新型纳米SiO2复合及纳米TiO2复合功能薄膜研究

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摘要

纳米SiO2薄膜有机械强度不够、易吸潮等缺点，限制了其应用范围因而对其性

能进行改进研究尤为重要。本文通过向多孔SiO2溶胶网络中引入有机硅烷疏水基甲

基三乙氧基硅烷（MTES）来提高复合薄膜的疏水性、引入Al2O3提高复合薄膜的

硬度和机械强度，引入表面活性剂十六烷基三甲基溴化氨(CTAB)增加复合薄膜的

孔洞率进而降低复合薄膜的折射率以至透过率增大，制备了

SiO2-MTES-Al2O3-CTAB疏水硬质透明复合薄膜。TiO2薄膜具有优异的光催化特

性，在光催化降解有机物、染料敏化太阳能电池以及防雾、自清洁等领域有着广

阔的应用前景。提高TiO2薄膜光催化效率便成了一个非常具有实际意义的研究课

题。本文通过Fe3+、

Bi3+、

CTAB掺杂以及共掺制备纳米TiO2光催化剂来提高其光催

化活性并对其光催化机理进行深入研究。

本文采用溶胶-凝胶法，以正硅酸乙酯（TEOS）、异丙醇铝[（Al（C3H7O）3）

]

为前驱体，盐酸（HCl）为催化剂，甲基三乙氧基硅烷（MTES）为有机硅烷，表

面活性剂十六烷基三甲基溴化氨(CTAB)为模板剂，通过酸/酸两步水解法，利用提

拉法制备了 SiO2-MTES-Al2O3-CTAB 疏水透明硬质复合薄膜。通过红外光谱、原

子力显微镜、透过率、疏水角测量等测试复合薄膜的疏水、表面形貌、光学等性

能。

本文采用溶胶-凝胶法以钛酸丁酯、硝酸铁、硝酸铋、正硅酸乙酯为原料，制

备了掺杂过渡金属 Fe3+、

Bi3+、表面活性剂十六烷基三甲基溴化铵 CTAB 以及共掺

制备的 TiO2纳米复合薄膜。通过 XRD 谱图分析得离子掺杂以及共掺的纳米 TiO2

复合薄膜在煅烧 500℃后晶型均为锐钛矿，掺杂离子已高度分散进入了 TiO2中，

形成掺杂或共掺杂的纳米 TiO2复合薄膜。通过对甲基橙溶液光降解的研究，在离

子掺杂和共掺杂的作用下的 TiO2的光催化活性有了显著地提高，并讨论了各掺杂

体系以及共掺体系、光降解时间、煅烧温度等对 TiO2复合薄膜光降解甲基橙的影

响机理。

最后，对论文工作进行总结，并对今后进一步的研究做了展望。

关键词：溶胶-凝胶法 SiO2TiO2CTAB 疏水硬质光催化降解复合

薄膜

ABSTRACT

The hydrophobic nano-films of silica sol were needed in some applications.

However, in practical applications, the material is required to have hydrophobic and

transparent as well as mechanical property, simultaneously, so increasing the

mechanical properties without decreasing hydrophobicity and transparent of these

coatings is very important. In this paper, the SiO2-MTES-Al2O3-CTAB composite films

with the hydrophobic and transparent were prepared by the sol-gel process. The

SiO2-MTES-Al2O3-CTABcomposite films with the hydrophobic transparent can be

widely used in more applications as functional materials in optical, microelectronics,

and photo electronics industries, and for the purpose of protection as well. MTES is

used to provide the hydrophobic character to a silica matrix. The

SiO2-MTES-Al2O3-CTAB composite films with the hydrophobic and transparent now

have been developed by the addition of aluminous sol into silica sol for improving their

rigidities without decreasing hydrophobicity and transparent. And the agglomerations

cause poor dispersion capacity in the organic polymer matrix. CTAB is atypical cationic

surfactant with sixteen long-chain carbons and used to resolve this problem. TiO2film

has excellent photocatalytic characteristic. It has broad application prospects in fields of

catalytic degradation oforganic matter in the light, desensitized solar cells, antifogging

and self-cleaning. It was important to raise the photocatalytic rate of TiO2film. The Bi3+,

Fe3+ and CTAB doping or co-doping of TiO2composite nano-films is used to improve

the photocatalytic activity of TiO2composite nano-films.

