海藻酸钠/微晶纤维素复合水凝胶对水中甲基橙和亚甲基蓝的吸附性能与机理

doi:10.16085/j.issn.1000-6613.2023-1028

化工进展 ›› 2024, Vol. 43 ›› Issue (8): 4681-4693.DOI: 10.16085/j.issn.1000-6613.2023-1028

• 资源与环境化工 • 上一篇

海藻酸钠/微晶纤维素复合水凝胶对水中甲基橙和亚甲基蓝的吸附性能与机理

武哲¹(), 曲树光², 冯练享², 曾湘楚¹()

^1.河池学院广西蚕桑生态学与智能化技术应用重点实验室，广西河池 546300
^2.齐河力厚化工有限公司，山东德州 251100

收稿日期:2023-06-21 修回日期:2023-09-16 出版日期:2024-08-15 发布日期:2024-09-02
通讯作者: 曾湘楚
作者简介:武哲（1993—），女，硕士，研究方向为生物质功能材料。E-mail：hcxywz75@163.com。
基金资助:
2024年度中国博士后科学基金第75批面上项目(2024M751270);2023年河池市本级财政科技计划(河科AC231107);2023年度广西高校中青年教师科研基础能力提升项目(2024KY0623);河池学院2023年高层次人才科研启动项目(2023GCC015);广西现代蚕桑丝绸协同创新中心2023年开放课题(2023GXCSSC03)

Adsorption performance and mechanism of sodium alginate/microcrystalline cellulose composite hydrogel for aqueous methyl orange and methylene blue

WU Zhe¹(), QU Shuguang², FENG Lianxiang², ZENG Xiangchu¹()

^1.Guangxi Key Laboratory of Sericulture Ecology and Applied Intelligent Technology, Hechi University, Hechi 546300, Guangxi, China
^2.Qihe Leahou Chemical Co. , Ltd. , Dezhou 251100, Shandong, China

Received:2023-06-21 Revised:2023-09-16 Online:2024-08-15 Published:2024-09-02
Contact: ZENG Xiangchu

摘要/Abstract

摘要：

以海藻酸钠（SA）和微晶纤维素（MCC）为原料，合成海藻酸钠/微晶纤维素复合水凝胶（SA/MCC），对制备的复合水凝胶进行结构表征，并研究其对水中甲基橙（MO）和亚甲基蓝（MB）的吸附性能、模型和机理。结果表明，SA/MCC-20去除MO和MB的最佳pH分别为2和12，吸附模型更符合拟二级模型和Langmuir模型，最大吸附容量可达331.25mg/g、253.31mg/g。通过改变水溶液的pH，MO和MB均可在SA/MCC-20表面实现有效的吸附和解吸从而回收利用。经过5次吸附-解吸循环后，在最佳pH下SA/MCC-20对MO和MB的解吸率仍达91.52%和85.41%。SA/MCC对MO和MB具有较强的吸附能力，吸附机理主要包括静电吸引、范德华力、氢键作用、π-π堆积、孔扩散、孔填充等，并以化学吸附为主，物理吸附为辅。

关键词: 吸附剂, 海藻酸钠, 微晶纤维素, 水凝胶, 偶氮染料

Abstract:

A sodium alginate/microcrystalline cellulose (SA/MCC) composite hydrogel was synthesized using sodium alginate (SA) and microcrystalline cellulose (MCC) as raw material. The structure of the prepared hydrogel was characterized, and the adsorption properties, model and mechanism of the hydrogel for aqueous methyl orange (MO) and methylene blue (MB) were studied. The results showed that the optimal pH of SA/MCC-20 removing MO and MB were 2 and 12, respectively. The adsorption model was more consistent with the pseudo-second-order model and Langmuir model, and the maximum adsorption capacity of MO and MB could reach 331.25mg/g and 253.31mg/g, respectively. By changing the pH of the aqueous solution, both MO and MB could achieve effective adsorption and desorption on SA/MCC-20 for recycling. After 5 times of sorption-desorption cycles, the desorption efficiency of MO and MB of SA/MCC-20 remained 91.52% and 85.41% at optimal pH. SA/MCC possessed excellent adsorption capacity for MO and MB, and the adsorption mechanism mainly included electrostatic attraction, van der Waals force, hydrogen bonding, π-π stacking, pore diffusion and filling, etc, and chemisorption played a leading role with the auxiliary of physical adsorption.

