Abstract
The surface energetic heterogeneity of Aerosil OX50 silica is investigated before and after modification by the grafting of various amounts of hydrophobic hexadecyltrichlorosilane (HTS). A detailed study is conducted to obtain new insight into the grafting process using volumetric techniques based on molecular probing. The surface of the silica particles has been thoroughly characterized using classical N2 Brunauer–Emmett–Teller measurements and by low-pressure quasi-equilibrium volumetry using nitrogen and argon as probe molecules. The experimental data are analyzed using the derivative isotherm summation method in order to gain quantitative information on the specific surface area, the surface energy and the polarity of the bare and HTS-covered silica, in terms of adsorption energy sites and heterogeneity. The modification process is also studied by Fourier transform infrared spectroscopy (FTIR) and total carbon mass measurements performed on solid samples (TOC). The combination of these three techniques leads to a better description of organosilane grafting onto the particles. The bare silica surface appears energetically heterogeneous due to the use of 5 different adsorption sites to describe the low pressure adsorption results. The HTS molecules are mainly located on the polar high and medium energy domains. At the largest HTS coverage (2.1 µmol/m2), the surface becomes energetically homogeneous (one site of low energy) and fully apolar. The data obtained from the low-pressure gas adsorption have been employed to estimate the grafted organic content in contact with the gas. The surface coverages derived from volumetry analysis and TOC measurements are in acceptable agreement but some difference can be recognized. The discrepancy is discussed in terms of conformation of the HTS molecules at the solid surface. The proposed conformational changes are supported by the FTIR results.
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Ahmed, G.S., Gilbert, M., Mainprize, S., Rogerson, M.: FTIR analysis of silane grafted high density polyethylene. Plast. Rubber Compos. 38, 13–20 (2009)
Aldeek, F., Mustin, C., Balan, L., Roques-Carmes, T., Fontaine-Aupart, M.P., Schneider, R.: Surface-engineered quantum dots for the labeling of hydrophobic microdomains in bacterial biofilms. Biomaterials 32, 5459–5470 (2011)
Alem, H., Schejn, A., Roques-Carmes, T., Ghanbaja, J., Schneider, R.: Thermo-responsive and aqueous dispersible ZnO/PNIPAM core/shell nanoparticles. Nanotechnology 26, 335605 (2015)
Ali Ahmad, M., Prelot, B., Razafitianamaharavo, A., Douillard, J.M., Zajac, J., Dufour, F., Durupthy, O., Chaneac, C., Villiéras, F.: Influence of morphology and crystallinity on surface reactivity of nanosized anatase TiO2 studied by adsorption techniques. 1. The use of gaseous molecular probes. J. Phys. Chem. C 116, 24596–24606 (2012)
Alloul, H., Roques-Carmes, T., Hamieh, T., Razafitianamaharavo, A., Barres, O., Toufaily, J., Villiéras, F.: Effect of chemical modification on surface free energy components of Aerosil silica powders determined with capillary rise technique. Powder Technol. 246, 575–582 (2013)
Balard, H., Saada, A., Papirer, E., Siffert, B.: Energetic surface heterogeneity of illites and kaolinites. Langmuir 13, 1256–1259 (1997)
Bégin-Colin, S., Gardalla, A., Le Caer, G., Humbert, O., Thomas, F., Barres, O., Villiéras, F., Toma, L.F., Bertrand, G., Zahraa, O., Gallart, M., Hönerlage, B., Gilliot, P.: On the origin of the decay of the photocatalytic activity of TiO2 powders ground at high energy. J. Phys. Chem. C 113, 16589–16602 (2009)
