Cu-BTC@聚合物复合球的制备及其对水中NaCl的去除性能

doi:10.19965/j.cnki.iwt.2025-0124

摘要/Abstract

摘要：

以Cu²⁺交联的羧甲基纤维素（CMC）/海藻酸钠（SA）聚合物凝胶球为前驱体，采用简单溶剂热法在球体内部原位合成了铜-均苯三甲酸金属有机框架（Cu-BTC）。对Cu-BTC@聚合物（Cu-BTC@CMC/SA）的微观形貌、官能团及晶体结构进行了表征，考察了其吸附去除水中NaCl的性能和机理。结果表明，该复合材料在中性条件（pH=7）对NaCl的吸附效果最佳，且吸附过程迅速，初始20 min内即可达到平衡吸附量的90.7%。该复合材料吸附NaCl的过程符合准二级反应动力学模型和Langmuir模型，符合单分子层化学吸附，在298 K时的最大吸附量高达236.98 mg/g。经过5次循环使用，该复合材料的吸附能力有所下降，但对NaCl的脱附率仍维持在41%以上。经过5级连续吸附后，原溶液中NaCl质量浓度从10 g/L降至0.92 g/L，显示出良好的脱盐能力。机理研究表明，吸附作用主要源于Cu-BTC的强相互作用以及CuCl沉淀的生成。该复合材料无需外部能源即可实现高效脱盐，且具备固液易分离的特性，在节能型海水/苦咸水淡化领域具有较大应用潜力。

关键词: Cu-BTC, 海藻酸钠, 聚合物复合球, 吸附, 海水脱盐

Abstract:

Cu-benzene-1, 3, 5-tricarboxylate metal-organic framework (Cu-BTC) was successfully synthesized in-situ in polymer hydrogel beads by a simple solvothermal method using copper ions-crosslinked polymer hydrogel beads of carboxymethylcellulose (CMC)/sodium alginate (SA) as a precursor. The microscopic morphology, functional groups and crystal structure of Cu-BTC@polymer composite (Cu-BTC@CMC/SA) were characterized, and its performance and mechanism for adsorbing and removing NaCl from water were investigated. The results showed that the composite material had the best adsorption effect on NaCl under neutral conditions (pH=7), and the adsorption process was rapid with 90.7% of the equilibrium adsorption capacity within the initial 20 minutes. The adsorption process of NaCl by the composite material conformed to the pseudo-second-order reaction kinetic model and Langmuir model, and conformed to the monolayer chemical adsorption. The maximum adsorption capacity of NaCl at 298 K was as high as 236.98 mg/g. After 5 cycles, the adsorption capacity of the composite material decreased, while the desorption rate of NaCl remained above 41%. After 5 stages of continuous adsorption, the mass concentration of NaCl in the original solution decreased from 10 g/L to 0.92 g/L, demonstrating good desalination ability. The mechanism of NaCl adsorption might involve the strong interaction of Cu-BTC and the formation of CuCl precipitation. This composite material could achieve efficient desalination without external energy and had the characteristic of easy solid-liquid separation, which had great potential for application in energy-saving seawater/brackish water desalination.

Key words: Cu-BTC, sodium alginate, polymer composite beads, adsorption, seawater desalination

中图分类号:

P747
TQ424

骆华勇, 龚晨, 陈智伦, 曾珏僖, 刘雨, 陈锦文, 徐振华. Cu-BTC@聚合物复合球的制备及其对水中NaCl的去除性能[J]. 工业水处理, 2026, 46(1): 114-121.

Huayong LUO, Chen GONG, Zhilun CHEN, Juexi ZENG, Yu LIU, Jinwen CHEN, Zhenhua XU. Preparation of Cu-BTC@polymer composite beads and their removal performance for NaCl in water[J]. Industrial Water Treatment, 2026, 46(1): 114-121.

https://www.iwt.cn/CN/Y2026/V46/I1/114

图/表 12

图1 CMC/SA-Cu和吸附水中NaCl前后Cu-BTC@CMC/SA的SEM （a，d）CMC/SA-Cu；（b，e）吸附前的Cu-BTC@CMC/SA；（c，f）吸附后的Cu-BTC@CMC/SA。

Fig.1 SEM images of CMC/SA-Cu，and Cu-BTC@CMC/SA before and after adsorption of NaCl in water

图2 CMC/SA-Cu和Cu-BTC@CMC/SA的FTIR谱图

Fig.2 FTIR spectra of CMC/SA-Cu and Cu-BTC@CMC/SA

图3 Cu-BTC@CMC/SA吸附NaCl前后的XRD

Fig.3 XRD spectra of Cu-BTC@CMC/SA before and after NaCl adsorption

图4 溶液pH对Cu-BTC@CMC/SA吸附水中NaCl性能的影响

Fig.4 Effect of solution pH on adsorption of NaCl in water by Cu-BTC@CMC/SA

图5 Cu-BTC@CMC/SA投加量对其吸附水中NaCl性能的影响

Fig.5 Effect of adsorbent dosage on adsorption of NaCl in water by Cu-BTC@CMC/SA

图6 Cu-BTC@CMC/SA吸附NaCl的动力学拟合曲线

Fig.6 Kinetics fitting curves of NaCl adsorption onto Cu-BTC@CMC/SA

表1 Cu-BTC@CMC/SA对水中NaCl的吸附动力学模型拟合参数

Table 1 Fitting parameters of kinetic models for NaCl adsorption in water by Cu-BTC@CMC/SA

动力学模型	参数	数值
准一级反应动力学模型	q _e/（mg·g^-1）	55.62
	k ₁/min^-1	0.175
	R ²	0.951
准二级反应动力学模型	q _e/（mg·g^-1）	57.51
	k ₂/（g·mg^-1·min^-1）	4.98×10^-3
	R ²	0.962
颗粒内扩散模型	k _1d	11.30
	C ₁	6.59
	R ²	0.906
	k _2d	0.14
	C ₂	53.16
	R ²	0.970

图7 Cu-BTC@CMC/SA对水中NaCl的吸附等温线

Fig.7 Isotherms for NaCl adsorption in water by Cu-BTC@CMC/SA

表2 Cu-BTC@CMC/SA对NaCl的等温吸附线拟合参数

Table 2 Fitting parameters of isotherms for NaCl adsorption by Cu-BTC@CMC/SA

吸附等温线模型	参数	温度/K
吸附等温线模型	参数	298	308	318
Langmuir	q _max/（mg·g^-1）	236.98	241.10	241.61
	k _L/（L·mg^-1）	5.71×10^-5	6.21×10^-5	6.91×10^-5
	R ²	0.972	0.961	0.943
Freundlich	k _F	0.922	0.108	0.133
	n	1.354	1.372	1.401
	R ²	0.946	0.931	0.904

图8 Cu-BTC@CMC/SA的再生性能

Fig.8 The regeneration property of Cu-BTC@CMC/SA

图9 原料液剩余盐浓度比例随吸附次数的变化

Fig.9 Variation of salt concentration fraction remaining in feed solution with the number of adsorptions

图10 Cu-BTC@CMC/SA吸附NaCl前后的XPS谱图

Fig.10 XPS spectra of Cu-BTC@CMC/SA before and after NaCl adsorption

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