MIL-121的制备优化及对Cu（Ⅱ）的温控吸附脱附性能研究

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

摘要/Abstract

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

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

中图分类号:

X703.1

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.

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.

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

图/表 15

图1 不同溶剂pH下制备出材料的SEM （a） pH=0.5；（b） pH=1.0；（c）对照组（pH=1.4）；（d） pH=2.0；（e） pH=3.0；（f） pH=4.0。

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

图2 不同溶剂pH下制备所得材料的FTIR光谱

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

图3 不同溶剂pH下制备所得材料的XRD

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

图4 不同溶剂pH下制备出的材料对Cu（Ⅱ）的去除率（a）和热脱附率（b）以及温度对相关材料溶液pH的影响（c）

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）

图5 不同温度活化后的MIL-121对Cu（Ⅱ）的去除率（a）和热水脱附效率（b）以及溶液温度对MIL-121-200 ℃中Cu（Ⅱ）脱附效率的影响（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）

图6 MIL-121-200 ℃吸附Cu（Ⅱ）的准一级和准二级反应动力学模型

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

表1 MIL-121-200 ℃吸附Cu（Ⅱ）的准一级和准二级反应动力学模型拟合参数

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）

图7 MIL-121-200 ℃吸附Cu（Ⅱ）的Langmuir和Freundlich等温模型

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

表2 MIL-121-200 ℃吸附Cu（Ⅱ）的Langmuir和Freundlich等温模型拟合参数

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）

图8 共存离子对MIL-121-200 ℃吸附Cu（Ⅱ）性能的影响

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

图9 MIL-121-200 ℃在25 ℃吸附和80 ℃脱附过程中的FTIR变化

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

图10 MIL-121-200 ℃对Cu（Ⅱ）25 ℃吸附和80 ℃脱附示意

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

图11 MIL-121-200 ℃在吸附-脱附循环过程中的性能测定（a）和XRD变化（b）

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

表3 相关材料的吸附、再生和循环次数的比较

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

图12 MIL-121-200 ℃对真实铜电镀废水的柱吸附实验

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

参考文献 22

[1]	许慕舰，计成汉，袁岭，等. 基于混合模型的重金属吸附树脂穿透曲线预测［J］. 工业水处理，2025，45（5）：54-61．
	XU Mujian， JI Chenghan， YUAN Ling，et al. Breakthrough curve prediction of resins for heavy metal adsorption by hybrid model［J］．Industrial Water Treatment，2025，45（5）：54-61．
[2]	计成汉，叶俊荣. UiO-66基材料的制备及去除水体污染物的研究进展［J］. 应用化工，2025，54（6）：1530-1533．
	JI Chenghan， YE Junrong. Preparation of UiO-66 based material and its application in water pollutant removal［J］. Applied Chemical Industry，2025，54（6）：1530-1533．
[3]	JI Chenghan， XU Mujian， YU Hang，et al. Mechanistic insight into selective adsorption and easy regeneration of carboxyl-functionalized MOFs towards heavy metals［J］. Journal of Hazardous Materials，2022，424：127684． doi:10.1016/j.jhazmat.2021.127684
[4]	JI Chenghan， GUO Jiahe， WANG Zhulai，et al. High-efficiency and selective lead capture using thermally regenerable MOF-based adsorbent：Role of thermoresponsive polymer［J］. Journal of Hazardous Materials，2025，495：138875． doi:10.1016/j.jhazmat.2025.138875
[5]	Ranwen OU， ZHANG Huacheng， TRUONG V X，et al. A sunlight-responsive metal-organic framework system for sustainable water desalination［J］. Nature Sustainability，2020，3（12）：1052-1058． doi:10.1038/s41893-020-0590-x
[6]	Ranwen OU， ZHANG Huacheng， WEI Jing，et al. Thermoresponsive amphoteric metal-organic frameworks for efficient and reversible adsorption of multiple salts from water［J］. Advanced Materials，2018，30（34）：1802767． doi:10.1002/adma.201802767
[7]	VOLKRINGER C， LOISEAU T， GUILLOU N，et al. High-throughput aided synthesis of the porous metal-organic framework-type aluminum pyromellitate，MIL-121，with extra carboxylic acid functionalization［J］. Inorganic Chemistry，2010，49（21）：9852-9862． doi:10.1021/ic101128w
