Adsorption Properties of Dyes from Aqueous Solutions by Covalent Organic Frameworks COF-TpPa-1

doi:10.12422/j.issn.1006-396X.2026.03.005

Abstract

Abstract:

Covalent organic frameworks (COFs) are a class of crystalline porous polymers formed by linking several light elements through covalent bonds. They feature large specific surface area, excellent chemical stability, and precisely tunable pore architecture, rendering them highly promising for adsorption applications. In this work, COF-TpPa-1 demonstrated effective performance as an adsorbent for the removal of two representative organic dyes (methyl green and congo red) from aqueous solutions. Comprehensive investigations were performed to analyze the effects of various factors while examining adsorption isotherms, kinetics, and thermodynamics. The results demonstrated that the adsorption of both methyl green and congo red onto COF-TpPa-1 followed the Langmuir isothermal adsorption model, indicating a predominant monolayer adsorption mechanism.Kinetic studies showed excellent accordance with the pseudo-second-order model, indicating chemisorption as the primary adsorption mechanism. The adsorption processes of COF-TpPa-1 for both dyes were endothermic and thermodynamically spontaneous.Remarkable maximum adsorption capacities of 253.17 mg/g for methyl green and 166.39 mg/g for congo red were achieved at 313 K. Furthermore, ethanol treatment enabled efficient dye desorption and adsorbent regeneration.

Key words: Covalent organic frameworks, Congo red, Methyl green, Kinetics, Thermodynamics

摘要：

共价有机骨架材料（COFs）是由几种轻元素以共价键相连而形成的一种结晶性多孔聚合物，具有比表面积大、性能稳定和孔隙结构可调控等优点，在吸附领域具有较大的应用潜力。将COF-TpPa-1作为吸附材料，对水中甲基绿和刚果红两种有机染料进行吸附，研究了影响吸附能力的多种因素以及吸附等温线、吸附动力学和吸附热力学。结果表明，COF-TpPa-1对甲基绿和刚果红的吸附都遵循Langmuir等温吸附模型，即都以单分子层吸附为主；吸附动力学都符合拟二级动力学模型，即主要以化学吸附为主；COF-TpPa-1对两种染料的吸附过程都是吸热且自发的；在温度为313 K的条件下，甲基绿和刚果红在COF-TpPa-1上的最大理论吸附量分别为253.17、166.39 mg/g；乙醇可以有效地脱附染料，使吸附剂再生。

关键词: 共价有机骨架材料, 刚果红, 甲基绿, 吸附动力学, 吸附热力学

CLC Number:

TQ201

Yang XIA, Ningning LIU. Adsorption Properties of Dyes from Aqueous Solutions by Covalent Organic Frameworks COF-TpPa-1[J]. Journal of Petrochemical Universities, 2026, 39(3): 39-47.

夏阳, 刘宁宁. 共价有机骨架材料COF-TpPa-1对水中染料的吸附研究[J]. 石油化工高等学校学报, 2026, 39(3): 39-47.

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URL: https://journal.lnpu.edu.cn/syhg/EN/10.12422/j.issn.1006-396X.2026.03.005

https://journal.lnpu.edu.cn/syhg/EN/Y2026/V39/I3/39

Figures/Tables 11

Fig.1 XRD pattern, FT-IR spectra, SEM image and TEM image of COF-TpPa-1

Fig.2 Effects of adsorbent dose on removal ratio of methyl green and congo red

Fig.3 Effects of initial mass dye concentrations on the adsorption of methyl green and congo red onto COF-TpPa-1

Fig.4 Effects of contact time and temperatures on the adsorption of methyl green and congo red onto COF-TpPa-1

Fig.5 Fitted curves of Langmuir and Freundlich isotherm models for methyl green and congo red adsorption onto COF-TpPa-1

Table 1 Fitted parameters of the isothermal adsorption model at 313 K

染料	Langmuir模型			Freundlich模型
染料	q_m/（mg·g^—1）	K_L/（L·mg^—1）	R²	n	K_F/（mg·g^—1）	R²
甲基绿	253.17	0.014 0	0.998 8	2.585	22.363	0.923 4
刚果红	166.39	0.015 2	0.998 0	1.751	7.187	0.973 4

Fig.6 Pseudo-first-order and pseudo-second-order kinetics plots for methyl green and congo red adsorption onto COF-TpPa-1

Table 2 Fitting parameters of the dynamic model

染料	T/K	q_e，exp/ （mg·g^-1）	拟一级动力学模型			拟二级动力学模型
染料	T/K	q_e，exp/ （mg·g^-1）	q_e，cal/ （mg·g^-1）	k₁/ min^-1	R²	q_e，cal/ （mg·g^-1）	k₂×10³/ （g·mg^-1·min^-1）	R²
	303	79.97	80.09	0.024	0.967 7	94.61	0.32	0.997 3
甲基绿	313	86.75	86.24	0.023	0.975 4	103.20	0.28	0.995 4
	323	89.98	90.42	0.025	0.947 5	107.07	0.27	0.994 1
	303	65.81	72.68	0.024	0.952 8	78.31	0.35	0.995 7
刚果红	313	68.94	64.79	0.022	0.969 8	79.62	0.41	0.998 1
	323	71.67	62.43	0.023	0.928 6	80.40	0.50	0.995 1

Table 3 Thermodynamic parameters at various temperatures

染料	T/K	ΔH/ （kJ·mol^-1）	ΔS/ （J·mol^-1·K^-1）	ΔG/ （kJ·mol^-1）
甲基绿	303	7.39	15.93	-2.57
	313	7.39	15.93	-2.41
	323	7.39	15.93	-2.25
刚果红	303	4.25	18.63	-5.64
	313	4.25	18.63	-5.83
	323	4.25	18.63	-6.01

Fig.7 The structures of methyl green and congo red

Fig.8 Adsorption-desorption cycle experimental results of COF-TpPa-1

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