ZIF-67对模拟废水中Co(Ⅱ)和Mn(Ⅱ)的吸附研究

周义朋; 门金凤; 王晓伟; 杜志辉; 梁成强; 贾铭椿

doi:10.13832/j.jnpe.2022.06.0209

ZIF-67对模拟废水中Co(Ⅱ)和Mn(Ⅱ)的吸附研究

doi: 10.13832/j.jnpe.2022.06.0209

海军工程大学核科学技术学院，武汉，430033

基金项目: 国家自然科学基金（51573208）

详细信息

作者简介:
周义朋（1996—），男，博士研究生，现主要从事放射性废液处理方面的研究，E-mail: 15926279722@139.com

通讯作者:
门金凤，E-mail: mjfmoon2001@sina.com

中图分类号: TL941
计量
- 文章访问数: 202
- HTML全文浏览量: 36
- PDF下载量: 25
- 被引次数: 0
出版历程
- 收稿日期: 2021-11-16
- 修回日期: 2022-07-27
- 刊出日期: 2022-12-14

Study on the Adsorption of Co(Ⅱ) and Mn(Ⅱ) in Simulated Wastewater by ZIF-67

Department of Nuclear Science and Engineering, Naval University of Engineering, Wuhan, 430033, China

摘要

摘要: 为开发出对放射性废液中长寿期活化产物具有高效选择性的吸附剂，在室温下制备了金属-有机框架（MOFs）材料ZIF-67，并对该材料进行了热稳定性测试以及结构的表征。首次考察了初始pH值、吸附时间和溶液初始浓度等因素对ZIF-67吸附Co(Ⅱ)和Mn(Ⅱ)的影响。结果表明：ZIF-67属于微孔材料，具有良好的水热稳定性。在pH为6.0、温度为30℃、初始浓度为500 mg/L的条件下，ZIF-67对Co(Ⅱ)和Mn(Ⅱ)的饱和吸附容量分别达到305.63 mg/g和197.43 mg/g。ZIF-67在混合金属离子溶液中对Co(Ⅱ)、Mn(Ⅱ)和Ni(Ⅱ)具有良好的选择吸附性能。因此，ZIF-67在实际放射性废液中活化产物的处理中有良好的应用前景。
- 金属-有机框架（MOFs） /
- ZIF-67 /
- 吸附 /
- Co(Ⅱ) /
- Mn(Ⅱ)
Abstract: In order to develop an adsorbent with high efficiency and selectivity for long-lived activation products in radioactive liquid waste, metal-organic frameworks (MOFs) material ZIF-67 was prepared at room temperature, and the thermal stability test and structural characterization of the material were carried out. The influence of the initial pH values, adsorption time and initial concentration of the solution on the adsorption of Co(II) and Mn(II) by ZIF-67 was investigated for the first time. The results show that ZIF-67 is a microporous material with good hydrothermal stability. Under the conditions of pH=6.0, temperature of 30℃, and initial concentration of 500 mg/L, the saturated adsorption capacities of ZIF-67 for Co(II) and Mn(II) reached 305.63 mg/g and 197.43 mg/g, respectively. ZIF-67 has adsorption selectivity for Co(II), Mn(II) and Ni(II) in mixed metal ion solution. Therefore, ZIF-67 has a good application prospect in the treatment of activation products in actual radioactive liquid waste.
- MOFs /
- ZIF-67 /
- Adsorption /
- Co(Ⅱ) /
- Mn(Ⅱ)

HTML全文

图 1 ZIF-67样品的SEM图像

Figure 1. SEM Image of ZIF-67 Sample

下载: 全尺寸图片幻灯片

图 2 ZIF-67的TGA测试曲线

Figure 2. TGA Test Curve of ZIF-67

下载: 全尺寸图片幻灯片

图 3 ZIF-67的氮气吸附-脱附等温线

Figure 3. N₂ Adsorption-desorption Isotherm of ZIF-67

下载: 全尺寸图片幻灯片

图 4 ZIF-67的孔径分布

Figure 4. Pore Diameter Distribution of ZIF-67

下载: 全尺寸图片幻灯片

图 5 ZIF-67吸附前后的XRD谱

Figure 5. XRD Patterns of ZIF-67 Before and After Adsorption　　　　　　

下载: 全尺寸图片幻灯片

图 6 溶液初始pH值对吸附容量的影响

Figure 6. Effect of Initial Solution pH Values on Adsorption Capacity

下载: 全尺寸图片幻灯片

图 7 吸附时间对ZIF-67吸附容量的影响

Figure 7. Effect of Adsorption Time on Adsorption Capacity of ZIF-67

下载: 全尺寸图片幻灯片

图 8 溶液初始浓度对ZIF-67吸附容量的影响

Figure 8. Effect of Initial Solution Concentrations on Adsorption Capacity of ZIF-67