The SiO2-MTES-Al2O3-CTAB composite films with the hydrophobic and

transparent properties were prepared by the sol-gel process and evaporation Induced

Self-assembly method, using tetraethoxysliane (TEOS) and aluminum isopropoxide as

precursor, methyltriethoxysilane (MTES) as organic silicon, surfactant cetyltrimethyl

ammonium bromide (CTAB) as the template, by two-step acid-catalyzed and

dip-coating method. The chemical structure properties, the optical transmittance and

hydrophobicity of the composite nano-films were studied by FT-IR, AFM, UV-VIS

spectrum and the contact-angle machine and so on.

The Bi3+,Fe3+ and CTAB doping or co-doping of TiO2composite nano-films were

prepared by the sol-gel process, using butyl titanate、bismuth nitrate and ferric nitrate

as raw materials. The Bi3+, Fe3+ and CTAB doping or co-doping of TiO2composite

nano-films were investigated by means of XRD, SEM, UV-VIS and degradation rate.

The influence of Bi3+,Fe3+ and CTAB doping or co-doping of TiO2composite nano-films

on its performance as a photocatalyst in methyl orange has been studied. The

experimental results show that under the effect of Bi3+, Fe3+ and CTAB, the

photocatalytic activity of TiO2composite nano-films has been greatly improved. The

preparation of catalyzer and various factors which influenced on the photocatalytic

degradation of methyl orange were also discussed.

At the end, the paper was summarized and a prospect to the further study was

taken.

Keywords: sol-gel, SiO2, TiO2,CTAB ，hydrophobic ，hardness,

photocatalytic degradation，composite films

摘要

ABSTRACT

第一章绪论 .................................................................................................................................1

§1.1 溶胶-凝胶(Sol-Gel)技术 .................................................................................................... 3

§1.1.1 溶胶-凝胶技术发展的基本历程 ................................................................................ 3

§1.1.2 溶胶-凝胶法的基本过程 ............................................................................................ 4

§1.1.3 溶胶-凝胶法的影响因素 ............................................................................................ 5

§1.1.4 溶胶-凝胶法制备薄膜工艺 ........................................................................................ 6

§1.1.5 溶胶-凝胶法制备薄膜的优点 .................................................................................... 9

§1.2 疏水硬质复合薄膜的研究概况 .........................................................................................9

§1.2.1 疏水薄膜的研究概况 ..................................................................................................9

§1.2.2 硬质薄膜的研究概况 ................................................................................................11

§1.2.3 疏水硬质复合薄膜的研究概况 ................................................................................12

§1.3 纳米 TiO2光催化复合薄膜的研究概况 ..........................................................................13

§1.4 论文研究的目的和意义 ...................................................................................................14

第二章本论文相关的理论基础 .................................................................................................16

§2.1 纳米材料学的基本理论 ................................................................................................... 16

§2.1.1 量子尺寸效应 .............................................................................................................16

§2.1.2 小尺寸效应（体积效应） .........................................................................................17

§2.1.3 表面效应 .....................................................................................................................18

§2.1.4 宏观量子遂道效应 .....................................................................................................18

§2.1.5 介电限域效应 .............................................................................................................19

§2.1.6 光学性质 .....................................................................................................................19

§2.2 纳米复合薄膜的疏水理论 ...............................................................................................20

§2.3 纳米复合薄膜的硬质理论 ...............................................................................................21

§2.4 纳米 TiO2的光催化原理 ................................................................................................. 21

