热活化酸浸托贝莫来石制备多孔SiO<sub>2</sub>材料及其吸附性能

王志增; 李通; 王冬云; 崔晓昱; 丁锡锋; 崔崇

doi:10.14135/j.cnki.1006-3080.20201229002

热活化酸浸托贝莫来石制备多孔SiO₂材料及其吸附性能

doi: 10.14135/j.cnki.1006-3080.20201229002

1.
南京理工大学材料科学与工程学院材料科学与工程学院，江苏南京 210094
2.
浙江中劲环保科技有限公司，浙江宁波 315105

基金项目: 国家自然科学基金（51772153）；浙江清华长三角研究院宁波分院鄞州区专项（20191218）

详细信息

作者简介:
王志增（1993—），男，山东菏泽人，博士生，主要研究方向为矿物材料功能化。E-mail：775717646@qq.com

通讯作者:
崔　崇，E-mail：cuichong@njust.edu.cn

中图分类号: TQ170.1
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出版历程
- 收稿日期: 2020-12-29
- 网络出版日期: 2021-04-27
- 刊出日期: 2022-04-22

Preparation of Porous SiO₂ Materials from Tobermorite and Their Adsorption Performances

1.
School of Materials Science and Engineering，Nanjing University of Science and Technology, Nanjing 210094, China
2.
Zhejiang Zhongjin Environmental Protection Technology Co. Ltd, Ningbo 315105, Zhejiang, China

摘要

摘要: 通过水热合成法制备具有良好结晶形态的托贝莫来石（TOB），采用不同温度(300、500、700 ℃)对TOB进行加热活化（产物分别表示为300H-TOB、500H-TOB、800H-TOB），然后对热活化后的TOB进行酸处理（产物分别表示为300AH-TOB、500AH-TOB、800AH-TOB），成功制备出多孔二氧化硅材料。采用X射线多晶衍射（XRD）、N₂吸附-脱附、扫描电子显微镜（SEM）、透射电子显微镜（TEM）等测试方法对多孔SiO₂材料进行表征，结果表明，300AH-TOB样品的比表面积为570.25 m²/g，总孔容为0.747 m³/g。TOB经过热活化和酸处理后，钙离子选择性溶出，TOB的SiO₂骨架保留下来，在TOB的链状八元环结构上原位形成大量的纳米尺度的孔结构。通过静态吸附实验探讨了TOB、300H-TOB、300AH-TOB 3种样品对碱性红2和结晶紫2种有机染料的吸附性能，结果表明在碱性红2和结晶紫中在分别加入0.4 g 3种样品时，TOB的吸附率分别为56.35%、47.69%，300H-TOB的吸附率分别为25.57%、42.69%，300AH-TOB的吸附率分别为91.46%、88.86%。
- 托贝莫来石 /
- 选择性酸浸 /
- 多孔二氧化硅 /
- 吸附
Abstract: Tobermorite (TOB) was a major phase of calcium silicate board and autoclaved aerated concrete, which was widely used refractory materials and thermal insulation materials in the field of civil engineering . However, these materials were easy to wear so that a large number of solid wastes have been produced. The problem of functionalized utilization of TOB needed to be resolved urgently. In the present paper, TOB samples with good crystal morphology were prepared by hydrothermal synthesis and were calcined at different temperatures (H-TOB). Then the porous SiO₂ material (AH-TOB) was successfully prepared by acid treatment of H-TOB, and AH-TOB material was characterized by XRD, N₂ adsorption-desorption, SEM, TEM and other testing methods to investigate the formation mechanism. The results of BET and pore size distribution test analysis showed that the specific surface area of 300AH-TOB after thermal activation at 300 ℃ and hydrochloric acid modification was 570.25 m²/g, and the total pore volume was 0.747 m³/g. After heat treatment and hydrochloric acid treatment, the calcium ions in TOB were selectively dissolved, and the main component of the acid-insoluble material was silica. Therefore, it was inferred that the silicon oxide exhibited an eight-membered ring double-chain deformation structure composed of a silicon-oxygen tetrahedron, resulting in an increase in mesopores and micropores. The adsorption performances of TOB, 300H-TOB and 300AH-TOB on two organic dyes, Safranine T (ST) and crystal violet (CV）, were investigated by static adsorption experiments. When the mass of adsorbent was added at 0.4 g, the adsorption rates of ST and CV were 56.35% and 47.69% on TOB; 25.57% and 42.69% on 300H-TOB; and 91.46% and 88.86% on 300AH-TOB, respectively. The porous material prepared from TOB had favorable adsorption of organic dyes, indicating its promising potential in adsorption application.
- tobermorite /
- selective acid leaching /
- porous silica /
- adsorption

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图 1 TOB（a）和300AH-TOB（b）的TG和DSC曲线

