通过四乙氧基硅烷和(3-氨基丙基)三乙氧基硅烷的共缩合可控合成氨基官能化二氧化硅颗粒。

IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Langmuir Pub Date : 2024-11-17 DOI:10.1021/acs.langmuir.4c03433
Chang Liu, Yang Hu, Lin Zhang, Wensheng Yang
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引用次数: 0

摘要

由于氨基功能化二氧化硅具有高表面活性和在各个领域的多种应用潜力,因此引起了人们的极大兴趣。虽然经典的共缩合方法常用于合成氨基功能化二氧化硅颗粒,但(3-氨基丙基)三乙氧基硅烷(APTES)和四乙氧基硅烷在不同条件下的反应机理仍不清楚,导致二氧化硅颗粒之间出现意外的自核或交联,从而阻碍了对功能化程度的合理控制。为了解决这个问题,我们通过研究 APTES 浓度和含水量对硅烷水解和缩合的影响,系统地探索了 Stöber 法中氨基官能化二氧化硅颗粒的共缩合生长机理。实验结果表明,APTES 可降低水解/缩合速率,而适度的水含量则可促进水解/缩合速率和硅胶粒子的整体质量。因此,我们成功地合理合成了直径为 213 至 670 nm、氮含量≤2.8 wt % 的氨基功能化二氧化硅颗粒。APTES 浓度与颗粒特性之间的关系呈现双相趋势。在 APTES 浓度较低(≤2.0 mM)时,颗粒尺寸保持稳定,而等电点迅速升高。由于 APTES 对二氧化硅生长的抑制作用,APTES 浓度从 2.0 mM 进一步增加到 100.0 mM 会导致粒径减小,即使等电点保持不变,氮含量也会继续增加。这些具有不同表面氨基密度的二氧化硅颗粒被用作载入金纳米粒子的基质。由此产生的功能化颗粒在还原 4-硝基苯胺时表现出独特的催化能力,在各个领域的应用潜力巨大。
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Controllable Synthesis of Amino-Functionalized Silica Particles via Co-condensation of Tetraethoxysilane and (3-Aminopropyl)triethoxysilane.

Amino-functionalized silica has attracted a great deal of interest due to its high surface reactivity and potential for diverse applications across various fields. While the classical co-condensation method is commonly used to synthesize amino-functionalized silica particles, the mechanism of the reaction between (3-aminopropyl)triethoxysilane (APTES) and tetraethoxysilane under different conditions remains unclear, leading to unexpected self-nucleation or cross-linking between silica particles and consequently hindering rational control over the extent of functionalization. To address this issue, we systematically explored the co-condensation growth mechanism of amino-functionalized silica particles in the Stöber method by investigating the effects of APTES concentration and water content on the hydrolysis and condensation of silanes. The experimental results revealed that APTES could decrease the rate of hydrolysis/condensation, while the moderate water content promoted both the rate of hydrolysis/condensation and the overall quality of the silica particles. Consequently, we successfully demonstrated the rational synthesis of amino-functionalized silica particles with diameters ranging from 213 to 670 nm and a nitrogen content of ≤2.8 wt %. The relationship between the APTES concentration and particle properties exhibited a biphasic trend. At low APTES concentrations (≤2.0 mM), the particle size remained stable while the isoelectric point increased rapidly. Further increasing the APTES concentration from 2.0 to 100.0 mM induced a decrease in particle size due to APTES's inhibitory effect on silica growth, with nitrogen content continuing to increase even after the isoelectric point remained unchanged. These silica particles, featuring varying surface amino group densities, were utilized as matrices for loading Au nanoparticles. The resulting functionalized particles exhibited distinctive catalytic ability in the reduction of 4-nitroaniline, demonstrating significant potential for applications across various fields.

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来源期刊
Langmuir
Langmuir 化学-材料科学:综合
CiteScore
6.50
自引率
10.30%
发文量
1464
审稿时长
2.1 months
期刊介绍: Langmuir is an interdisciplinary journal publishing articles in the following subject categories: Colloids: surfactants and self-assembly, dispersions, emulsions, foams Interfaces: adsorption, reactions, films, forces Biological Interfaces: biocolloids, biomolecular and biomimetic materials Materials: nano- and mesostructured materials, polymers, gels, liquid crystals Electrochemistry: interfacial charge transfer, charge transport, electrocatalysis, electrokinetic phenomena, bioelectrochemistry Devices and Applications: sensors, fluidics, patterning, catalysis, photonic crystals However, when high-impact, original work is submitted that does not fit within the above categories, decisions to accept or decline such papers will be based on one criteria: What Would Irving Do? Langmuir ranks #2 in citations out of 136 journals in the category of Physical Chemistry with 113,157 total citations. The journal received an Impact Factor of 4.384*. This journal is also indexed in the categories of Materials Science (ranked #1) and Multidisciplinary Chemistry (ranked #5).
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