下载: 全尺寸图片幻灯片

图 9 ZIF-67对不同金属离子的吸附容量比较

Figure 9. Comparison of Adsorption Capacity of ZIF-67 for Different Metal Ions

下载: 全尺寸图片幻灯片

图 10 ZIF-67对Co(Ⅱ)和Mn(Ⅱ)的分离系数R_L

Figure 10. Separation Coefficient R_L for Co(Ⅱ) and Mn(Ⅱ) on ZIF-67

下载: 全尺寸图片幻灯片

表 1 动力学模型拟合参数

Table 1. Fitting Parameters of Kinetic Model

动力学类型	参数	Co(Ⅱ)	Mn(Ⅱ)
准一级动力学	Q_e/(mg·g⁻¹)	23.47	8.67
	k₁/h⁻¹	0.88	0.37
	R²	0.921	0.960
准二级动力学	Q_e/(mg·g⁻¹)	24.39	25.51
	k₂/(g·mg⁻¹·h⁻¹)	0.09	0.07
	R²	0.999	0.999

下载: 导出CSV

表 2 吸附等温线模型拟合参数

Table 2. Fitting Parameters of Adsorption Isothermal Models

等温吸附模型	参数	Co(Ⅱ)	Mn(Ⅱ)
Langmuir	Q_m/(mg·g⁻¹)	312.50	200.00
	K_L/(L·mg⁻¹)	4.78×10⁻²	14.88×10⁻²
	R²	0.992	0.999
Freundlich	K_F/(mg·g⁻¹)	26.43	38.19
	n	2.22	3.18
	R²	0.985	0.952

下载: 导出CSV

表 3 吸附热力学模型拟合参数

Table 3. Fitting Parameters of Adsorption Thermodynamic Model

离子种类	ΔH⁰/ (kJ·mol⁻¹）	ΔS⁰/ （J·mol⁻¹·K⁻¹）	温度/K	Q_e /(mg·g⁻¹)	ΔG⁰ /(kJ·mol⁻¹)
Co(Ⅱ)	49.50	180.80	283	61.96	−1.67
			293	80.36	−3.47
			303	94.80	−5.28
			313	106.32	−7.09
			323	115.77	−8.90
Mn(Ⅱ)	62.12	229.08	283	77.82	−2.71
			293	91.24	−5.00
			303	105.07	−7.29
			313	117.18	−9.58
			323	122.16	−11.87

下载: 导出CSV

表 4 吸附扩散模型拟合参数

Table 4. Fitting Parameters of Adsorption-diffusion Models

吸附扩散模型类型	参数	Co(Ⅱ)	Mn(Ⅱ)
Boyd	K_B/h⁻¹	0.53	0.50
	I_B	0.26	0.27
	R²	0.999	0.959
Weber-Morris	K_W/(mg·g⁻¹·h^−0.5)	4.41	3.47
	I_W/(mg·g⁻¹)	12.86	14.63
	R²	0.955	0.755

下载: 导出CSV

表 5 ZIFs系列材料的构成与吸附性能比较

Table 5. Comparison of Composition and Adsorption Performance of ZIFs Series Materials

ZIFs种类	中心金属	有机框架	拓扑类型	Co(Ⅱ)/Mn(Ⅱ)吸附容量/(mg·g⁻¹)
ZIF-7	Zn	苯并咪唑	SOD	2.15/0.13
ZIF-11	Zn	苯并咪唑	RHO	3.98/0.21
ZIF-12	Co	苯并咪唑	RHO	3.76/0.52
ZIF-8	Zn	2-甲基咪唑	SOD	19.11/22.46
ZIF-67	Co	2-甲基咪唑	SOD	23.22/24.89
ZIF-90	Zn	咪唑-2-甲醛	SOD	6.59/9.48
RHO—结构为八元环连接的体心立方组成的铝硅酸盐分子筛

下载: 导出CSV

参考文献(22)

