Study on the Adsorption of Co(Ⅱ) and Mn(Ⅱ) in Simulated Wastewater by ZIF-67
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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。
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关键词:
- 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.-
Key words:
- MOFs /
- ZIF-67 /
- Adsorption /
- Co(Ⅱ) /
- Mn(Ⅱ)
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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 Qe/(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 Qe/(mg·g−1) 24.39 25.51 k2/(g·mg−1·h−1) 0.09 0.07 R2 0.999 0.999 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 Qm/(mg·g−1) 312.50 200.00 KL/(L·mg−1) 4.78×10−2 14.88×10−2 R2 0.992 0.999 Freundlich KF/(mg·g−1) 26.43 38.19 n 2.22 3.18 R2 0.985 0.952 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 Qe
/(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 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 KB/h−1 0.53 0.50 IB 0.26 0.27 R2 0.999 0.959 Weber-Morris KW/(mg·g−1·h−0.5) 4.41 3.47 IW/(mg·g−1) 12.86 14.63 R2 0.955 0.755 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 -
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