Brunel, D., Cauvel, A., Di Renzo, F., Fajula, F., Fubini, B., Chiche, B., Garrone, E.: Preferential grafting of alkoxysilane coupling agents on the hydrophobic portion of the surface of micelle-templated silica. New J. Chem. 24, 807–813 (2000)
Cahen, D., Hodes, G., Grätzel, M., Guillemoles, J.F., Riess, I.: Nature of photovoltaic action in dye-sensitized solar cells. J. Phys. Chem. B 104, 2053–2059 (2000)
Cases, J.M., Villiéras, F.: Thermodynamic model of ionic and non-ionic surfactant adsorption-abstraction on heterogeneous surfaces. Langmuir 8, 1251–1264 (1992)
Chamerois, M., François, F., Villiéras, F., Yvon, J.: Modification of calcium carbonate surface properties: macroscopic and microscopic investigations. J. Adhes. Sci. Technol. 13, 1481–1493 (1999)
Cheesman, B.T., Willott, J.D., Webber, G.B., Edmondson, S., Wanless, E.J.: pH-responsive brush-modified silica hybrids synthesized by surface-initiated ARGET ATRP. ACS Macro Lett. 1, 1161–1165 (2012)
Chen, Q., Yakovlev, N.L.: Adsorption and interaction of organosilanes on TiO2 nanoparticles. Appl. Surf. Sci. 257, 1395–1400 (2010)
Denoyel, R., Trens, P.: Influence of water on adsorption of triethylsilanol onto silica. J. Phys. Chem. 99, 3711–3714 (1995)
Feng, X., Zhang, S., Wu, H., Lou, X.: A novel folic acid-conjugated TiO2–SiO2 photosensitizer for cancer targeting in photodynamic therapy. Colloids Surf. B 125, 197–205 (2015)
Garcia-Gonzalez, C.A., Saurina, J., Ayllon, J.A., Domingo, C.: Preparation and characterization of surface silanized TiO2 nanoparticles under compressed CO2: reaction kinetics. J. Phys. Chem. C 113, 13780–13786 (2009)
Heng, J.Y.Y., Bismarck, A., Lee, A.F., Wilson, K., Williams, D.R.: Anisotropic surface energetics and wettability of macroscopic form I paracetamol crystals. Langmuir 22, 2760–2769 (2006)
Hoogeveen, N., Cohen Stuart, M.A., Fleer, G.J.: Polyelectrolyte adsorption on oxides II. Reversibility and exchange. J. Colloid Interface Sci. 182, 146–157 (1996)
Inumaru, K., Murashima, M., Kasahara, T., Yamanaka, S.: Enhanced photocatalytic decomposition of 4-nonylphenol by surface-organografted TiO2: a combination of molecular selective adsorption and photocatalysis. Appl. Catal. B 52, 275–280 (2004)
Jansson, M., Jonsson, M., Mohl, J.: Kinetic evaluation of sorption and desorption. Adsorption 16, 155–159 (2010)
Kagan, C.R., Mitzi, D.B., Dimitrakopoulos, C.D.: Organic-inorganic hybrid materials as semiconducting channels in thin-film field-effect transistors. Science 286, 945–947 (1999)
Kassir, M., Roques-Carmes, T., Hamieh, T., Razafitianamaharavo, A., Barres, O., Toufaily, J., Villiéras, F.: Surface modification of TiO2 nanoparticles with AHAPS aminosilane: distinction between physisorption and chemisorption. Adsorption 19, 1197–1209 (2013)
Kassir, M., Roques-Carmes, T., Assaker, K., Hamieh, T., Razafitianamaharavo, A., Toufaily, J., Villiéras, F.: Enhanced photocatalytic degradation of salicylic acid in water-ethanol mixtures from titanium dioxide grafted with hexadecyltrichlorosilane. Phys. Proced. 55, 403–408 (2014)
Kassir, M., Roques-Carmes, T., Hamieh, T., Toufaily, J., Akil, M., Barres, O., Villiéras, F.: Improvement of the photocatalytic activity of TiO2 induced by organic pollutant enrichment at the surface of the organografted catalyst. Colloids Surf. A 485, 73–83 (2015)
Kellou, H., Hamdi, B., Brendlé, E., Gottschalk-Gaudig, T., Barthel, H., Ridaoui, H., Balard, H., Donnet, J.B.: Surface properties of dimethylsilylated silicas assessed using IGC at finite concentration. Colloids Surf. A 327, 90–94 (2008)
Lazghab, M., Saleh, K., Guigon, P.: Functionnalisation of porous silica powders in a fluidized-bed reactor with glycidoxypropyltrimethoxysilane (GPTMS) and aminopropyltriethoxysilane (APTES). Chem. Eng. Res. Des. 88, 686–692 (2010)
