2-羟基-1-萘甲醛功能化SBA-15吸附剂的制备及其对Cr(III)的吸附性能

doi:10.15541/jim20210109

无机材料学报 ›› 2021, Vol. 36 ›› Issue (11): 1163-1170.DOI: 10.15541/jim20210109

所属专题：【能源环境】水体污染物去除

2-羟基-1-萘甲醛功能化SBA-15吸附剂的制备及其对Cr(III)的吸附性能

郭宇(), 姜晓庆, 吴红梅, 肖昱, 仵大富, 刘鑫

辽宁工业大学化学与环境工程学院, 交叉科学研究院, 锦州 121001

收稿日期:2021-02-23 修回日期:2021-04-26 出版日期:2021-11-20 网络出版日期:2021-04-30
作者简介:郭宇(1981-), 男, 教授. E-mail: guoyu@lnut.edu.cn
基金资助:
国家自然科学基金(21601075);辽宁省教育厅科学研究项目(JZL201715403);辽宁省教育厅科学研究项目(JZL201915402);辽宁省“兴辽英才计划”项目(XLTC2007171)

Preparation of 2-hydroxy-1-naphthalene Functionalized SBA-15 Adsorbent for the Adsorption of Chromium(III) Ions from Aqueous Solution

GUO Yu(), JIANG Xiaoqing, WU Hongmei, XIAO Yu, WU Dafu, LIU Xin

School of Chemical and Environmental Engineering, Institute of Interdisciplinary Research, Liaoning University of Technology, Jinzhou 121001, China

Received:2021-02-23 Revised:2021-04-26 Published:2021-11-20 Online:2021-04-30
About author:GUO Yu(1981-), male, professor. E-mail: guoyu@lnut.edu.cn
Supported by:
National Natural Science Foundation(21601075);Scientific Research Fund of Educational Department of Liaoning province(JZL201715403);Scientific Research Fund of Educational Department of Liaoning province(JZL201915402);Liaoning Revitalization Talents Program(XLTC2007171)

摘要/Abstract

摘要：

为去除水体中Cr(III)的污染, 本研究利用席夫碱反应原理制备了2-羟基-1-萘甲醛功能化SBA-15吸附剂(Q-SBA-15)。通过不同测试手段对所制备样品的形貌、孔道结构、元素组成和表面化学状态进行了系统表征。结果表明, SBA-15经2-羟基-1-萘甲醛修饰后, 其比表面积和孔径明显减小, 但表面形貌和晶体结构没有明显变化。为研究Q-SBA-15对Cr(III)的吸附性能, 详细分析了溶液pH和离子强度的影响, 以及吸附动力学、吸附等温线、吸附热力学和再生性能。结果表明, Q-SBA-15对Cr(III)吸附过程遵循准二级吸附动力学模型和Langmuir模型。当吸附温度为 40 ℃、pH为6、吸附时间为120 min时, Q-SBA-15对Cr(III)的吸附容量最大, 达到102.3 mg/g。Q-SBA-15对Cr(III)的吸附作用主要依靠其表面官能团与Cr(III)的配位螯合作用, 且为自发吸热过程。再生实验表明Q-SBA-15具有良好的重复使用性。该Q-SBA-15吸附剂在去除Cr(III)方面具有潜在的应用价值。

关键词: SBA-15, 功能化, 吸附, Cr(III)

Abstract:

SBA-15 mesoporous material functionalized with 2-hydroxy-1-naphthaldehyde denoted as Q-SBA-15 was synthesized by using Schiff’s base reaction to remove Cr(III) ions from aqueous solution. A series of characterizations were performed to analyze the morphology, pore structure, element distribution and chemical properties of Q-SBA-15. The results showed that BET surface area and pore size of SBA-15 decreased after modified with 2-hydroxy- 1-naphthaldehyde, but the surface morphology and crystal structure of SBA-15 did not change significantly. To investigate the adsorption properties of Q-SBA-15 toward Cr(III) ions, effects of solution pH and ionic strength were studied. Moreover, adsorption kinetics, adsorption isotherm models, adsorption thermodynamics, and regeneration performance of Q-SBA-15 were analyzed. Adsorption process toward Cr(III) ions onto Q-SBA-15 was well followed by pseudo-second order kinetic model and Langmuir isotherm model. The maximum adsorption capacity of Q-SBA-15 was 102.3 mg/g toward Cr(III) ions under the conditions of 40 ℃ and pH 6. The Cr(III) adsorption onto Q-SBA-15 was found to be spontaneous and endothermic process. The adsorption process mainly based on the coordination chelation of Cr(III) ions with the functionalized groups on Q-SBA-15. Furthermore, Q-SBA-15 exhibited good reusability. Therefore, Q-SBA-15 can be used as a promising adsorbent for removal of Cr(III) ions from aqueous solution.

Key words: SBA-15, functionalization, adsorption, Cr(III)

中图分类号:

O647

郭宇, 姜晓庆, 吴红梅, 肖昱, 仵大富, 刘鑫. 2-羟基-1-萘甲醛功能化SBA-15吸附剂的制备及其对Cr(III)的吸附性能[J]. 无机材料学报, 2021, 36(11): 1163-1170.

GUO Yu, JIANG Xiaoqing, WU Hongmei, XIAO Yu, WU Dafu, LIU Xin. Preparation of 2-hydroxy-1-naphthalene Functionalized SBA-15 Adsorbent for the Adsorption of Chromium(III) Ions from Aqueous Solution[J]. Journal of Inorganic Materials, 2021, 36(11): 1163-1170.