Figure 1. TG、DSC curves of TOB (a) and 300AH-TOB (b)

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图 2 不同温度热处理后TOB的XRD图谱(a)；煅烧TOB酸处理后的XRD图谱(b)

Figure 2. XRD patterns of TOB calcined at different temperatures (a); XRD patterns of calcined TOB after acid treatment (b)

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图 3 N₂吸附-脱附等温线（a）和由2D-NLDFT方法计算的孔径分布曲线（b）

Figure 3. Nitrogen adsorption-desorption isotherms (a) and pore size distribution curves calculated by 2D-NLDFT method (b)

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图 4 TOB、300H-TOB和300AH-TOB的SEM形貌

Figure 4. SEM morphology of TOB, 300H-TOB and 300AH-TOB

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图 5 TOB（a）、300H-TOB（b）和300AH-TOB（c）的透射电镜形貌及衍射斑点图

Figure 5. TEM morphology and diffraction spectrogram of TOB (a), 300H-TOB (b) and 300AH-TOB (c)

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图 6 TOB的多孔形成示意图

Figure 6. Schematic diagram of porous formation of TOB

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图 7 TOB、300H-TOB和300AH-TOB对碱性红2（a）和结晶紫（b）的吸附率

Figure 7. Adsorption rate of ST (a) and CV (b) on TOB、300H-TOB and 300AH-TOB

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图 8 TOB, 300H-TOB和300AH-TOB的Zata电位图（a）; pH对300AH-TOB吸附碱性红2和结晶紫的影响（b）

Figure 8. Zeta potential of TOB, 300H-TOB and 300AH-TOB（a）; Effect of pH on the adsorption ST and CV of 300AH-TOB（b)

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图 9 300AH-TOB吸附碱性红2的Langmuir（a）和Freundlich（b）等温吸附模型拟合结果

Figure 9. Fitting results of Langmuir (a) and Freundlich (b) isotherms for ST adsorption on 300AH-TOB

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图 10 300AH-TOB吸附结晶紫的Langmuir（a）和Freundlich（b）等温吸附模型拟合结果

Figure 10. Fitting results of Langmuir (a) and Freundlich (b) isotherms for CV adsorption on 300AH-TOB

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图 11 300AH-TOB的再生循环吸附结果

Figure 11. Regeneration cycle adsorption results of 300AH-TOB

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表 1 TOB、300H-TOB、300AH-TOB的化学成分

Table 1. Chemical composition of TOB, 300H-TOB, 300AH-TOB

Samples	w/%
Samples	SiO₂	CaO	Others
TOB	49.31	38.36	12.33
300H-TOB	54.71	42.56	2.73
300AH-TOB	90.11	0	9.89

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表 2 不同温度热活化TOB经过盐酸处理后的纳米孔道参数

Table 2. Porosity parameters of HCl acid treatment samples thermally activated at different temperatures

Sample	S_BET/(m²·g⁻¹)	S_External/(m²·g⁻¹)	S_Micro/(m²·g⁻¹)	V_Micro/(cm³·g⁻¹)	V_Meso/(cm³·g⁻¹)	V_Total/(cm³·g⁻¹)
TOB	152.14	123.81	28.33	0.011	0.607	0.611
300AH-TOB	570.25	437.76	132.49	0.057	0.652	0.747
500AH-TOB	539.15	421.21	117.94	0.050	0.651	0.734
700AH-TOB	440.18	337.93	102.25	0.043	0.514	0.576
S_BET—Specific surface area; S_Micro—Micropores specific surface area by t-plot method; S_External—External surface area by t-plot method; V_Total—Total pore volume; V_Micro—Microporous volume by t-plot method;V_Meso— Mesopore volume

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表 3 300AH-TOB吸附碱性红2的等温吸附模型拟合参数

Table 3. Isothermal adsorption model fitting parameters for ST adsorption on 300AH-TOB

T/K	Freundlich			Langmuir
T/K	K_f	1/n	R²	b/(L·mg⁻¹)	q_m/(mg·g⁻¹)	R²
298	3.85	0.41	0.953	0.14	22.57	0.970
308	3.03	0.42	0.949	0.09	20.53	0.989
318	2.94	0.31	0.765	0.08	14.82	0.978

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表 4 300AH-TOB吸附结晶紫的等温吸附模型拟合参数

Table 4. Isothermal adsorption model fitting parameters for CV adsorption on 300AH-TOB

T/K	Freundlich			Langmuir
T/K	K_f	1/n	R²	b/(L·mg⁻¹)	q_m/(mg·g⁻¹)	R²
298	7.52	0.19	0.821	0.26	18.66	0.902
308	6.02	0.33	0.952	0.13	27.73	0.968
318	7.13	0.34	0.798	0.08	38.41	0.986

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