第三章新型纳米 SiO2疏水硬质透明复合薄膜的制备 ........................................................... 23

§3.1 引言 ...................................................................................................................................23

§3.2 新型纳米 SiO2疏水硬质透明复合薄膜的制备 .............................................................. 24

§3.2.1 实验原料和实验仪器 ..............................................................................................24

§3.2.1.1 实验原料 .................................................................................................................24

§3.2.1.2 实验仪器 .................................................................................................................24

§3.2.2 溶胶制备过程 ..........................................................................................................25

§3.2.2.1 SiO2溶胶制备过程 ..................................................................................................25

§3.2.2.2 Al2O3溶胶的制备过程 ............................................................................................26

§3.2.2.3 新型纳米 SiO2疏水硬质透明复合溶胶的制备 ....................................................26

§3.2.3 新型纳米 SiO2疏水硬质透明复合薄膜 .................................................................27

§3.3 新型纳米 SiO2疏水硬质透明复合薄膜的性能测试 ...................................................... 27

§3.3.1 XRD 测试 ................................................................................................................... 27

§3.3.2 粘度测试 .....................................................................................................................28

§3.3.3 傅立叶红外光谱测试 .................................................................................................28

§3.3.4 可见透过光谱测试 .....................................................................................................29

§3.3.5 疏水性能测试 .............................................................................................................29

§3.3.6 机械性能测试 .............................................................................................................29

§3.3.7 表面形貌测试 .............................................................................................................29

§3.4 本章小结实验结果及分析 .............................................................................................30

§3.4.1 XRD 分析 ................................................................................................................... 30

§3.4.2 粘度的分析 .................................................................................................................31

§3.4.3 傅里叶红外光谱分析 .................................................................................................33

§3.4.4 光学特性分析 .............................................................................................................35

§3.4.5 薄膜的疏水性分析 .....................................................................................................36

§3.4.6 薄膜的硬度分析 .........................................................................................................39

§3.4.7 薄膜的形貌分析 .........................................................................................................41

§3.5 本章小结 .........................................................................................................................43

第四章纳米 TiO2复合薄膜的制备及其光催化性能 .............................................................44

§4.1 引言 ...................................................................................................................................44

§4.2 新型纳米 TiO2光催化复合薄膜的制备 ..........................................................................44

§4.2.1 实验原料和实验仪器 ..............................................................................................45

§4.2.1.1 实验原料 .................................................................................................................45

§3.2.1.2 实验仪器 .................................................................................................................45

§4.2.2 溶胶制备过程 ..........................................................................................................46

§4.2.2.1 Fe3+、CTAB 掺杂 TiO2溶胶制备过程 .................................................................. 46

§4.2.2.2 Bi3+、Fe3+掺杂 TiO2溶胶制备过程 ....................................................................... 46

§4.2.3 新型纳米 TiO2光催化复合薄膜制备 .......................................................................46

§4.2.4 光降解实验 .................................................................................................................47

§4.3 新型纳米 TiO2光催化复合薄膜的性能测试 ..................................................................47

§4.3.1 X 射线衍射分析 .........................................................................................................48

§4.3.2 扫描电子显微镜分析 .................................................................................................48

§4.3.3 紫外-可见吸收光谱分析 ........................................................................................... 50

§4.3.4 光催化活性分析 .........................................................................................................51

§4.4 本章小结 .........................................................................................................................55

第五章工作总结与展望 .............................................................................................................56

§5.1 工作总结 ...........................................................................................................................58

§5.2 工作展望 ...........................................................................................................................59

参考文献 .......................................................................................................................................60

在读期间公开发表的论文和承担科研项目及成果 .................................................................. 66

致谢 .............................................................................................................................................66

个人简历 .......................................................................................................................................69