[8]	DAI Dingliang， QIU Jianhao， LI Ming，et al ．Construction of two-dimensional BiOI on carboxyl-rich MIL-121 for visible-light photocatalytic degradation of tetracycline［J］. Journal of Alloys and Compounds，2021，872：159711． doi:10.1016/j.jallcom.2021.159711
[9]	JI Chenghan， WU Daowen， LU Junhe，et al. Temperature regulated adsorption and desorption of heavy metals to A-MIL-121：Mechanisms and the role of exchangeable protons［J］. Water Research，2021，189：116599． doi:10.1016/j.watres.2020.116599
[10]	LIU Jianhua， WANG Yumei， GUO Hao，et al ．A novel heterogeneous MOF membrane MIL-121/118 with selectivity towards hydrogen［J］. Inorganic Chemistry Communications，2020，111：107637． doi:10.1016/j.inoche.2019.107637
[11]	WAN Ye， CHEN Chao， XIAO Weiming，et al. Ni/MIL-120：An efficient metal-organic framework catalyst for hydrogenation of benzene to cyclohexane［J］. Microporous and Mesoporous Materials，2013，171：9-13． doi:10.1016/j.micromeso.2013.01.005
[12]	HU Na， HANG Fangxue， LI Kai，et al. Temperature-regulated formation of hierarchical pores and defective sites in MIL-121 for enhanced adsorption of cationic and anionic dyes［J］. Separation and Purification Technology，2023，314：123650． doi:10.1016/j.seppur.2023.123650
[13]	CHEN Shoushun， MUKHERJEE S， LUCIER B E G，et al. Cleaving carboxyls：Understanding thermally triggered hierarchical pores in the metal-organic framework MIL-121［J］. Journal of the American Chemical Society，2019，141（36）：14257-14271． doi:10.1021/jacs.9b06194
[14]	ZHANG Xiaolin， HUANG Ping， ZHU Siyao，et al ．Nanoconfined hydrated zirconium oxide for selective removal of Cu（Ⅱ）-carboxyl complexes from high. salinity water via ternary complex formation［J］. Environmental Science & Technology，2019，53（9）：5319-5327． doi:10.1021/acs.est.9b00745
[15]	WANG Shuo， GENG Xilin， ZHAO Ziyi，et al. Ammoniated-driven green synthesis of charged polyoxometalate supported ionic liquids for exceptional heavy metal remediation in actual industrial wastewater［J］. Water Research，2025，272：122939． doi:10.1016/j.watres.2024.122939
[16]	ABBAS N， HUSNAIN S M， ASIM U，et al. A novel green synthesis of MnO₂-coal composite for rapid removal of silver and lead from wastewater［J］. Water Research，2024，256：121526． doi:10.1016/j.watres.2024.121526
[17]	XIE Yaohui， GUO Xunsheng， WEI Yun，et al. Stable and antibacterial tannic acid-based covalent polymeric hydrogel for highly selective Pb²⁺ recovery from lead-acid battery industrial wastewater［J］. Journal of Hazardous Materials，2024，479：135654． doi:10.1016/j.jhazmat.2024.135654
[18]	BAI Tao， YAO Yuhu， ZHAO Jiaxin，et al. Adsorption performance and mechanism of H₃PO₄-modified banana peel hydrothermal carbon on Pb（Ⅱ）［J］. Separations，2024，11（1）：17． doi:10.3390/separations11010017
[19]	GHAEDI A M， PANAHIMEHR M， NEJAD A R S，et al. Factorial experimental design for the optimization of highly selective adsorption removal of lead and copper ions using metal organic framework MOF-2 （Cd）［J］. Journal of Molecular Liquids，2018，272：15-26． doi:10.1016/j.molliq.2018.09.051
[20]	LI Qimeng， JI Ming， LI Xiang，et al. Efficient co-removal of copper and tetracycline from aqueous solution by using permanent magnetic cation exchange resin［J］. Bioresource Technology，2019，293：122068． doi:10.1016/j.biortech.2019.122068
[21]	HUA Ming， JIANG Yingnan， WU Bian，et al. Fabrication of a new hydrous Zr（Ⅳ） oxide-based nanocomposite for enhanced Pb（Ⅱ） and Cd（Ⅱ） removal from waters［J］. ACS Applied Materials & Interfaces，2013，5（22）：12135-12142． doi:10.1021/am404031q
[22]	AHMADIJOKANI F， TAJAHMADI S， BAHI A，et al ．Ethylenediamine-functionalized Zr-based MOF for efficient removal of heavy metal ions from water［J］. Chemosphere，2021，264：128466． doi:10.1016/j.chemosphere.2020.128466

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