Designing Novel Hybrid Materials by One-Pot Co-condensation: From Hydrophobic Mesoporous Silica Nanoparticles to Superamphiphobic Cotton Textiles

Abstract

This work reports the synthesis and characterization of mesoporous silica nanoparticles (MSNs) functionalized with tridecafluorooctyltriethoxysilane (F13) and their in situ incorporation onto cotton textiles. The hybrid MSNs and the functional textiles were prepared by a one-pot co-condensation methodology between tetraethylorthosilicate (TEOS) and F13, with hexadecyltrimethylammonium chloride (CTAC) as the template and triethanolamine as the base. The influence of the F13 to TEOS molar ratio (1:10, 1:5 and 1:3) on the nanoparticle morphology, porosity, degree of functionalization, and hydro/oleophobic properties is discussed. The hybrid nanosilicas presented high colloidal stability and were spherical and monodispersed with average particle size of ∼45 nm. They also showed high surface areas, large pore volumes, and a wormhole-type mesoporous structure. The increase in the organosilane proportion during the co-condensation process led to a more radially branched wormhole-like mesoporosity, a decrease in the surface area, pore volume, and amount of surface silanol groups, and an enrichment of the surface with fluorocarbon moieties. These changes imparted hydrophobic and oleophobic properties to the materials, especially to that containing the highest F13 loading. Cotton textiles were coated with the F13-MSNs through an efficient and less time-consuming route. The combination between surface roughness and mesoporosity imparted by the MSNs, and the low surface energy provided by the organosilane resulted in superhydrophobic functional textiles. Moreover, the textile with the highest loading of fluorocarbon groups was superamphiphobic.

Recent developments in polymeric superoleophobic surfaces

“…The optical transmittance of the surface is higher than 90%. 118 Super Oil-Repellent Coatings The broadest application for superoleophobic surfaces is constructing super oil-repellent coatings for textiles, 46,82,89,90,105,106,[119][120][121][122] woods, 107 metal, 53,104,123 and other substrates. 83,88 Oil-repellent coatings can keep substrates from fouling or corrosion by oils and other liquids, and thus show great significance.…”

Effect of Template Removal on Synthesis of Organic-Inorganic Hybrid Mesoporous MCM-48

“…The solid-state 29 Si CP/MAS NMR spectra of the template removed MCM-48 showed three distinct peaks at −91 ppm, −101 ppm and −110 ppm as shown in Figure 6. These were assigned as the surface geminal silanol groups [Q 2 , Si(OH) 2 The Q 4 position of the sample obtained from the thermal decomposition, −111 ppm, slightly shifted to the low field region compared to that of the solvent extraction, −110 ppm, which indicated the more extensively cross-linked framework of the high temperature treated MCM-48 sample.…”

“…23 NMR spectra proved that the vinylsilyl group was succesfully grafted to MCM-48 and the sample after the solvent extraction was more reactive to VTES. Table 3 shows the framework connectivities of samples determined by the 29 Si CP/MAS NMR spectra. The Q 3 /Q 4 and Q 2 /Q 4 ratios of the sample after the solvent extraction showed a slightly higher value than the thermal decomposition.…”

“…The morphology of the crystal was obtained on a Field Emission Scanning Electron Microscope (FE-SEM) using JSM-7500F+EDS (Oxford) JEOL Co., Japan. Solid state 29 Si CP/MAS NMR spectra were performed by a 400 MHz solid state FT-NMR spectrometer (DSX 400 MHz), Bruker Anylytische GmbH.…”

“…It is generally believed that the organic units distributed more homogeneously in the case of the co-condensation method than the post-grafting method. 29 This study showed that the postgrafting method would be a good candidate to synthesize definable organic hybrid mesoporous sieves if the template is removed with solvent extraction in the final step of the synthesis of the base.…”