咪唑基阳离子聚合物对工业废水中钯的高效吸附分离研究

doi:10.6023/A26020047

摘要/Abstract

钯(Pd)作为一种稀有贵金属, 因其独特的物化性质和重要的工业应用而备受关注. 从工业废水中回收钯对于缓解贵金属资源短缺、降低废弃物污染具有关键意义. 基于此, 本研究通过N-烷基化反应制备了两种咪唑阳离子聚合物网络CPNs (CPN-1和CPN-2), 实现了对钯的高效吸附分离. CPN-1与CPN-2对Pd(II)的最大吸附量分别达到243 mg•g⁻¹和234 mg•g⁻¹, 且在3 min内实现吸附平衡. 在多种竞争离子共存下, CPNs对Pd(II)仍表现出优异的选择性, 去除率在83%以上. 同时, CPNs具有良好的可重复使用性, 5次循环后吸附率无显著下降. 吸附机理表明, CPNs对钯的吸附主要是通过Cl⁻与PdCl₄²⁻之间的阴离子交换作用. 此外, CPN-1在模拟钯废水的动态吸附实验中展现出出色的去除率(>90%), 证明了该类材料在钯回收领域的潜在应用价值.

关键词: 阳离子聚合物, 钯回收, 固液吸附, 离子交换, 废水治理

Palladium (Pd), as a rare precious metal, is highly valued due to its unique physical and chemical properties and ubiquitous applications in important industries. However, the use of palladium has several limitations, such as high cost, high toxicity, and the extremely limited availability of natural resources, which cannot meet the increasing industrial demands. Therefore, the recovery of palladium from industrial wastewater plays a crucial role in alleviating the risk of precious metal resource depletion and reducing environmental pollution. In this study, two imidazolium-based cationic polymer networks (CPNs, CPN-1 and CPN-2) with high charge density were prepared by N-alkylation reaction, and used for the recovery of Pd(II) from industrial wastewater. The materials were systematically characterized by Fourier transform infrared (FT-IR) spectroscopy, elemental analysis (EA), Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and scanning electron microscopy (SEM). Systematic adsorption experiments were carried out to investigate the adsorption performance of Pd(II). CPN-1 and CPN-2 exhibit fast adsorption kinetics (within 3 min for equilibrium) and high adsorption capacities (243 mg•g⁻¹ and 234 mg•g⁻¹, respectively). The adsorption behavior is consistent with the Langmuir adsorption isotherm model and the pseudo-second-order kinetic model, indicating that monolayer chemisorption is the predominant adsorption mechanism. In the presence of various cations and anions, CPNs still show excellent removal for Pd(II) with efficiencies over 85% (CPN-1) and 83% (CPN-2). In addition, CPN-1 and CPN-2 have good reusability, with no significant decrease in Pd(II) recovery performance after five cycles. In particular, CPN-1 also shows excellent removal efficiency (>90%) in the dynamic adsorption experiments with simulated palladium wastewater, demonstrating the application potential of CPNs materials in palladium recovery. Finally, energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations reveal that the removal of Pd(II) by CPNs is mainly achieved by anion exchange. This work demonstrates great application potential of CPNs for Pd(II) recovery from industrial wastes.

Key words: cationic polymer, palladium recovery, solid-liquid adsorption, ion exchange, wastewater remediation

引用此文

林雯霞, 周一丹, 林凡, 蔡益民, 冯文. 咪唑基阳离子聚合物对工业废水中钯的高效吸附分离研究[J]. 化学学报, 2026, 84(7): 1067-1076.

Wenxia Lin, Yidan Zhou, Fan Lin, Yimin Cai, Wen Feng. Efficient Adsorption and Separation of Palladium from Industrial Wastewater by Imidazolium Cationic Polymers[J]. Acta Chimica Sinica, 2026, 84(7): 1067-1076.

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图/表 6

图式1. CPN-1和CPN-2的合成路线及对PdCl42−的吸附示意图

Scheme 1. Synthetic routes of CPN-1 and CPN-2 and schematic illustration of their adsorption toward PdCl42−

图1. (a) CPN-1、DIB、TBPT、(b) CPN-2、DIBP的FT-IR光谱; (c) N2吸附/脱附等温线; (d) CPN-1和CPN-2的SEM图和元素分布图; (e) TGA曲线

Figure 1. (a) FT-IR spectra of CPN-1, DIB, TBPT; (b) CPN-2, DIBP; (c) Nitrogen adsorption/desorption isotherms; (d) SEM images and element mappings of CPN-1 and CPN-2; (e) TGA curve

材料	理论值/%			实际值/%
材料	C	H	N	C	H	N
CPN-1	59.94	5.01	14.51	54.12	5.24	13.31
CPN-2	61.00	4.98	12.34	63.32	5.39	12.99

表1. CPN-1和CPN-2的元素含量分布

Table 1. Element content distribution of CPN-1 and CPN-2

图2. (a) pH和(b)温度对CPN-1和CPN-2吸附Pd(II)的影响; (c) 吸附动力学曲线; (d), (e) Langmuir模型拟合的CPN-1和CPN-2的吸附等温线(插图为线性拟合和相关参数); (f) 竞争阴离子和(g) 阳离子对CPN-1和CPN-2吸附Pd(II)的影响; (h) 与其他钯吸附剂的性能比较

Figure 2. (a) The influence of pH and (b) temperature on the adsorption of Pd(II) by CPN-1 and CPN-2; (c) Adsorption kinetics curves; (d), (e) Adsorption isotherms of CPN-1 and CPN-2 fitted by the Langmuir model (insert shows the linear fitting and related parameter); The influence of competing anions (f) and cations (g) on the adsorption of Pd(II) by CPN-1 and CPN-2; (h) Comparison of performance with other palladium adsorbents

图3. (a)不同洗脱液的解吸效率; (b) CPN-1和CPN-2的可重复使用性; (c)动态吸附实验装置和吸附后的柱子图像; (d) PdCl42−分离动态洗脱曲线

Figure 3. (a) Desorption eﬃciency of various eluents; (b) Reusability of CPN-1 and CPN-2; (c) Photo of the dynamic adsorption experimental device (right) and column after adsorption (left); (d) Dynamic elution curve for PdCl42− separation

图4. (a) CPN-1-Pd和(b) CPN-2-Pd的SEM和EDS图像; (c) CPN-1和CPN-1-Pd的全XPS光谱; (d) CPN-1-Pd的Pd 3d XPS图; (e) CPN-1和CPN-1-Pd的N 1s XPS图; (f) CPN-2和CPN-2-Pd的全XPS光谱; (g) CPN-2-Pd的Pd 3d XPS图; (h) CPN-2和CPN-2-Pd的N 1s XPS图; (i) CPN-1、CPN-2和PdCl42−的吸附能(Ea)

Figure 4. SEM and EDS images of (a) CPN-1-Pd and (b) CPN-2-Pd; (c) Full XPS spectra of CPN-1 and CPN-1-Pd; (d) Pd 3d XPS survey of CPN-1-Pd; (e) N 1s XPS survey of CPN-1 and CPN-1-Pd; (f) Full XPS spectra of CPN-2 and CPN-2-Pd; (g) Pd 3d XPS survey of CPN-2-Pd; (h) N 1s XPS survey of CPN-2 and CPN-2-Pd; (i) The adsorption energies (Ea) between CPN-1, CPN-2, and PdCl42−

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