高容量双酚A分子印迹聚合物的可控合成及其在环境水样检测中的应用

doi:10.3724/SP.J.1123.2025.04029

摘要/Abstract

摘要：

针对环境水样中双酚A（BPA）迁移污染问题，本研究构建了Co/Ni双金属有机框架（MOF）基分子印迹材料（CoNi-MOF-MIPs）。通过盐酸多巴胺（DA）自聚合策略，在双金属MOF表面构筑选择性识别位点，系统优化功能单体（DA）与模板分子（BPA）的配比，其最佳质量比为5∶4。同时，优化了聚合时间及吸附pH等关键参数，最终确定最佳聚合时间为5 h，最佳吸附pH为4.0。扫描电子显微镜（SEM）表征证实材料具有纳米花状结构，该结构能提供较多的吸附位点。材料的吸附动力学符合拟二级模型（R²=0.987 9），最大吸附量达39.29 mg/g，印迹因子较高（3.48），且经6次重复利用后仍保持93.2%的吸附效率。结合高效液相色谱构建的检测体系在0.17~40μg/mL范围内呈现良好的线性关系（R²=0.997 4），对环境水样的加标回收率为80.3%~91.7%（相对标准偏差<1.8%），该方法的检出限为0.05 μg/mL，可实现对环境水样中BPA的高效富集和检测。本工作所开发的BPA表面分子印迹聚合物具有良好的实际应用能力。

关键词: 分子印迹聚合物, 双酚A, 高效液相色谱, 选择性吸附

Abstract:

Bisphenol A （BPA） is an endocrine-disrupting chemical that mimics estrogen， thereby interfering with human hormonal balance and leading to reproductive abnormalities， developmental disorders， and increased risks of obesity， diabetes， and cancer. Commonly found in plastic products and food packaging materials， BPA can readily leach from packaging under thermal stress or exposure to acidic/alkaline conditions， subsequently migrating into the environment. This results in its widespread presence in surface water， groundwater， and drinking water systems. Prolonged exposure poses significant health threats， while conventional wastewater treatment processes prove inadequate for its complete removal. Therefore， developing an efficient， highly specific， and reusable material for removing BPA from water systems is of substantial practical significance. Molecularly imprinted polymers （MIPs） have emerged as promising candidates for targeted pollutant removal due to their artificially created recognition sites that exhibit both structural and functional complementarity to template molecules. The unique advantages of MIPs， including their exceptional specificity， chemical stability， and reusability， make them particularly suitable for environmental applications. To address the challenge of BPA contamination in water systems， we developed a novel cobalt-nickel bimetallic metal-organic framework-based molecularly imprinted polymer （CoNi-MOF-MIPs） through an innovative surface imprinting approach. The fabrication process involved multiple carefully controlled steps. Initially， a crystalline CoNi-MOF substrate was synthesized as the supporting matrix， providing high surface area and structural stability. Dopamine hydrochloride （DA） was then employed as the functional monomer， which underwent self-polymerization under weakly alkaline conditions to form a polydopamine （PDA） coating while simultaneously immobilizing BPA template molecules through synergistic hydrogen bonding and π-π interactions. Subsequent template removal using an eluent created well-defined recognition cavities on the MOF surface. For comparison， non-imprinted polymers （CoNi-MOF-NIPs） were prepared following identical procedures without BPA addition. Critical synthesis parameters were systematically optimized through comprehensive experiments. The mass ratio of functional monomer to template molecule was determined to be optimal at 5∶4 （DA∶BPA）， while the polymerization duration and adsorption pH were optimized to 5 h and 4.0， respectively. Material characterization revealed crucial structural features： scanning electron microscopy （SEM） images confirmed the preservation of nanoflower-like morphology with hierarchical structures， providing abundant adsorption sites， while Fourier-transform infrared spectroscopy （FT-IR） demonstrated successful imprinting through characteristic peak shifts-notably the O-H stretching vibration migration from 3 443 cm⁻¹ to 3 752 cm⁻¹ and aromatic C=C bending transition from 1 633 cm⁻¹ to 1 457 cm⁻¹. Adsorption performance evaluation demonstrated remarkable efficiency across multiple aspects. Kinetic studies revealed rapid uptake conforming to pseudo-second-order behavior （R²=0.987 9 for CoNi-MOF-MIPs and R²=0.976 8 for CoNi-MOF-NIPs）， reaching equilibrium within 30 min and suggesting that the adsorption process was controlled by the availability of binding sites rather than diffusion limitations. Isotherm analysis showed excellent agreement with the Langmuir model， indicating monolayer adsorption on homogeneous surfaces with a maximum capacity of 39.29 mg/g and an impressive imprinting factor of 3.48. Competitive adsorption experiments against structural analogs （diphenolic acid and phenol） demonstrated exceptional selectivity， with selectivity factors of 5.07 and 7.35 respectively， confirming the material’s ability to specifically recognize BPA in complex matrices. The CoNi-MOF-MIPs maintained 93.2% of their initial adsorption capacity after six consecutive adsorption-desorption cycles， demonstrating excellent reusability. When coupled with high performance liquid chromatography （HPLC）， the developed analytical method exhibited a wide linear detection range （0.17-40 μg/mL， R²=0.997 4） and low detection limit （0.05 μg/mL）. Practical application to environmental water samples spiked at three concentration levels （10， 20， and 30 μg/mL） achieved satisfactory recoveries of 80.3%-91.7% with excellent reproducibility （relative standard deviation<1.8%）. The CoNi-MOF-MIPs material developed in this study combines the exceptional adsorption capacity of bimetallic MOFs with the molecular recognition precision of imprinted polymers. This innovative material demonstrates outstanding performance in both BPA enrichment and detection from environmental water samples， showing great promise for practical applications in water treatment and environmental monitoring.

