氧化石墨烯/ZIF-7复合材料的制备与性能

何乃普; 张学辉; 赵学瑞; 乔瑶雨; 李雯; 赵晓竹; 郭凤钏; 李宗馨

doi:10.13801/j.cnki.fhclxb.20221228.001

氧化石墨烯/ZIF-7复合材料的制备与性能

doi: 10.13801/j.cnki.fhclxb.20221228.001

1.
兰州交通大学　化学化工学院，兰州 730070
2.
兰州交通大学　研究院，兰州 730070

基金项目: 甘肃省科技计划 (20YF8GA032)

详细信息

通讯作者:
何乃普，博士，教授，硕士生导师，研究方向为智能与功能高分子　E-mail: henaipu@mail.lzjtu.cn

中图分类号: TB333
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出版历程
- 收稿日期: 2022-11-09
- 修回日期: 2022-12-13
- 录用日期: 2022-12-15
- 网络出版日期: 2022-12-29
- 刊出日期: 2023-10-15

Preparation and performance of graphene oxide/ZIF-7 composites

1.
School of Chemistry and Chemical Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China
2.
Research Institute, Lanzhou Jiaotong University, Lanzhou 730070, China

Funds: Science and Technology Plan of Gansu Province (20YF8GA032)

摘要

摘要: 本文采用3种合成路线实现了ZIF-7在氧化石墨烯(GO)上的原位生长，并通过PXRD、FTIR、SEM、TEM和N₂吸附-脱附等对氧化石墨烯/ZIF-7复合材料(GO/ZIF-7，简写为GZR-n，其中n 代表合成路线 I、II、III)进行了表征。研究了合成路线对ZIF-7晶体在GO上的原位生长、结晶度、微观形貌和孔径大小的影响。结果显示：通过3种合成路线均可实现ZIF-7晶体在GO表面及其片层间的原位生长，且其结晶度明显增强，部分ZIF-7晶体被GO包裹。ZIF-7晶体形貌和粒径大小在GZR-n上的原位生长受到合成路线的影响，其中，ZIF-7晶体在GZR-II中呈50 nm的纳米球状颗粒，在GZR-I和GZR-III中则形成200 nm的规则多面体。进一步研究了ZIF-7、GO和GZR-n在不同极性溶剂中的分散性能及其对有机染料的吸附性能和动力学行为。GZR-n在甲醇和氯仿中表现出良好的分散性。与ZIF-7晶体相比，GZR-I、GZR-II和GZR-III对亚甲基蓝的吸附能力分别提高了226%、302%和278%，动力学模拟结果显示，GZR-II和GZR-III对亚甲基蓝的吸附属于化学吸附，而GZR-I对亚甲基蓝的吸附属于物理吸附。
- 氧化石墨烯 /
- 金属有机框架 /
- ZIF-7 /
- 复合材料 /
- 染料吸附
Abstract: ZIF-7 crystals were in situ grown on graphene oxide (GO) by three synthetic routes, and the resulting graphene oxide/ZIF-7 composites (GZR-n) were characterized by PXRD, FTIR, SEM, TEM, and N₂ isothermal adsorption-desorption. The effects of the synthetic routes on the growth, crystallinity, microscopic morphology and pore size of ZIF-7 crystals on GO were investigated. ZIF-7 crystals were grown on the surface and sheet of GO by three synthetic routes. The crystallinity of ZIF-7 crystals on GZR-n was significantly enhanced and some were wrapped by GO. The shape and size of ZIF-7 crystals growing on GZR-n were modulated by the synthesis routes. In particular, the ZIF-7 crystals are spherical particle with a diameter of 50 nm in GZR-II. For GZR-I and GZR-III, the ZIF-7 crystals are regular polyhedron with a size of 200 nm. Additional, their dispersion properties in solvents, adsorption properties and kinetic simulations for organic dyes were explored. GZR-n show good dispersion in methanol and chloroform. Compared with ZIF-7 crystals, the adsorption capacities of GZR-I, GZR-II and GZR-III for methylene blue are increased by 226%, 302% and 278%, respectively. The kinetic simulations indicate that the adsorption of GZR-II and GZR-III for methylene blue are chemisorption and that of GZR-I is physical adsorption.
- graphene oxide /
- metal organic framework /
- ZIF-7 /
- composite materials /
- dye adsorption

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图 1 采用3种合成方法制备氧化石墨烯(GO)/ZIF-7复合材料(GZR-n，其中n为制备过程中的合成路线)

Figure 1. Preparation of graphene oxide (GO)/ZIF-7 composites (GZR-n, where n is the synthetic route in the preparation process) by three synthetic routes

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图 2 GO、ZIF-7晶体和GZR-n的PXRD图谱

Figure 2. PXRD patterns of GO, ZIF-7 crystals and GZR-n

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图 3 GO、ZIF-7晶体和GZR-n的FTIR图谱

Figure 3. FTIR spectra of GO, ZIF-7 crystals and GZR-n

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图 4 ZIF-7晶体和GZR-n的N₂吸附-脱附等温线(a)和孔径分布(b)