Lee, S.H., Saito, N., Takai, O.: Self-assembly of human plasma fibrinogens on binary organosilane monolayers with micro domains. Appl. Surf. Sci. 255, 7912–7917 (2009)
Lux, F., Mignot, A., Mowat, P., Louis, C., Dufort, S., Bernhard, C., Denat, F., Boschetti, F., Brunet, C., Antoine, R., Dugourd, P., Laurent, S., Vander Elst, L., Muller, R., Sancey, L., Josserand, V., Coll, J.L., Stupar, V., Barbier, E., Rémy, C., Broisat, A., Ghezzi, C., Le Duc, G., Roux, S., Perriat, P., Tillement, O.: Ultrasmall rigid particles as multimodal probes for medical applications. Angew. Chem. Int. Ed. 50, 12299–12303 (2011)
Macyk, W., Szaciłowski, K., Stochel, G., Buchalska, M., Kuncewicz, J., Labuz, P.: Titanium(IV) complexes as direct TiO2 photosensitizers. Coord. Chem. Rev. 254, 2687–2701 (2010)
Michot, L.J., François, M., Cases, J.M.: Surface heterogeneity studied by a quasi-equilibrium gas adsorption procedure. Langmuir 6, 677–681 (1990)
Mutin, P.H., Guerrero, G., Vioux, A.: Hybrid materials from organophosphorus coupling molecules. J. Mater. Chem. 15, 3761–3768 (2005)
Nagappan, S., Choi, M.C., Sung, G., Park, S.S., Moorthy, M.S., Chu, S.W., Lee, W.K., Ha, C.S.: Highly transparent hydrophobic fluorinated polymethylsiloxane/silica organic-inorganic hybrids for anti-stain coating. Macromol. Res. 21, 669–680 (2013)
Oh, S.J., Cho, J.C., Kim, C.O., Park, J.W.: Characteristics of DNA microarray fabricated on the various aminosilane layers. Langmuir 18, 1764–1769 (2002)
Papirer, E., Balard, H., Sidqi, M.: The grafting of perfluorinated silanes on to the surface of silica: characterization by inverse gas chromatography. J. Colloid Interface Sci. 169, 238–242 (1993)
Pardal, F., Lapinte, V., Robin, J.J.: Modification of silica nanoparticles by grafting of copolymers containing organosilane and fluorine moities. J. Polym. Sci. Part A 47, 4617–4628 (2009)
Park, J.W., Park, Y.J., Jun, C.H.: Post-grafting of silica surfaces with pre-functionalized organosilanes: new synthetic equivalents of conventional trialkoxysilanes. Chem. Commun. 47, 4860–4871 (2011)
Prelot, B., Villiéras, F., Pelletier, M., Gérard, G., Gaboriaud, F., Ehrhardt, J.J., Perrone, J., Fedoroff, M., Jeanjean, J., Lefèvre, G.: Morphology and surface heterogeneities in synthetic goethites. J. Colloid Interface Sci. 261, 244–254 (2003)
Ridaoui, H., Donnet, J.B., Balard, H., Kellou, H., Hamdi, B., Barthel, H., Gotteschalk-Gaudig, T., Legrand, A.P.: Silane modified fumed silicas and their behaviours in water: influence of grafting ratio and temperature. Colloids Surf. A 330, 80–85 (2008)
Roques-Carmes, T., Membrey, F., Kaisheva, M., Filiâtre, C., Foissy, A.: Reflectometric study of the adsorption of poly(vinyl imidazole) on a gold electrode, effects of pH, and applied potential. J. Colloid Interface Sci. 299, 504–512 (2006)
Roques-Carmes, T., Aldeek, F., Balan, L., Corbel, S., Schneider, R.: Aqueous dispersions of core/shell CdSe/CdS quantum dots as nanofluids for electrowetting. Colloids Surf. A 377, 269–277 (2011)
Sabzi, M., Mirabedini, S.M., Zohuriaan-Mehr, J., Atai, M.: Surface modification of TiO2 nano-particles with silane coupling agent and investigation of its effect on the properties of polyurethane composite coating. Prog. Organ. Coat. 65, 222–228 (2009)
Sah, A., Castricum, H.L., Bliek, A., Blank, D.H.A., ten Elshof, J.E.: Hydrophobic modification of γ-alumina membranes with organochlorosilanes. J. Membr. Sci. 243, 125–132 (2004)
Siddiquey, I.A., Ukaji, E., Furusawa, T., Sato, M., Suzuki, N.: The effects of organic surface treatment by methacryloxypropyltrimethoxysilane on the photostability of TiO2. Mater. Chem. Phys. 105, 162–168 (2007)