Key words: molecularly imprinted polymers （MIPs）, bisphenol A （BPA）, high performance liquid chromatography （HPLC）, selective adsorption

中图分类号:

O658

程云, 林宇乐, 田苗苗. 高容量双酚A分子印迹聚合物的可控合成及其在环境水样检测中的应用[J]. 色谱, 2026, 44(1): 92-100.

CHENG Yun, LIN Yule, TIAN Miaomiao. Controlled synthesis of high-capacity bisphenol A molecularly imprinted polymer and its application to the detection of environmental water samples[J]. Chinese Journal of Chromatography, 2026, 44(1): 92-100.

图/表 10

图1 CoNi-MOF-MIPs的制备过程

Fig. 1 Preparation process of CoNi-MOF-MIPs2-MeIM： 2-methylimidazole； CoNi-MOF-MIPs： cobalt-nickel metal organic framework molecularly imprinted polymers； BPA： bisphenol A； DA： dopamine hydrochloride.

图2 （a）DA用量、（b）聚合时间及（c）吸附pH对CoNi-MOF-MIPs/CoNi-MOF-NIPs吸附BPA效果的影响（n=3）

Fig. 2 Effect of （a） DA amount，（b） polymerization time and （c） adsorption pH on the adsorption performance of CoNi-MOF-MIPs/CoNi-MOF-NIPs for BPA （n=3） IF： imprinting factor.

图3 （a）CoNi-MOF和（b）CoNi-MOF@BPA@DA的扫描电镜图

Fig. 3 Scanning electron microscopy （SEM） images of （a） CoNi-MOF and （b） CoNi-MOF@BPA@DA

图4 （a）CoNi-MOF和（b）CoNi-MOF@BPA@DA的红外光谱图

Fig. 4 FT-IR spectra of （a）CoNi-MOF and （b） CoNi-MOF@BPA@DA

图5 （a）动力学吸附图、（b）等温吸附、（c）拟二级动力学拟合曲线和（d）热力学Langmuir模型拟合曲线（n=3）

Fig. 5 （a） Adsorption kinetics diagram，（b） isothermal adsorption，（c） pseudo-second-order kinetic fitting curve， and （d） thermodynamic Langmuir model fitting curve （n=3）

图6 CoNi-MOF-MIPs和CoNi-MOF-NIPs对BPA及两种竞争物的（a）选择性与（b）竞争性吸附考察（n=3）

Fig. 6 Evaluation of （a） selective and （b） competitive adsorption performance of CoNi-MOF-MIPS and CoNi-MOF-NIPs for BPA and two competitive substances （n=3）

图7 CoNi-MOF-MIPs和CoNi-MOF-NIPs的重复使用性（n=3）

Fig. 7 Reusability of CoNi-MOF-MIPs and CoNi-MOF-NIPs （n=3）

表1 环境水样中BPA在3个水平下的加标回收率（n=3）

Table 1 Recoveries of BPA in environmental water samples at three levels （n=3）

Sample	Spiked/（µg/mL）	Detected/（µg/mL）	Recovery/%	RSD/%
Lake water	10	9.17	91.7	0.6
	20	17.95	89.7	0.8
	30	26.45	88.2	1.3
River water	10	8.03	80.3	0.8
	20	16.47	82.3	0.9
	30	24.82	82.7	1.7

图 8 （a）BPA标准溶液和加标（10 μg/mL）湖水样品经CoNi-MOF-MIPs（b）富集前、（c）富集后的色谱图

Fig. 8 Chromatograms of （a） BPA standard solution， spiked lake water sample （10 μg/mL）（b） before enrichment and （c） after enrichment with CoNi-MOF-MIPs

表2 不同吸附剂对BPA分析性能的比较

Table 2 Comparison of analytical performance to BPA with different adsorbents

Adsorbents	Q/（mg/g）	IF	LOD	LOQ	RSD/%	Ref.
rFe₃O₄@ZIF-8@MIP^a	10.10	2.72	0.1 µg/L	—	3.6	［10］
VTTS-MGO@mSiO₂@MIPs^b	16.81	4.18	0.010 µg/L	2.68 µg/L	5.01-5.73	［11］
DES-MIP^c	17.72	2.02	—	—	—	［12］
S-MIPs^d	36.00	1.76	0.0017 mg/L	—	—	［13］
E-TBBPA-MIM^e	—	6.31	—	—	—	［14］
CoNi-MOF-MIPs	39.29	3.48	0.05 µg/mL	0.17 µg/mL	0.60-1.7	this work

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