DFT study on effects of hydrolysis degrees of 3-mercaptopropyltriethoxysilane on grafting mechanisms of nano-silica

SHANG Zhixin; ZHANG Xianglan

doi:10.11949/j.issn.0438-1157.20180940

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DFT study on effects of hydrolysis degrees of 3-mercaptopropyltriethoxysilane on grafting mechanisms of nano-silica

Thermodynamics | 更新时间：2026-07-24

- DFT study on effects of hydrolysis degrees of 3-mercaptopropyltriethoxysilane on grafting mechanisms of nano-silica
- CIESC Journal Vol. 70, Issue 5, Pages: 1663-1673(2019)
- 作者机构：
  
  中国矿业大学(北京)化学与环境工程学院，北京 100083
- 作者简介：
- 基金信息：
- DOI：10.11949/j.issn.0438-1157.20180940
  CLC： O 643.12
- Received：20 August 2018，
  
  Revised：2019-02-14，
  
  Online First：24 July 2026，
  
  Published：05 May 2019
- 稿件说明：
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尚志新, 张香兰. γ-巯丙基三乙氧基硅烷水解程度对纳米二氧化硅接枝机理影响的DFT研究[J]. 化工学报, 2019, 70(5): 1663-1673

SHANG Zhixin, ZHANG Xianglan. DFT study on effects of hydrolysis degrees of 3-mercaptopropyltriethoxysilane on grafting mechanisms of nano-silica[J]. CIESC Journal, 2019, 70(5): 1663-1673
尚志新, 张香兰. γ-巯丙基三乙氧基硅烷水解程度对纳米二氧化硅接枝机理影响的DFT研究[J]. 化工学报, 2019, 70(5): 1663-1673 DOI： 10.11949/j.issn.0438-1157.20180940.

SHANG Zhixin, ZHANG Xianglan. DFT study on effects of hydrolysis degrees of 3-mercaptopropyltriethoxysilane on grafting mechanisms of nano-silica[J]. CIESC Journal, 2019, 70(5): 1663-1673 DOI： 10.11949/j.issn.0438-1157.20180940.

摘要

为探索

-巯丙基三乙氧基硅烷(MPTS)水解程度对纳米二氧化硅接枝机理的影响，采用基于密度泛函理论(DFT)的量子化学方法，选择合适的泛函和合理的模型，系统研究了MPTS及其不同水解程度产物的反应活性及与纳米二氧化硅的接枝机理，为纳米二氧化硅改性工艺优化及改性效果的提升提供重要理论基础。结果表明：经数据对比确定GGA-PBE泛函优化后的纳米二氧化硅团簇模型为最合理模型。二氧化硅表面硅羟基中的氧原子为亲核活性中心，氢原子为亲电活性中心，MPTS及其水解产物中氧原子为亲核活性中心，硅原子为亲电活性中心。水解引起LUMO轨道向硅原子偏移，硅原子亲电指数提高，而HOMO轨道向氧原子偏移，氧原子的亲核指数提高，引起MPTS水解产物更容易受到二氧化硅表面硅羟基攻击，进而提高了接枝反应活性。MPTS的水解降低了接枝反应的活化能，不同水解程度产物接枝反应活化能(

)顺序为M0＞M3＞M1＞M2(M0、M1、M2和M3分别表示MPTS及其一级、二级和三级水解产物)，接枝反应属于S

2亲核取代，且为放热反应。M0、M1和M2都是通过脱醇机理发生接枝反应，空间位阻效应和偶联剂中心硅原子的亲电性能为反应主要控制因素，而M3是通过脱水机理发生接枝反应。

Abstract

In order to investigate the effects of hydrolysis degrees of 3-mercaptopropyltriethoxysilane (MPTS) on the grafting mechanisms of nano-silica

the grafting activities and grafting mechanisms of the hydrolyzed products in different degrees are systematically investigated based on density functional theory (DFT). The results show that the cluster model of nano-silica optimized by the GGA-PBE function is the most reasonable. The O atoms in surface silanols of nano-silica are the nucleophilic sites and the H atoms are the electrophilic sites. For MPTS and its hydrolyzed products

the O atoms are the nucleophilic sites and the Si atoms are the electrophilic sites. The LUMO orbitals shift to Si atoms and the HOMO orbitals to O atoms after hydrolysis. The electrophilic indexes of Si atoms and nucleophilic indexes of O atoms are all increased according to the Fukui function

indicating that the hydrolyzed products are more susceptible to be attacked by the surface silanols of nano-silica and the activities of grafting reaction are improved after hydrolysis. The active energies (

) of grafting reactions for M0—M3 follow the order of M0＞M3＞M1＞M2 (M0 is short for MPTS

M3 are short for the hydrolyzed products of first

second

and third ord

respectively)

the active energies are obviously reduced after hydrolysis. The grafting reactions of M0-M3 are S

2 nucleophilic substitution and exothermal reactions

but the mechanisms of the grafting reactions are quite different. For M0 — M2 the grafting reactions occur

via

the reaction channels of eliminating ethanol

but for M3 the grafting reaction occurs

via

the reaction channels of eliminating H

O. The steric hindrance and the electrophilicity of Si atoms have a significant effect on the grafting reactions of M0—M2.

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references

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