[1]	陈小明, 张杰鹏. 金属-有机框架材料[M]. 北京: 化学工业出版社, 2017: 26-28.
[2]	LUAN Y, ZHENG N N, QI Y, et al. Development of a SO₃H-functionalized UiO-66 metal-organic framework by postsynthetic modification and studies of its catalytic activities[J]. European Journal of Inorganic Chemistry, 2014, 2014(26): 4268-4272. doi: 10.1002/ejic.201402509
[3]	KIM S N, YANG S T, KIM J, et al. Post-synthesis functionalization of MIL-101 using diethylenetriamine: a study on adsorption and catalysis[J]. CrystEngComm, 2012, 14(12): 4142-4147. doi: 10.1039/c2ce06608d
[4]	ZHANG Z H, ZHANG J L, LIU J M, et al. Selective and competitive adsorption of azo dyes on the metal-organic framework ZIF-67[J]. Water, Air, & Soil Pollution, 2016, 227(12): 471.
[5]	杨清香,陈从涛,赵翠真,等. 类沸石咪唑酯骨架材料ZIF-67对重金属离子镉、铜和铅的吸附性能研究[J]. 功能材料,2020, 51(2): 2072-2077. doi: 10.3969/j.issn.1001-9731.2020.02.012
[6]	MAHMOODI N M, TAGHIZADEH M, TAGHIZADEH A, et al. Bio-based magnetic metal-organic framework nanocomposite: ultrasound-assisted synthesis and pollutant (heavy metal and dye) removal from aqueous media[J]. Applied Surface Science, 2019, 480: 288-299. doi: 10.1016/j.apsusc.2019.02.211
[7]	LI X Y, GAO X Y, AI L H, et al. Mechanistic insight into the interaction and adsorption of Cr(VI) with zeolitic imidazolate framework-67 microcrystals from aqueous solution[J]. Chemical Engineering Journal, 2015, 274: 238-246. doi: 10.1016/j.cej.2015.03.127
[8]	SU S Z, CHE R, LIU Q, et al. Zeolitic Imidazolate Framework-67: a promising candidate for recovery of uranium (VI) from seawater[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2018, 547: 73-80.
[9]	DU X D, WANG C C, LIU J G, et al. Extensive and selective adsorption of ZIF-67 towards organic dyes: performance and mechanism[J]. Journal of Colloid and Interface Science, 2017, 506: 437-441. doi: 10.1016/j.jcis.2017.07.073
[10]	LI Y, ZHOU K, HE M, et al. Synthesis of ZIF-8 and ZIF-67 using mixed-base and their dye adsorption[J]. Microporous and Mesoporous Materials, 2016, 234: 287-292. doi: 10.1016/j.micromeso.2016.07.039
[11]	HU Z G, PENG Y W, KANG Z X, et al. A modulated hydrothermal (MHT) approach for the facile synthesis of UIO-66-Type MOFs[J]. Inorganic Chemistry, 2015, 54(10): 4862-4868. doi: 10.1021/acs.inorgchem.5b00435
[12]	HU G Z, ZHANG W, CHEN Y T, et al. Removal of boron from water by GO/ZIF-67 hybrid material adsorption[J]. Environmental Science and Pollution Research, 2020, 27(22): 28396-28407. doi: 10.1007/s11356-020-08018-6
[13]	LOPACHIN R M, GAVIN T, DECAPRIO A, et al. Application of the hard and soft, acids and bases (HSAB) theory to toxicant-target interactions[J]. Chemical Research in Toxicology, 2012, 25(2): 239-251. doi: 10.1021/tx2003257
[14]	GUO W L, CHEN R, LIU Y, et al. Preparation of ion-imprinted mesoporous silica SBA-15 functionalized with triglycine for selective adsorption of Co(II)[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2013, 436: 693-703. doi: 10.1016/j.colsurfa.2013.08.011
[15]	ZHU Q, LI Z K. Hydrogel-supported nanosized hydrous manganese dioxide: Synthesis, characterization, and adsorption behavior study for Pb²⁺, Cu²⁺, Cd²⁺ and Ni²⁺ removal from water[J]. Chemical Engineering Journal, 2015, 281: 69-80. doi: 10.1016/j.cej.2015.06.068
[16]	LI H C, CAO X Y, ZHANG C, et al. Enhanced adsorptive removal of anionic and cationic dyes from single or mixed dye solutions using MOF PCN-222[J]. RSC Advances, 2017, 7(27): 16273-16281. doi: 10.1039/C7RA01647F
[17]	CRINI G. Recent developments in polysaccharide-based materials used as adsorbents in wastewater treatment[J]. Progress in Polymer Science, 2005, 30(1): 38-70. doi: 10.1016/j.progpolymsci.2004.11.002
[18]	YUAN G Y, TIAN Y, LIU J, et al. Schiff base anchored on metal-organic framework for Co (II) removal from aqueous solution[J]. Chemical Engineering Journal, 2017, 326: 691-699. doi: 10.1016/j.cej.2017.06.024
[19]	VIEGAS R M C, CAMPINAS M, COSTA H, et al. How do the HSDM and Boyd’s model compare for estimating intraparticle diffusion coefficients in adsorption processes[J]. Adsorption, 2014, 20(5-6): 737-746. doi: 10.1007/s10450-014-9617-9
[20]	HASSANZADEH M, GHAEMY M. Preparation of bio-based keratin-derived magnetic molecularly imprinted polymer nanoparticles for the facile and selective separation of bisphenol A from water[J]. Journal of Separation Science, 2018, 41(10): 2296-2304. doi: 10.1002/jssc.201701452
[21]	PARK K S, NI Z, CÔTÉ A P, et al. Exceptional chemical and thermal stability of Zeolitic Imidazolate frameworks[J]. Proceedings of the National Academy of Sciences of the United States of America, 2006, 103(27): 10186-10191. doi: 10.1073/pnas.0602439103
[22]	JIANG S H, NIE C M, LIN D, et al. The relationship between inductive effect descriptor and the ionization potential for amines, alcohols, ethers, thio-alcohols and thio-ethers[J]. Journal of Molecular Science, 2007, 23(6): 410-415.