二元阴、 阳离子表面活性剂调控合成不同形貌的介孔二氧化硅

doi:10.7503/cjcu20140371

摘要/Abstract

摘要：

经过简单的水热处理, 以二元阴、阳离子表面活性剂[十六烷基三甲基溴化铵(CTAB)和十二烷基磺酸钠(SDS)分别作为阳离子表面活性剂和阴离子表面活性剂]为模板剂合成了不同形貌的介孔二氧化硅. 通过调控2种表面活性剂摩尔分数R(R=n(SDS)/[n(SDS)+n(CTAB)]), 合成了多种形貌的介孔二氧化硅. 对合成的不同形貌样品通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、 X射线粉末衍射仪(XRD) 及比表面和孔隙分析仪进行了表征. 结果表明, 随着R值从0.01变化到0.50, 介孔二氧化硅的形貌经历了一系列规律性的变化, 出现了二维六方、层状相和反相堆积的形貌: 在R=0.01~0.18之间, 主要产物为六方相棒状结构, 且长径比随着R值增大而增大; 在R=0.20~0.28之间主要得到空心泡状结构且具有明显的演变过程; 在R=0.32~0.40之间发生了多层囊泡到单层囊泡的结构转变; 当R值超过一定范围时会产生反相堆积的形貌. 分析认为, SDS在加入过程中通过影响堆积参数g影响胶束的形貌变化, 调控了不同形貌介孔二氧化硅的合成. 各阶段产物形貌和R值的变化有直接关系, 可通过改变R值来合成特定形貌的产物.

关键词: 形貌调控, 介孔二氧化硅, 阴、阳离子表面活性剂, 结构转变, 组装

Abstract:

Mesoporous silica with various morphologies were obtained using binary cationic-anionic surfactant as template after a facile hydrothermal treatment. Cetyltrimethyl ammonium bromide(CTAB) and sodium dodecyl sulfonate(SDS) were selected as cationic and anionic structure direct agent respectively. Mechanism of morphological control during this process was investigated by regulating the molar ratio of SDS/CTAB. The as-synthesized samples were characterized by scanning electron microscopy(SEM), small angle X-ray diffraction(SXRD), transmission electron microscopy(TEM) and nitrogen adsorption-desorption isotherms measurements. Formation of the different stable morphologies were attributed to the structural transition of SDS/CTAB assembly from micelle to bilayer commitment with the ascending ratio of SDS.

Key words: Morphological control, Mesoporous silica, Cationic-anionic surfactant, Structural transition, Assembly

中图分类号:

O613.72

TrendMD:

彭策, 牟鸣薇, 谢诗航, 蔡强. 二元阴、阳离子表面活性剂调控合成不同形貌的介孔二氧化硅. 高等学校化学学报, 2014, 35(9): 1864.

PENG Ce, MU Mingwei, XIE Shihang, CAI Qiang. Morphological Transformation of Mesoporous Silica Using Binary Cationic-anionic Surfactant as Template^†. Chem. J. Chinese Universities, 2014, 35(9): 1864.

图/表 10

Fig.1 XRD patterns of as-synthesized samples with various R values R: a. 0.01; b. 0.05; c. 0.10; d. 0.14.

Fig.2 TEM images of as-synthesized samples with various R values R: (A) 0.01; (B) 0.05; (C) 0.10; (D) 0.14.

Fig.3 Concentric morphological transition with different R values R: (A) 0.08; (B) 0.14; (C) 0.16, the inset shows the low-magnification image.

Fig.4 XRD patterns of as-synthesized sample with various R values R: (A) a. 0.20, b. 0.24, c. 0.28; (B) a. 0.32, b. 0.40, c. 0.42, d. 0.48.

Fig.5 TEM images of samples with various R values R: (A) 0.20; (B) 0.24; (C) 0.28.

Fig.6 TEM images of samples with R values of 0.32(A) and 0.40(B)

Fig.7 Morphological transition of silica from R=0.42 to R=0.48 (A) R=0.42, TEM; (B) R=0.48, TEM; (C) R=0.48, SEM.

Table 1 Silica samples prepared with different typical R values

R	Morphology	d₁₀₀/nm	S_BET/(m²·g^-1)	BJH pore width/nm	BJH pore volume/(cm³·g^-1)
0.01	Hexagonal	3.65	1033.78	2.67	0.781
0.10	Hexagonal rod	3.68	971.01	2.84	0.763
0.14	Hexagonal fiber, concentric	3.71	921.40	2.94	0.707
0.32	Multilayer vesicle	3.70	702.59	1.8~2.7	0.681
0.40	Monolayer vesicle	5.0	626.89	3.78, 29.65	1.129
0.48	Inverted micelles		491.19	44.66	2.542

Fig.8 N2 adsorption-desorption isotherms of as-synthesized typical samples with various R values(A, B) and pore size distribution of sample with R=0.48(inset) AD: adsorption; DE: desorption.

Fig.9 Linear fitting of BET surface area of the as- synthesized samples with different R values

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