Figure 4. N₂ adsorption-desorption isotherms (a) and pore distribution (b) of ZIF-7 crystals and GZR-n

V—Pore volume; w—Pore width; STP—Standard temperature and pressure

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图 5 SEM图像：(a) GO；(b) ZIF-7 crystals；((c), (d)) GZR-I；((e), (f)) GZR-II；((g), (h)) GZR-III

Figure 5. SEM images: (a) GO; (b) ZIF-7 crystals; ((c), (d)) GZR-I; ((e), (f)) GZR-II; ((g), (h)) GZR-III

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图 6 TEM图像：(a) GO；(b) ZIF-7；((c), (d)) GZR-I；((e), (f)) GZR-II；((g), (h)) GZR-III

Figure 6. TEM images: (a) GO; (b) ZIF-7; ((c), (d)) GZR-I; ((e), (f)) GZR-II; ((g), (h)) GZR-III

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图 7 GO、ZIF-7晶体和GZR-n的分散性：(a) 石油醚；(b) 苯；(c) 氯仿；(d) 乙酸乙酯；(e) 甲醇；(f) 乙酸；(g) 水

Figure 7. Solubility and dispersibility of GO, ZIF-7 crystals and GZR-n: (a) Petroleum ether; (b) Benzene; (c) Chloroform; (d) Ethyl acetate; (e) Methanol; (f) Acetic acid; (g) Water

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图 9 GO、ZIF-7晶体和GZR-n对MB吸附的伪一级动力学模拟(a)和伪二级动力学模拟(b)

Figure 9. Pseudo first-order (a) and pseudo second-order (b) kinetics simulation of MB adsorption capacity of GO, ZIF-7 crystals and GZR-n

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图 8 GO、ZIF-7和GZR-n对MB的吸附作用

Figure 8. Adsorption of GO, ZIF-7 and GZR-n for MB

q_t—Adsorption capacity at adsorption time t

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图 10 GO、ZIF-7晶体和GZR-n对MB的吸附量(a)、Langmuir吸附等温线(b)、Freundlich吸附等温线(c)

Figure 10. Adsorption of GO, ZIF-7 and GZR-n for MB (a), Langmuir adsorption isotherm (b) and Freundlich adsorption isotherm (c)

c_e—Concentration at adsorption equilibrium

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表 1 GZR-n的制备

Table 1. Experimental of GZR-n

GZR-n^a	Zn(NO₃)₂·6H₂O/g	BIM/g	Route
GZR-I	0.32	0.79	I
GZR-II	0.80	1.99	II
GZR-III	0.32	0.79	III
Notes: GZR-n^a were prepared in N, N-dimethylformamide (DMF) dispersion of graphene oxide by three routes (The molar ratio of Zn²⁺ to benzimidazole was kept at 4∶25); BIM—Benzimidazole.

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表 2 GZR-n对亚甲基蓝(MB)、甲基橙(MO)、孔雀石绿(MG)的平衡吸附容量q_e

Table 2. Equilibrium adsorption capacity q_e of methylene blue (MB), methyl orange (MO) and malachite green (MG) onto GZR-n

Adsorption	q_e/(mg·g⁻¹)
Adsorption	MB	MO	MG
GO	6.45	9.16	11.29
ZIF-7	3.88	5.56	7.01
GZR-I	13.22	11.90	11.47
GZR-II	16.34	14.61	15.76
GZR-III	15.34	13.48	11.77

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表 3 GO、ZIF-7和GZR-n对MB的吸附动力学参数

Table 3. Adsorption kinetic parameters of GO, ZIF-7 and GZR-n for MB

Sample		GO	ZIF-7	GZR-I	GZR-II	GZR-III
Experimental q_e/(mg·g⁻¹)		6.45	3.88	13.22	16.34	15.34
Calculated q_e/(mg·g⁻¹)		6.38	3.77	12.99	16.34	16.07
Pseudo first-order kinetic	k₁/min	0.869	0.745	0.737	0.841	0.707
Pseudo first-order kinetic	R²	0.960	0.799	0.951	0.848	0.890
Pseudo second-order kinetic	k₂/(g·mg⁻¹·min⁻¹)	0.066	0.085	0.008	0.003	0.003
Pseudo second-order kinetic	R²	0.994	0.979	0.939	0.905	0.895
Notes: R²—Fitting constant; k₁, k₂—Adsorption kinetics constant.

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表 4 GO、ZIF-7和GZR-n对MB的吸附等温线参数

Table 4. Adsorption isotherm parameters of GO, ZIF-7 and GZR-n for MB

Sample	Langmuir adsorption isotherm	Freundlich adsorption isotherm
Sample	R²	K_F	1/n	R²
GO	0.9379	1.884	0.5581	0.8673
ZIF-7	0.7481	1.2432	0.5238	0.7171
GZR-I	0.9843	1.002	1.1167	0.9983
GZR-II	0.8566	1.252	1.1127	0.9972
GZR-III	0.7705	1.1466	1.2329	0.9741
Notes: K_F—Freundlich constant; 1/n—Freundlich isotherm deviates from linearity.

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