Key words: adsorbent, sodium alginate, microcrystalline cellulose, hydrogel, azo dye

中图分类号:

O636.9

武哲, 曲树光, 冯练享, 曾湘楚. 海藻酸钠/微晶纤维素复合水凝胶对水中甲基橙和亚甲基蓝的吸附性能与机理[J]. 化工进展, 2024, 43(8): 4681-4693.

WU Zhe, QU Shuguang, FENG Lianxiang, ZENG Xiangchu. Adsorption performance and mechanism of sodium alginate/microcrystalline cellulose composite hydrogel for aqueous methyl orange and methylene blue[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4681-4693.

图/表 16

图1 水凝胶的X射线衍射谱图、傅里叶变换红外光谱、扫描电镜图和N2吸附-解吸曲线

图2 四种水凝胶对MO、MB的去除率和脱色效果

图3 pH对甲基橙和亚甲基蓝吸附容量的影响

图4 吸附动力学及拟一级动力学、拟二级动力学和Weber-Morris模型拟合

表1 MO和MB的吸附动力学参数

染料	Q_e,exp/mg·g^-1	拟一级动力学模型			拟二级动力学模型
染料	Q_e,exp/mg·g^-1	Q_e,cal/mg·g^-1	k₁/min^-1	R₁²	Q_e,cal/mg·g^-1	k₂/g·mg^-1·min^-1	R₂²
MO	287.86	217.56	1.64×10^-3	0.82814	267.22	1.92×10^-5	0.99488
MB	218.18	198.57	1.54×10^-3	0.87415	214.09	1.78×10^-5	0.99458

表2 内扩散模型特征参数

染料	k_i,1	c₁	R²_i,1	k_i,2	c₂	R²_i,2	k_i,3	c₃	R²_i,3
MO	18.9747	-58.3997	0.9952	7.8893	96.8279	0.9954	0.9894	263.0684	0.8406
MB	14.3116	-51.5588	0.9994	6.6769	57.6226	0.9837	1.8811	172.9448	0.8999

图5 SA/MCC-20对MO和MB的吸附等温线、拟合模型及吸附热力模型

表3 等温模型拟合参数

染料	Q_m,exp	Langmuir模型			Freundlich模型
染料	Q_m,exp	Q_m,exp/mmol·g^-1	K_L/L·mg^-1	R_L²	K_F/mg·g^-1·L^1/ⁿ ·mg^-1/ⁿ	n	R_F²
MO	331.25	322.82	0.01089	0.99704	29.14527	2.73950	0.94719
MB	253.31	248.43	0.01452	0.99304	30.9725	3.12315	0.94020

表4 吸附热力学参数

染料	T/K	∆G/kJ·mol^-1	∆H/kJ·mol^-1	∆S/kJ·mol^-1·K^-1
MO	293	-3.58	6.07	32.92
	303	-3.98
	313	-4.24
MB	293	-3.31	3.41	22.95
	303	-3.58
	313	-3.77

