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

氧化石墨烯/ZIF-7复合材料的制备与性能

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 (20 YF8 GA032)

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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- 文章访问数: 269
- HTML全文浏览量: 121
- 被引次数: 0
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: 2023-01-03

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(No. 20 YF8 GA032)

摘要

摘要: 金属有机框架(Metal organic frameworks，MOFs)因其大的比表面积和孔隙率、可调节的孔径和可变的功能基团等优点，在水资源净化领域吸引了越来越多的研究。但是MOFs材料在水中分散性差、不能长期稳定存在，对染料的吸附性能也有一定的限度，严重阻碍了它的实际应用。本文通过原位生长法制备了系列氧化石墨烯/ZIF-7复合材料(GZR-n)。实现了ZIF-7晶体在氧化石墨烯表面及其片层间的原位生长，部分ZIF-7晶体被氧化石墨烯包裹。由于氧化石墨烯表面的含氧官能团以及ZIF-7晶体在其表面的均匀装饰，为染料吸附提供了额外的活性位点和结合位点(π-π共轭作用和氢键作用)，同时，复合材料形成的新孔隙，极大地增强了复合材料对染料的吸附性能。其最大吸附量较ZIF-7晶体分别提高了226%、302%和278%。1氧化石墨烯/ZIF-7复合材料的制备、形貌和吸附亚甲基蓝的对比
- 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, FT-IR, 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 graphene oxide were investigated. ZIF-7 crystals were grown on the surface and sheet of graphene oxide by three synthetic routes. The crystallinity of ZIF-7 crystals on GZR-n was significantly enhanced and some were wrapped by graphene oxide. The shape and size of ZIF-7 crystals growing on GZR-n were modulated by the synthesis routes. In particular, the ZIF-7 crystals were spherical particle with a dimeter of 50 nm in GZR-II. For GZR-I and GZR-III, the ZIF-7 crystals were 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 showed 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 were increased by 226%, 302% and 278%, respectively. The kinetic simulations indicated that the adsorption of GZR-II and GZR-III for methylene blue was chemisorption and that of GZR-I was physical adsorption.
- graphene oxide /
- metal organic framework /
- ZIF-7 /
- composite materials /
- dye adsorption

HTML全文

图 1 采用三种合成方法制备石墨烯/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/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 氧化石墨烯(Go)、ZIF-7晶体和GZR-n的PXRD图谱

Figure 2. PXRD patterns of graphene oxide (Go), ZIF-7 crystals and GZR-n

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图 3 Go、ZIF-7晶体和GZR-n的FT-IR光谱图

Figure 3. FT-IR 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. (a) N₂ adsorption-desorption isotherms and (b) pore distribution of ZIF-7 crystals and GZR-n.

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

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

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

Figure 6. TEM images of (a) Go, (b) ZIF-7, (c, d) GZR-I, (e, f) GZR-II and (g, h) GZR-III

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图 7 ZIF-7晶体, Go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 ZIF-7 crystals, Go and GZR-n in polar solutions (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对亚甲基蓝吸附的动力学模拟(a)伪一级动力学模拟和(b)伪二级动力学模拟

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

q_e−Equilibrium adsorption capacity

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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

t − Adsorption time; qt − Adsorption capacity at time t

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图 10 Go、ZIF-7晶体和GZR-n对亚甲基蓝的吸附量(a) Langmuir吸附等温线(b)Freundlich吸附等温线(c)

Figure 10. (a) The adsorption of Go, ZIF-7 and GZR-n for methylene blue, (b) Langmuir adsorption isotherm and (c) Freundlich adsorption isotherm

c_e − Concentration at adsorption equilibrium; q_e − Adsorption capacity at adsorption equilibrium

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表 1 GZR-n的制备

Table 1. Experimental of GZR-n

GZR-n^a	m(Zn(NO₃)₂·6 H₂O)/g	m(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: ^a Go/ZIF-7 composites (GZR-n, where n is the synthetic routes in the preparation process.) were prepared in DMF dispersion of graphene oxide by three routes; The molar ratio of Zn²⁺ to benzimidazole was kept at 4:25.

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表 2 GZR-n对亚甲基蓝、甲基橙、孔雀石绿的平衡吸附容量

Table 2. Adsorption Capacity of MB, MO and 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
Notes: q_e−Equilibrium adsorption capacity

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表 3 Go、ZIF-7和GZR-n对亚甲基蓝的吸附动力学参数

Table 3. The adsorption kinetic parameter of Go, ZIF-7 and GZR-n for methylene blue

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·mmol⁻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; q_e−Equilibrium adsorption capacity; k−Adsorption kinetics constant.

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表 4 Go、ZIF-7和GZR-n对亚甲基蓝的吸附等温线参数

Table 4. The Adsorption isotherm parameters of Go, ZIF-7 and GZR-n for methylene blue

Sample		Go	ZIF-7	GZR-I	GZR-II	GZR-III
Langmuir adsorption isotherm	R²	0.9379	0.7481	0.9843	0.8566	0.7705
Freundlich adsorption isotherm	K_F	1.884	1.2432	1.002	1.252	1.1466
	1/n	0.5581	0.5238	1.1167	1.1127	1.2329
	R²	0.8673	0.7171	0.9983	0.9972	0.9741
Notes: R²−Fittingconstant; K_F−Freundlich constants related to adsorption capacity; n−Freundlich constants related to adsorption strength.

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