巯基改性SBA-15的制备及其对Cr6+的吸附

doi:10.15541/jim20190103

摘要/Abstract

摘要：

环境中存在的重金属铬对人体健康有严重的危害, 本研究采用水热共缩聚法制备了一种对Cr ⁶⁺有较高吸附能力的介孔材料SBA-15-SH。经红外光谱证实, 通过使用改性硅源3-巯丙基三甲氧基硅烷, 对SBA-15成功实现了巯基改性。经扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察, 所制备的材料呈棒状, 具有均匀的孔道结构, 孔径约为7 nm。将制备材料用于重金属Cr ⁶⁺的吸附, 研究了吸附时间、环境温度、Cr ⁶⁺溶液pH和初始浓度以及吸附剂用量对吸附剂吸附性能的影响。研究表明: 该材料吸附Cr ⁶⁺的平衡吸附时间约10 min, 吸附过程符合Langmuir方程与伪二级动力学模型。当Cr ⁶⁺溶液pH为4.0、吸附温度在25~45 ℃时, 介孔材料SBA-15-SH对Cr ⁶⁺吸附量最大, 达到6.85 mg/g。将本方法用于自来水和工业废水中Cr ⁶⁺的吸附, 回收率介于95%~105%之间。

关键词: 介孔材料, 巯基改性, Cr⁶⁺, 吸附性能

Abstract:

Chromium ion accumulation in environment is a health hazard to human being. A thiohydroxy-functionalized mesoporous material SBA-15-SH as adsorbent was prepared by the hydrothermal polycondensation method in this study. When 3-mercaptopropyltrimethoxysilane was used as the silicon source, SBA-15 was successfully modified with the thiohydroxy group confirmed by FTIR. This designed mesoporous material was rod-like with regular and well-defined channel systems of 7 nm. The adsorption capacity of SBA-15-SH to Cr ⁶⁺ was affected by the adsorption temperature, Cr ⁶⁺ solution pH and its initial concentration together with the adsorbent dosage. The adsorption equilibrium was reached in 10 min which obeyed the Langmuir adsorption equation and the pseudo second-order kinetic mode. The maximum adsorption capacity of SBA-15-SH to Cr ⁶⁺ was 6.85 mg/g when the Cr ⁶⁺ solution pH and adsorption temperature was controlled at 4.0 and 25-45 ℃, respectively. This functionalized mesoporous material was successfully applied in spiked tap-water and industrial waste water, and the recovery rate can reach 95%-105%.

Key words: mesoporous materials, thiohydroxy-functionalized, Cr⁶⁺, adsorption performance

中图分类号:

O647

程福强,吉田田,薛敏,孟子晖,吴玉凯. 巯基改性SBA-15的制备及其对Cr⁶⁺的吸附[J]. 无机材料学报, 2020, 35(2): 193-198.

CHENG Fu-Qiang,JI Tian-Tian,XUE Min,MENG Zi-Hui,WU Yu-Kai. Thiohydroxy-functionalized Mesoporous Materials: Preparation and its Adsorption to Cr⁶⁺[J]. Journal of Inorganic Materials, 2020, 35(2): 193-198.

图/表 11

图1 SBA-15改性前后形貌表征

Fig.1 Morphologies of SBA-15 and thiohydroxy-functionalized mesoporous material SBA-15-SH (a) SEM image and (b) TEM image of SBA-15; (c) SEM image and (d) TEM image of SBA-15-SH

图2 介孔材料的红外衍射图谱

Fig. 2 FT-IR spectra of the as-prepared mesoporous materials

图3 溶液pH对改性材料吸附Cr6+的影响

Fig. 3 Effect of solution pH on Cr6+ adsorption by SBA-15-SH

图4 环境温度对SBA-15-SH吸附Cr6+的影响

Fig. 4 Effect of environment temperature on Cr6+ adsorption by SBA-15-SH

图5 改性前后对Cr6+吸附动力学研究

Fig. 5 Adsorption kinetic study of SBA-15/SBA-15-SH on Cr6+ adsorption

表1 吸附动力学拟合结果

Table 1 Adsorption kinetics fitting results

Adsorption equation	k	q_e/(mg·g^-1)	R²
Lagergren first order equation $In(q_{e}- q_{1})= Inq_{e}-kt$	0.351	5.737	0.9662
Lagergren second order equation $\frac{t}{q_{t}}=\frac {1}{kq^{2}_{e}}+\frac {t}{q_{e}}$	1.44×10^-4	6.930	0.9950

图6 Cr6+初始浓度对吸附的影响

Fig. 6 Effect of the initial concentration of Cr6+ on its adsorption

表2 等温吸附数据拟合

Table 2 Isothermal adsorption data fitting

Isothermal model	K	q_m	1/n	R²
Langmuir $\frac{c_{e}}{q_{e}}=\frac{c_{e}}{q_{m}}+\frac{1}{Kq_{m}}$	2.89	6.86	-	0.9899
Freundlich $Inq_{e}= InK_{F}+\frac{Inc_{e}}{n}$	-	-	1.849	0.7494

图7 吸附剂用量对Cr6+吸附的影响

Fig. 7 Effect of adsorbent dosage on Cr6+ adsorption

图8 巯基和重金属离子的螯合机理

Fig. 8 Chelation mechanism of sulfhydryl group and heavy metal ions

表3 实际水样中Cr6+的测定

Table 3 Determination of Cr6+ in spiked real water sample

Sample	Added/(mg·L^-1)	Found/(mg·L^-1)	Recovery /%
Tap water	0	0.01	-
	0.2	0.20	95
	0.5	0.50	98
	1.0	0.97	96
Industry waste water	0	0.20	-
	0.2	0.41	105
	0.5	0.68	96
	1.0	1.21	101

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巯基改性SBA-15的制备及其对Cr⁶⁺的吸附

Thiohydroxy-functionalized Mesoporous Materials: Preparation and its Adsorption to Cr⁶⁺

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