Skip to main content
SpringerLink
Log in

Surface modification of TiO2 nanoparticles with AHAPS aminosilane: distinction between physisorption and chemisorption

  • Published:
Adsorption Aims and scope Submit manuscript

Abstract

This paper addresses the surface modification of TiO2 nanoparticles with n-(6-aminohexyl)aminopropyltrimethoxysilane (AHAPS) using various initial aminosilane concentrations. The main objective of this article is to show experimentally the importance of the physisorption during the grafting process. The distinction between chemisorbed and physisorbed aminosilane molecules on TiO2 is thoroughly analyzed. The surface of bare and modified TiO2 particles has been characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) to gain a better understanding of the adsorption mechanism of AHAPS on TiO2. Quantitative information on surface energy of TiO2, in terms of adsorption energy sites and heterogeneity, has been investigated by quasi-equilibrium low-pressure adsorption technique using nitrogen and argon as probe molecules. The FTIR and XPS data are combined to estimate and discuss the chemisorbed and physisorbed contribution. The results demonstrate that both physisorption and chemisorption occurs but they display a different behavior. The physisorbed amounts are much higher than the chemisorbed amounts. This shows that the main part of the adsorbed layer is composed of physisorbed molecules. The physisorbed uptake depends highly on the AHAPS concentration while the chemisorbed amount remains constant. Quasi-equilibrium Ar derivative adsorption isotherms reveal that the AHAPS molecules are mostly located on the {101} and {001} faces of titania and that the two faces display the same reactivity toward AHAPS sorption. Nitrogen adsorption experiments show that the sorption takes place on the three polar surface sites of high energy. The molecules are chemisorbed onto the site displaying the highest energy while they are physisorbed on the two lower energy sites.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  • 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)

    Article  CAS  Google Scholar 

  • 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)

    Article  CAS  Google Scholar 

  • 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)

    Article  Google Scholar 

  • Billingham, J., Breen, C., Yarwood, J.: In situ determination of Bronsted/Lewis acidity on cation-exchanged clay mineral surfaces by ATR-IR. Clay Miner. 31, 513–522 (1996)

    Article  Google Scholar 

  • Blin, J.L., Stébé, M.J., Roques-Carmes, T.: Use of ordered mesoporous titania with semi-crystalline framework as photocatalyst. Colloids Surf. A 407, 177–185 (2012)

    Article  CAS  Google Scholar 

  • Bowen, P.: Particle size distribution measurement from millimeters to nanometers and from rods to platelets. J. Disper. Sci. Technol 23, 631–662 (2002)

    Article  CAS  Google Scholar 

  • Brandow, S.L., Chen, M.S., Aggarwal, R., Dulcey, C.S., Calvert, J.M., Dressick, W.J.: Fabrication of patterned amine reactivity templates using 4-chloromethylphenylsiloxane self-assembled monolayer films. Langmuir 15, 5429–5432 (1999)

    Article  CAS  Google Scholar 

  • Brunette, D., Tengvall, P., Textor, M., Thomsen, P.: Titanium in Medicine: Material Science, Surface Science, Engineering, Biological Responses and Medical Applications. Springer, Heidelberg (2001)

    Google Scholar 

  • Chen, Q., Yakovlev, N.L.: Adsorption and interaction of organosilanes on TiO2 nanoparticles. Appl. Surf. Sci. 257, 1395–1400 (2010)

    Article  CAS  Google Scholar 

  • Durupthy, O., Bill, J., Aldinger, F.: Bioinspired synthesis of crystalline TiO2: effect of amino acids on nanoparticles structure and shape. Cryst. Growth Des. 7, 2696–2704 (2007)

    Article  CAS  Google Scholar 

  • Fadley, C.S.: Angle-resolved X-ray photoelectron spectroscopy. Prog. Surf. Sci. 16, 275–388 (1984)

    Article  CAS  Google Scholar 

  • Grätzel, M.: Photoelectrochemical cells. Nature 414, 338–344 (2001)

    Article  Google Scholar 

  • Harnett, C.K., Satyalakshmi, K.M., Craighead, H.G.: Bioactive templates fabricated by low-energy electron beam lithography of self-assembled monolayers. Langmuir 17, 178–182 (2001)

    Article  CAS  Google Scholar 

  • Herrero, J., Pajares, J.A., Blanco, C.: Surface acidity of palygorskite-supported rhodium catalysts. Clays Clay Miner. 39, 651–657 (1991)

    Article  CAS  Google Scholar 

  • Herrmann, J.M.: Photocatalysis fundamentals revisited to avoid several misconceptions. Appl. Catal. B Environ. 99, 461–468 (2010)

    Article  CAS  Google Scholar 

  • 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)

    Article  CAS  Google Scholar 

  • Jansson, M., Jonsson, M., Mohl, J.: Kinetic evaluation of sorption and desorption. Adsorption 16, 155–159 (2010)

    Article  CAS  Google Scholar 

  • Kneuer, C., Sameti, M., Haltner, E.G., Schiestel, T., Schirra, H., Schmidt, H., Lehr, C.M.: Silica nanoparticles modified with aminosilanes as carriers for plasmid DNA. Int. J. Pharm. 196, 257–261 (2000)

    Article  CAS  Google Scholar 

  • 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)

    Article  CAS  Google Scholar 

  • 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)

    Article  CAS  Google Scholar 

  • Lercher, J.A., Grundling, C., Eder-Mirth, G.: Infrared studies of the surface acidity of oxides and zeolites using adsorbed probe molecules. Catal. Today 27, 353–376 (1996)

    Article  CAS  Google Scholar 

  • Michot, L.J., François, M., