中孔炭的水玻璃模板法制备、结构调控及球形功能化

doi:10.15541/jim20150036

无机材料学报 ›› 2015, Vol. 30 ›› Issue (8): 848-854.DOI: 10.15541/jim20150036

中孔炭的水玻璃模板法制备、结构调控及球形功能化

张川¹, 王际童^{1, 2}, 李旭¹, 龙东辉¹, 乔文明^{1, 3}, 凌立成^{1, 3}

(1. 华东理工大学化学工程联合国家重点实验室, 上海200237; 2. 中国科学院山西煤炭化学研究所, 炭材料重点实验室, 山西太原030001; 3. 华东理工大学特种功能高分子材料及相关技术教育部重点实验室, 上海200237)

收稿日期:2015-01-20 修回日期:2015-03-16 出版日期:2015-08-20 网络出版日期:2015-07-21
作者简介:张川(1985–), 男, 硕士研究生. E-mail: zhangch412@hotmail.com
基金资助:
国家自然科学基金(51302083, 51172071, 51272077);上海市自然科学基金(14ZR1410400)National Science Foundation of China (51302083, 51172071, 51272077);Shanghai Municipal Natural Science Foundation (14ZR1410400)

Facile Preparation, Structural Control and Spheroidization of Mesoporous Carbons Using Hydrolyzed Water Glass as a Template

ZHANG Chuan¹, WANG Ji-Tong^{1, 2}, LI Xu¹, LONG Dong-Hui¹, QIAO Wen-Ming^{1, 3}, LING Li-Cheng^{1, 3}

(1. The State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China; 2. Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China; Key Laboratory of Specially Functional Polymeric Materials and Related Technology, East China University of Science and Technology, Shanghai 200237, China)

Received:2015-01-20 Revised:2015-03-16 Published:2015-08-20 Online:2015-07-21
About author:ZHANG Chuan. E-mail: zhangch412@hotmail.com

摘要/Abstract

摘要：

以廉价水玻璃为原料, 通过控制水解条件, 合成出具有不同尺寸的SiO₂溶胶, 并与间苯二酚-甲醛(RF)溶胶形成均相的凝胶复合物, 经常压干燥、炭化、酸洗, 得到具有可控结构的中孔炭材料。考察了水解温度、水解时间和反应物组成对孔结构的影响, 并通过氮气吸附、扫描电镜和透射电镜对材料的微观结构进行了表征。结果表明: 中孔炭的孔隙反相复制于SiO₂凝胶网络, 其平均孔径随水解时间的延长或水解温度的升高而增大, 并在6~12 nm范围内精细调控, 而其总孔隙率可以通过改变炭、SiO₂前驱体比例调节。对液相复合溶胶通过悬浮聚合法和喷雾干燥法处理, 分别制备出毫米级和微米级的中孔炭球, 进而实现了中孔炭在宏观形貌上的调控。本工作为中孔炭的低成本制备、精细结构调控以及球形功能化提供了重要参考。

关键词: 中孔炭, 水玻璃, 结构调控, 球形形貌

Abstract:

Mesoporous carbons (MC) with controlled pore structure were synthesized using hydrolyzed water glass (sodium silicate) as hard template precursor. The mixture of carbon precursor (resorcinol-formaldehyde) sol and silica sol followed by Sol-Gel process generated a polymer/silica dual hydrogels. After ambient drying, carbonization and HF etching, mesoporous carbons with developed mesoporous structure were obtained. The hydrolysis conditions of water glass including hydrolysis temperature and hydrolysis time, and the weight ratio of RF polymer to silica were studied respectively to investigate their effects on the mesoporous structure. The microstructures of the mesoporous carbons were characterized by N₂ adsorption, SEM and TEM observations. It was found that as-prepared mesoporous carbons displayed disordered mesoporous channels which replicated from the initial colloidal silica networks. The average mesopore size could be precisely adjusted in the range from 6 nm to 12 nm by tuning the hydrolysis time and hydrolysis temperature, while the total porosity could be controlled by changing the weight ratio of polymer precursor to silica. Furthermore, with the assistant of suspension polymerization and spray drying technologies, spherical mesoporous carbons with millimetre and micrometer-sized particles were produced, respectively. The present work provides a low-cost approach for deliberately controlling the mesoporous structure and spherical morphology to mesoporous carbons that can be extended to many different applications.