图6 SA/MCC-20对MO和MB的再吸附能力和实际应用中的去除能力

图7 SA/MCC-20吸附前的XPS谱图

图8 SA/MCC-20吸附MO后的XPS谱图

图9 SA/MCC-20吸附MB后的XPS谱图

图10 SA/MCC-20吸附MO/MB后的XPS谱图

表5 XPS高分辨率谱图

SA/MCC-20			SA/MCC-20-MO			SA/MCC-MB			SA/MCC-MO/MB
吸收峰	结合能/eV	含量/%	吸收峰	结合能/eV	含量/%	吸收峰	结合能/eV	含量/%	吸收峰	结合能/eV	含量/%
C 1s						C 1s
C—C/C—H	284.8	76.9	C—C/C—H	284.8	38.1	C—C/C—H	284.8	69.9	C—C/C—H	284.8	36.5
C—O	286.3	13.1	C—O	286.5	40.0	C—O	286.4	16.8	C—O	286.4	40.2
C＝O	288.2	10.0	C $̿$ O	288.3	21.5	C $̿$ O	288.6	13.3	C $̿$ O	288.2	23.3
O 1s						O 1s
C $̿$ O	531.0	48.1	C $̿$ O	531.0	28.8	C $̿$ O	531.0	28.8	C $̿$ O	531.0	27.9
C—O	532.6	26.9	C－O	532.1	36.5	C—O	532.1	36.5	C—O	532.4	44.2
—OH	533.4	22.6	—OH	533.3	34.7	—OH	533.3	34.7	—OH	533.5	27.9
H₂O	536.2	2.4	—	—	—
N 1s						N 1s
			C $̿$ N	399.5	41.4	C $̿$ N	399.5	65.8	C $̿$ N	399.5	32.8
			C—N	400.4	44.1	C—N	400.4	19.1	C—N	400.3	54.6
			N $̿$ N	402.3	14.5	N $̿$ N	401.8	15.1	N $̿$ N	402.0	12.6
S 2p						S 2p
			C—S 2p_3/2	164.2	21.8	C—S 2p_3/2	163.6	55.1	C—S 2p_3/2	164.1	46.8
			C—S 2p_1/2	165.5	21.8	C—S 2p_1/2	164.9	55.1	C—S 2p_1/2	165.4	46.8
			SO₃^- 2p_3/2	168.4	78.2	SO₃^- 2p_3/2	168.0	44.9	SO₃^- 2p_3/2	168.3	53.2
			SO₃^- 2p_3/2	169.7	78.2	SO₃^- 2p_3/2	169.3	44.9	SO₃^- 2p_3/2	169.6	53.2

表5 XPS高分辨率谱图

SA/MCC-20			SA/MCC-20-MO			SA/MCC-MB			SA/MCC-MO/MB
吸收峰	结合能/eV	含量/%	吸收峰	结合能/eV	含量/%	吸收峰	结合能/eV	含量/%	吸收峰	结合能/eV	含量/%
C 1s						C 1s
C—C/C—H	284.8	76.9	C—C/C—H	284.8	38.1	C—C/C—H	284.8	69.9	C—C/C—H	284.8	36.5
C—O	286.3	13.1	C—O	286.5	40.0	C—O	286.4	16.8	C—O	286.4	40.2
C＝O	288.2	10.0	C $̿$ O	288.3	21.5	C $̿$ O	288.6	13.3	C $̿$ O	288.2	23.3
O 1s						O 1s
C $̿$ O	531.0	48.1	C $̿$ O	531.0	28.8	C $̿$ O	531.0	28.8	C $̿$ O	531.0	27.9
C—O	532.6	26.9	C－O	532.1	36.5	C—O	532.1	36.5	C—O	532.4	44.2
—OH	533.4	22.6	—OH	533.3	34.7	—OH	533.3	34.7	—OH	533.5	27.9
H₂O	536.2	2.4	—	—	—
N 1s						N 1s
			C $̿$ N	399.5	41.4	C $̿$ N	399.5	65.8	C $̿$ N	399.5	32.8
			C—N	400.4	44.1	C—N	400.4	19.1	C—N	400.3	54.6
			N $̿$ N	402.3	14.5	N $̿$ N	401.8	15.1	N $̿$ N	402.0	12.6
S 2p						S 2p
			C—S 2p_3/2	164.2	21.8	C—S 2p_3/2	163.6	55.1	C—S 2p_3/2	164.1	46.8
			C—S 2p_1/2	165.5	21.8	C—S 2p_1/2	164.9	55.1	C—S 2p_1/2	165.4	46.8
			SO₃^- 2p_3/2	168.4	78.2	SO₃^- 2p_3/2	168.0	44.9	SO₃^- 2p_3/2	168.3	53.2
			SO₃^- 2p_3/2	169.7	78.2	SO₃^- 2p_3/2	169.3	44.9	SO₃^- 2p_3/2	169.6	53.2

图11 SA/MCC-20吸附MO和MB后的扫描电镜和能谱面扫

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海藻酸钠/微晶纤维素复合水凝胶对水中甲基橙和亚甲基蓝的吸附性能与机理

Adsorption performance and mechanism of sodium alginate/microcrystalline cellulose composite hydrogel for aqueous methyl orange and methylene blue

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