图/表 17

图1 Q-SBA-15合成路线示意图

Fig. 1 Schematic diagram of the synthetic process for Q-SBA-15

图2 (a, c)SBA-15和(b, d)Q-SBA-15的(a, b)SEM照片, (c, d)EDX分析, (e)XRD图谱和(f)TG曲线

Fig. 2 (a, b) SEM images, (c, d) EDX elemental analyses, (e) XRD patterns and (f) TG curves of (a, c) SBA-15 and (b, d) Q-SBA-15 samples

图3 SBA-15和Q-SBA-15的(a)N2吸附-解吸等温线和(b)孔径分布; (c, d)Q-SBA-15的TEM照片

Fig. 3 (a) N2 adsorption-desorption isotherms, (b) pore size distributions of SBA-15 and Q-SBA-15, (c, d) TEM images of Q-SBA-15

表1 样品的孔结构分析

Table 1 Textural properties of the synthesized samples

Sample	S_BET/(cm²·g^-1)	Pore size/nm
SBA-15	757	9.6
Q-SBA-15	283	6.7

图4 Q-SBA-15和SBA-15的(a)FT-IR谱图, (b)Q-SBA-15的XPS全谱

Fig. 4 (a) FT-IR spectra of Q-SBA-15 and SBA-15, and (b) XPS survey spectrum of Q-SBA-15

图5 Q-SBA-15的溶液pH对吸附Cr(III)的影响

Fig. 5 Effect of solution pH on the adsorption of Cr(III) with Q-SBA-15

图6 Q-SBA-15离子强度对Cr(III)吸附的影响

Fig. 6 Effects of ionic strength on Cr(III) adsorption

图7 Q-SBA-15吸附Cr(III)的(a)Langmuir方程和(b)Freundlich方程拟合曲线

Fig. 7 Linearized fitting curves of (a) Langmuir model and (b) Freundlich model for adsorption of Cr(III) on Q-SBA-15

表2 不同温度下Q-SBA-15吸附Cr(III)的吸附等温线拟合常数

Table 2 Different model parameters for adsorption of Cr(III) by Q-SBA-15 at different temperatures

Temperature /℃	Langmuir			Freundlich
Temperature /℃	q_m/(g·mg^-1)	K_L	R²	K_F	n	R²
30	106.84	0.09	0.988	24.59	3.12	0.836
40	108.23	0.25	0.997	48.39	5.47	0.913
50	112.74	0.41	0.997	42.72	4.27	0.697

图8 Q-SBA-15吸附Cr(III)前/后的XPS谱图

Fig. 8 XPS spectra of Q-SBA-15 (a) Overview spectra of Q-SBA-15 before and after Cr(III) adsorption; (b) Cr2p spectrum of Q-SBA-15 after Cr(III) adsorption; C1s spectra of (c) Q-SBA-15 (before adsorption) and (d) Q-SBA-15 (after adsorption); N1s spectra of (e) Q-SBA-15 (before adsorption) and (f) Q-SBA-15 (after adsorption)

图9 Q-SBA-15吸附剂的再生性能

Fig. 9 Regeneration property of Q-SBA-15

图S1 (a)Q-SBA-15随着时间变化对Cr(III)的吸附性能和(b)Q-SBA-15吸附Cr(III)后的EDX元素分析

Fig. S1 (a) Effect of contacting time on the adsorption capacity of Cr(III) by Q-SBA-15 and (b) EDX analyses of Q-SBA-15 after adsorption of Cr(III)

图S2 Q-SBA-15吸附Cr(III)的(a)准一级和(b)准二级动力学模型拟合曲线

Fig. S2 Fitting curves for adsorption of Cr(III) by (a) pseudo-first-order model and (b) pseudo-first-order model

表S1 Q-SBA-15吸附Cr(III)的动力学方程拟合参数

Table S1 Kinetic parameters for Cr(III) adsorption onto Q-SBA-15

Sample	q_e,exp/(mg·g^-1)	Pseudo first-order model			Pseudo second-order model
Sample	q_e,exp/(mg·g^-1)	K₁/ min^-1	q_e,_cal/(mg·g^-1)	R²	K₂/(g·mg^-1·min^-1)	q_e,_cal/(mg·g^-1)	R²
Q-SBA-15	102.3	0.0647	61.75	0.857	4.26×10^-4	119.19	0.979

表S2 不同吸附剂对Cr(III)的吸附性能对比

Table S2 Comparison of Cr(III) adsorption performance with different materials selected from literature

Adsorbent	q_m/(mg·g^-1)	References
Biomass-based hydrogel	41.7	[1]
m-MCM-41-NH₂	36.92	[2]
Graphene oxide	13.3	[3]
Thiol-functionalized MCM-41	15.34	[4]
TS-SBA-15	95.68	[5]
NH₂-SBA-15	24.88	[6]
Q-SBA-15	102.3	This work

图S3 Q-SBA-15对Cr(III)的吸附热力学拟合曲线

Fig. S3 Plots of lnKc versus 1/T for the adsorption of Cr(III) by Q-SBA-15

表S3 Q-SBA-15吸附Cr(III)的热力学参数

Table S3 Thermodynamic parameters of Cr(III) adsorption on Q-SBA-15

Sample	Tempera- ture/K	K_c	ΔG/ (kJ·mol^-1)	ΔS/ (kJ·mol·K^-1)	ΔH/ (kJ·mol^-1)
Q-SBA-15	293	1.846	-4.386	0.128	33.118
	303	2.095	-5.666
	313	2.650	-6.946
	318	2.780	-7.586
	323	3.088	-8.226

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2-羟基-1-萘甲醛功能化SBA-15吸附剂的制备及其对Cr(III)的吸附性能

Preparation of 2-hydroxy-1-naphthalene Functionalized SBA-15 Adsorbent for the Adsorption of Chromium(III) Ions from Aqueous Solution

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