第一章绪论

有机-无机纳米复合材料被誉为“21世纪的新材料”[1]。有机-无机纳米复合材

料与传统的复合材料相比，因为纳米粒子带来的界面与表面效应，纳米复合材料

具有由于相同化学成分常规复合材料的热性能和力学性能。但要充分发挥纳米粒

子的性能就要对其进行表面处理或修饰[2-4]。

纳米SiO2薄膜具有良好的力学、光学、电学、透明性等特性，在厨房用具、建

筑玻璃、光学、微电子等领域有着广泛的应用前景，是目前国际上广泛关注的功

能材料[5-7]。传统的溶胶-凝胶法制备多孔SiO2薄膜多是采用碱性催化，缺点是制备

的薄膜机械强度较差；如用酸性催化则可以大大增强薄膜的机械强度，但由于酸

性催化的SiO2薄膜孔洞率较低，折射率、介电常数较高，很难满足一些实际需要。

而用溶胶-凝胶技术的同时采用蒸发诱导自组装工艺（EISA）制备多孔SiO2复合薄

膜则可很好的解决这些问题[8]，并且制备的多孔薄膜均匀、透明。添加表面活性剂

可以在酸性条件下制备出具有有序介孔SiO2复合薄膜及大孔径的多孔结构SiO2复

合薄膜，而在酸性催化时溶胶中颗粒生长的特点使得制备出的多孔SiO2复合薄膜的

机械性能远好于传统溶胶-凝胶过程中使用碱催化制备的多孔SiO2复合薄膜，于是

本实验采用酸性催化。

随着科学技术的发展，薄膜的应用也越来越广泛，对薄膜的性能也提出了越

来越高的要求，因此对薄膜的性能进行改善是非常必要的。在纳米多孔SiO2薄膜广

泛应用的同时发现多孔SiO2薄膜有机械强度不够、易吸潮等缺点，并且多孔SiO2

薄膜孔洞率高，膜层中含有大量亲水性Si-OH基团，容易吸附空气中的水分子，导

致膜层的折射率上升，透过率在暴露在空气中几个月以后明显下降，因而对其性

能进行研究进而改进尤为重要。近年来有报道Tsutomu Minami、Hong B S和Akira

Nakajima等人[9]利用增加膜层表面粗糙度的方法提高膜的疏水性，但光的散射与表

面粗糙度有关，因此疏水性与透明性相矛盾，如此获得的薄膜表面粗糙度增加，

疏水性能提高而透明度降低。利用氟烷基硅烷FAS作为常用的疏水前驱物制备疏水

薄膜，但仅仅使用FAS进行薄膜表面修饰所得薄膜透光性差。经研究发现可利用具

有疏水性质的有机官能团修饰SiO2颗粒表面。颗粒形成多孔薄膜时，疏水基团填充

在孔隙中，这样可大大减少水对孔隙的润湿，起到对多孔薄膜保护的作用。

近年来由于硬质薄膜能减少工件的磨损和摩擦，有效提高表面硬度、耐磨性、

韧性、高温稳定性，大幅度提高薄膜涂层产品的使用寿命，因此能广泛应用于很

多领域[10]，但其缺点是不具备疏水性能。但在实际应用中，有些硬质薄膜还需要

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摘要：

摘要纳米SiO2薄膜有机械强度不够、易吸潮等缺点，限制了其应用范围因而对其性能进行改进研究尤为重要。本文通过向多孔SiO2溶胶网络中引入有机硅烷疏水基甲基三乙氧基硅烷（MTES）来提高复合薄膜的疏水性、引入Al2O3提高复合薄膜的硬度和机械强度，引入表面活性剂十六烷基三甲基溴化氨(CTAB)增加复合薄膜的孔洞率进而降低复合薄膜的折射率以至透过率增大，制备了SiO2-MTES-Al2O3-CTAB疏水硬质透明复合薄膜。TiO2薄膜具有优异的光催化特性，在光催化降解有机物、染料敏化太阳能电池以及防雾、自清洁等领域有着广阔的应用前景。提高TiO2薄膜光催化效率便成了一个非常具有实际意义的研究课题。本...

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