promoting the formation of superoxide free radicals and NO photocatalytic oxidation performance with a large specific surface area; (3) the photogenerated holes in the composite can be transferred to the surface of AgCl to oxidate Cl^- to Cl⁰, which possess more strong oxidation ability for improving the photocatalytic oxidation of NO. On the other hand, it effectively inhibits the recombination of photogenerated electrons and holes, which improves the stability of the catalyst.

Key words: nitrogen oxides, photocatalytic oxidation, metal organic framework materials, ZIF-8 composite

引用此文

朱鹏飞, 娄晨思, 史雨翰, 王传义. Ag/AgCl/ZIF-8复合材料的制备及其对NO光催化氧化性能的研究[J]. 化学学报, 2022, 80(10): 1385-1393.

Pengfei Zhu, Chensi Lou, Yuhan Shi, Chuanyi Wang. Study on Preparation of Ag/AgCl/ZIF-8 Composite and Photocatalytic NO Oxidation Performance[J]. Acta Chimica Sinica, 2022, 80(10): 1385-1393.

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图/表 15

图1. (a) ZIF-8, Ag/AgCl, Ag/ZIF-8, AgCl/ZIF-8和AACZ8-0.075的XRD图谱; (b) Ag/AgCl, Ag/ZIF-8和AACZ8-0.075的局部放大XRD图谱

Figure 1. (a) XRD patterns of ZIF-8, Ag/AgCl, Ag/ZIF-8, AgCl/ZIF-8 and AACZ8-0.075; (b) the X-ray diffraction patterns of Ag/AgCl, Ag/ZIF-8 and AACZ8-0.075 were locally amplified

图2. (a, b) ZIF-8与AACZ8-0.075的SEM图像; (c、d) ZIF-8与AACZ8-0.075的TEM图像

Figure 2. (a, b) SEM images of ZIF-8 and AACZ8-0.075; (c, d) TEM images of ZIF-8 and AACZ8-0.075

图3. (a, b) AACZ8-0.075的HRTEM图像

Figure 3. (a, b) HRTEM images of AACZ8-0.075

图4. AACZ8-0.075的EDS元素图

Figure 4. EDS element mappings of AACZ8-0.075

图5. ZIF-8与AACZ8-0.075的N2吸附-脱附等温曲线

Figure 5. N2 adsorption-desorption isotherms of ZIF-8 and AACZ8-0.075

样品	比表面积/ (m²•g^-1)	孔径/nm	孔隙体积/ (cm³•g^-1)
ZIF-8	1270.4993	0.3633	0.551171
AACZ8-0.075	822.8584	0.3621	0.353376

表1. ZIF-8和AACZ8-0.075复合材料的比表面积、孔径和孔体积

Table 1. The specific surface area, pore size and pore volume of ZIF-8 and AACZ8-0.075 composites

图6. ZIF-8和AACZ8-0.075的XPS全谱图(a); 元素高分辨光谱图: (b) C1 s; (c) N 1s; (d) Zn 2p; (e) Cl 2p; (f) Ag 3d

Figure 6. XPS spectra of ZIF-8 and AACZ8-0.075: (a) full spectra, (b) C 1s, (c) N 1s, (d) Zn 2p, (e) Cl 2p, (f) Ag 3d

图7. (a) 样品的紫外-可见吸收光谱图; (b) ZIF-8和AACZ8-0.075的禁带宽度图

Figure 7. (a) UV-Vis absorption spectra of the samples; (b) band gap widths of ZIF-8 and AACZ8-0.075

图8. (a) 样品的光电流曲线图(i-t); (b) 样品的电化学阻抗图(EIS)

Figure 8. Photocurrent graph of the samples (i-t) (a) and electrochemical impedance spectroscopy (EIS) of the samples

图9. 样品的PL发射光谱图

Figure 9. PL spectra of the samples

图10. (a) 光催化NO氧化活性图; (b) 样品AACZ8-0.075的循环反应图

Figure 10. (a) Photocatalytic activity for the removal of NO; (b) cyclic test for the sample AACZ8-0.075

图11. AACZ8-0.075光催化NO氧化的自由基捕获实验图

Figure 11. Free radical trapping experiment on photocatalytic NO oxidation for the sample AACZ8-0.075

图12. (a) DMPO-•OH的ESR谱图; (b) DMPO-•O2-的ESR谱图

Figure 12. (a) The ESR spectra of DMPO-•OH; (b) the ESR spectra of DMPO-•O2-

图13. ZIF-8的Mott-Schottky曲线

Figure 13. The Mott-Schottky plots of ZIF-8

图14. AACZ8-0.075光催化去除NO的机理图

Figure 14. Mechanism diagram of NO removal by AACZ8-0.075 photocatalysis

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