Key words: mesoporous carbon, water glass, structure control, spherical morphology

中图分类号:

TQ174

张川, 王际童, 李旭, 龙东辉, 乔文明, 凌立成. 中孔炭的水玻璃模板法制备、结构调控及球形功能化[J]. 无机材料学报, 2015, 30(8): 848-854.

ZHANG Chuan, WANG Ji-Tong, LI Xu, LONG Dong-Hui, QIAO Wen-Ming, LING Li-Cheng. Facile Preparation, Structural Control and Spheroidization of Mesoporous Carbons Using Hydrolyzed Water Glass as a Template[J]. Journal of Inorganic Materials, 2015, 30(8): 848-854.

图/表 8

图1 中孔炭的制备过程示意图(a)及中孔炭MC-60-2-1的典型SEM(b)和TEM(c)照片

Fig. 1 Schematic diagram of the formation process for the mesoporous carbons (a) and typical SEM image (b) and TEM image (c) of the as-prepared MC-60-2-1

图2 不同水解时间制备的中孔炭的氮气吸附-脱附曲线(a)和BJH孔径分布曲线(b)

Fig. 2 Nitrogen adsorption-desorption isotherms (a) and the BJH pore size distributions (b) of the mesoporous carbons prepared with different hydrolysis time

表1 中孔炭孔结构参数

Table 1 Porous structure parameters of the as-prepared mesoporous carbons

Sample	S_BET/(m²∙g^-1)	V_mic/(cm³∙g^-1)	V_t/(cm³∙g^-1)	D_p/nm
MC-60-0-1	1148	0.08	1.5	6.5
MC-60-2-1	1124	0.09	1.7	7.7
MC-60-4-1	1084	0.15	1.8	10.7
MC-60-6-1	1131	0.12	1.9	12.4
MC-40-4-1	928	0.07	1.8	9.5
MC-80-4-1	845	0.09	1.9	12.0
MC-60-2-0.75	1244	0.09	2.3	7.7
MC-60-2-1.25	839	0.20	1.1	7.7

图3 不同水解温度制备的中孔炭的氮气吸附-脱附曲线(a)和BJH孔径分布曲线(b)

Fig. 3 Nitrogen adsorption-desorption isotherms (a) and the BJH pore size distributions (b) of the mesoporous carbons prepared at different hydrolysis temperatures

图4 不同反应物组成制备的中孔炭的氮气吸附-脱附曲线(a)和BJH孔径分布曲线(b)

Fig. 4 Nitrogen adsorption-desorption isotherms (a) and the BJH pore size distributions (b) of the mesoporous carbons prepared at different mass ratios of polymer to silica

图5 球形中孔炭的SEM(a, b)、TEM(c)照片及中孔炭微球的SEM(d, e)、TEM(f)照片

Fig. 5 Typical SEM images of the mesoporous carbon spheres (a, b) and mesoporous carbon microspheres (d, e) and the typical TEM images of the mesoporous carbon spheres (c) and mesoporous carbon microspheres (f)

图6 球形中孔炭以及中孔炭微球的氮气吸附-脱附曲线(a)和BJH孔径分布曲线(b)

Fig. 6 Nitrogen adsorption-desorption isotherms (a) and the BJH pore size distributions (b) of the mesoporous carbon spheres and mesoporous carbon microspheres

表2 球形中孔炭与中孔炭微球的孔结构参数

Table 2 Porous structure parameters of the as-prepared mesoporous carbon spheres and mesoporous carbon microspheres

Sample	S_BET/ (m²·g^-1)	V_mic/ (cm³·g^-1)	V_t/ (cm³·g^-1)	D_p /nm
MCSs	853	0	2.3	9.5
MCMSs	1165	0.21	1.7	6.5

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中孔炭的水玻璃模板法制备、结构调控及球形功能化

Facile Preparation, Structural Control and Spheroidization of Mesoporous Carbons Using Hydrolyzed Water Glass as a Template

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