Smith, R.R., Williams, D.R., Burnett, D.J., Heng, J.Y.Y.: A new method to determine dispersive surface energy site distributions by inverse gas chromatography. Langmuir 30, 8029–8035 (2014)
Song, Y.Y., Hildebrand, H., Schmuki, P.: Optimized monolayer grafting of 3-aminopropyltriethoxysilane onto amorphous anatase and rutile TiO2. Surf. Sci. 604, 346–353 (2010)
Stevanovic, S., Ali Ahmad, M., Razafitianamaharavo, A., Villiéras, F., Barrès, F., Prelot, B., Zajac, J., Douillard, J.M., Chanéac, C.: Evidences for the relationship between surface structure and reactivity of goethite nanoparticles based on advanced molecular-probe methods. Adsorption 16, 185–195 (2010)
Teleki, A., Bjelobrk, N., Pratsinis, S.E.: Continuous surface functionalization of flame-made TiO2 nanoparticles. Langmuir 26, 5815–5822 (2010)
Tomovska, R., Daniloska, V., Asua, J.M.: UV/Vis photocatalytic functionalization of TiO2 nanoparticle surfaces toward water repellent properties. J. Mater. Chem. 21, 17492–17497 (2011)
Trens, P., Denoyel, R., Glez, J.C.: Comparative adsorption of argon and nitrogen for the characterisation of hydrophobized surfaces. Colloids Surf. A 245, 93–98 (2004)
Ukaji, E., Furusawa, T., Sato, M., Suzuki, N.: The effect of surface modification with silane coupling agent on suppressing the photocatalytic activity of fine TiO2 particles as inorganic UV filter. Appl. Surf. Sci. 254, 563–569 (2007)
Villiéras, F., Cases, J.M., François, M., Michot, L.J., Thomas, F.: Texture and surface energetic heterogeneity of solids from modeling of low pressure gas adsorption isotherms. Langmuir 8, 1789–1795 (1992)
Villiéras, F., Michot, L.J., Bardot, F., Cases, J.M., François, M., Rudzinski, W.: An improved derivative isotherm summation method to study surface heterogeneity of clay minerals. Langmuir 13, 1104–1117 (1997)
Villiéras, F., Leboda, R., Charmas, B., Bardot, F., Gérard, G., Rudzinski, W.: High resolution argon and nitrogen adsorption of the surface heterogeneity of carbosils. Carbon 36, 1501–1510 (1998)
Villiéras, F., Michot, L.J., Bardot, F., Chamerois, M., Eypert-Blaison, C., François, M., Gérard, G., Cases, J.M.: Surface heterogeneity of minerals. C.R. Geosci. 334, 597–609 (2002)
Villiéras, F., Chamerois, M., Yvon, J., Cases, J.M.: Surface heterogeneity at the solid-gas interface of hydrophilic solids modified by water-repellent molecules. Adsorpt. Sci. Technol. 25, 561–571 (2007)
Wang, C., Mao, H., Wang, C., Fu, S.: Dispersibility and hydrophobicity analysis of titanium dioxide nanoparticles grafted with silane coupling agent. Ind. Eng. Chem. Res. 50, 11930–11934 (2011)
Wight, A.P., Davis, M.E.: Design and preparation of organic-inorganic hybrid catalysts. Chem. Rev. 102, 3589–3614 (2002)
Xing, L., Zheng, H., Cao, Y., Che, S.: Coordination polymer coated mesoporous silica nanoparticles for pH-responsive drug release. Adv. Mater. 24, 6433–6437 (2012)
Yla-Maihaniemi, P.P., Heng, J.Y.Y., Thielmann, F., Williams, D.R.: Inverse gas chromatographic method for measuring the dispersive surface energy distribution for particulates. Langmuir 24, 9551–9557 (2008)
Zhang, Z.Y., Xu, Y.D., Ma, Y.Y., Qiu, L.L., Wang, Y., Kong, J.L., Xiong, H.M.: Biodegradable ZnO@polymer core–shell nanocarriers: pH-triggered release of doxorubicin in vitro. Angew. Chem. Int. Ed. 52, 4127–4131 (2013)
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Alloul, H., Roques-Carmes, T., Toufaily, J. et al. Towards a better description of organosilane grafting onto silica particles using volumetric techniques based on molecular probing. Adsorption 22, 923–937 (2016). https://doi.org/10.1007/s10450-016-9800-2
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DOI: https://doi.org/10.1007/s10450-016-9800-2