Preparation and optimization of MIL-121 and its performance of temperature-controlled adsorption and desorption of Cu(Ⅱ)

doi:10.19965/j.cnki.iwt.2025-0727

Abstract

Abstract:

The adsorption method has been widely used for the advanced treatment of heavy metal pollutants in water due to the advantages of simple operation, low cost, and high removal efficiency. However, the additional treatment costs, environmental safety risks, and damage to the characteristic structure of materials caused by the commonly used chemical reagent regeneration method have limited the practical application. This study developed a thermally regenerable metal-organic framework(MOFs) material, MIL-121, and analyzed the optimized design of the material through SEM, FTIR, and XRD. The results indicated that the material(MIL-121-200 ℃) synthesized at pH of 1.0 and activation temperature of 200 ℃ exhibited optimal performance with adsorption rate of 99.3% for Cu(Ⅱ)(1.0 mg/L) at 25 ℃ and regeneration rate of 95.8% at 80 ℃. During the consecutive five adsorption-desorption cycles, the adsorption and desorption of Cu(Ⅱ) by MIL-121-200 ℃ was stable. Additionally, the MIL-121-200 ℃ adsorption column achieved an effective treatment volume of approximately 2 000 mL/g for real copper electroplating wastewater, with no significant performance loss observed during three adsorption-hot water desorption cycles.

Key words: heavy metal, adsorbent, MIL-121, Cu(Ⅱ) adsorption, hot water regeneration

摘要：

吸附法因具有操作简便、成本低、去除效率高等优点，已被广泛用于水中重金属污染物的深度处理。但目前普遍采用的化学试剂再生方式会带来额外的成本、不利的环境影响以及材料特征结构的潜在破坏，限制了其实际应用。开发了一种热可再生的金属有机框架（MOFs）材料MIL-121，并通过扫描电子显微镜（SEM）、傅里叶变换红外光谱（FTIR）和X射线衍射仪（XRD）对材料的优化设计结果进行分析。结果表明，pH=1.0，活化温度为200 ℃时合成的MIL-121-200 ℃具有最佳性能：25 ℃时对Cu（Ⅱ）（1.0 mg/L）的去除率达99.3%，80 ℃时再生率达95.8%。在连续5次吸附-解吸循环过程中，MIL-121-200 ℃对Cu（Ⅱ）的吸附和脱附性能稳定。此外，MIL-121-200 ℃吸附柱对真实铜电镀废水的有效处理量达约2 000 mL/g，且3次吸附-热水脱附循环过程中没有明显的处理性能损失。

关键词: 重金属, 吸附剂, MIL-121, Cu（Ⅱ）吸附, 热水再生

CLC Number:

X703.1

Chenghan JI, Weiming ZHANG. Preparation and optimization of MIL-121 and its performance of temperature-controlled adsorption and desorption of Cu(Ⅱ)[J]. Industrial Water Treatment, 2025, 45(12): 38-46.

计成汉, 张炜铭. MIL-121的制备优化及对Cu（Ⅱ）的温控吸附脱附性能研究[J]. 工业水处理, 2025, 45(12): 38-46.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2025-0727

https://www.iwt.cn/EN/Y2025/V45/I12/38

Figures/Tables 15

Fig.1 SEM images of the materials prepared under different solvent pH

Fig.2 FTIR spectra of the materials prepared under different solvent pH

Fig.3 XRD spectra of the materials prepared under different solvent pH

Fig.4 Removal rate of Cu（Ⅱ） by materials prepared with different solvent pH （a），corresponding hot water desorption efficiency（b），and effect of temperature on the solution pH of the relevant materials（c）

Fig.5 Cu（Ⅱ） removal efficiency of MIL-121 activated at different temperatures（a），the corresponding hot water desorption efficiency（b），and effect of solution temperature on the Cu（Ⅱ） desorption efficiency from MIL-121-200 ℃（c）

Fig.6 Pseudo-first-order and pseudo-second-order kinetic models for Cu（Ⅱ） adsorption on MIL-121-200 ℃

Table 1 Fitting parameters of the pseudo-first-order and pseudo-second-order kinetic models for Cu（Ⅱ） adsorption on MIL-121-200 ℃

k ₁/min^-1

k ₂/

（g·mg^-1·min^-1）

Fig.7 Langmuir and Freundlich isotherm models for Cu（Ⅱ） adsorption on MIL-121-200 ℃

Table 2 Fitting parameters of Langmuir and Freundlich isotherm models for Cu（Ⅱ） adsorption on MIL-121-200 ℃

K _F/

（L^1/ ⁿ ·mg^1-1/ ⁿ ·g^-1）

Fig.8 Effect of coexisting ions on the adsorption of Cu（Ⅱ） by MIL-121-200 ℃

Fig.9 Changes in FTIR spectra of MIL-121-200 ℃ during adsorption at 25 ℃ and desorption at 80 ℃

Fig.10 Schematic illustration of MIL-121-200 ℃ adsorption of Cu（Ⅱ） at 25 ℃ and desorption at 80 ℃

Fig.11 Performance（a） and XRD patterns（b） of MIL-121-200 ℃ during the adsorption-desorption cycles

Table 3 Comparison of adsorption，regeneration and cycle times of relevant materials

材料	目标离子	吸附容量/（mg·g^-1）	再生方式	再生效率/%	循环次数	参考文献
POM-SILs 复合材料	Pb²⁺	17.9	1% HNO₃+5% Ca（NO₃）₂	90	10	〔15〕
MnO₂-coal	Pb²⁺	61.9	1 mol/L HCl	75	4	〔16〕
TA@PMAM	Pb²⁺	196.6	H₂SO₄	79.6	5	〔17〕
P-HTC-2.0	Pb²⁺	40.7	0.1 mol/L H₂SO₄	73.5	5	〔18〕
MOF-2（Cd）	Cu²⁺	30.1	0.1 mol/kg HCl +超声	78	3	〔19〕
MCER	Cu²⁺	48	0.01 mol/kg HCl + 0.1 mol/kg NaOH	87.7	5	〔20〕
NZP	Cd²⁺	14.1	0.1 mol/L HNO₃ + 5% Ca（NO₃）₂	95	4	〔21〕
UiO-66-EDA	Cu²⁺	30.2	0.1 mol/L HCl	87	4	〔22〕
MIL-121-200 ℃	Cu²⁺	26.2	80 ℃水	90	5	本研究

Fig.12 Column adsorption experiment of MIL-121-200 ℃ on real copper electroplating wastewater

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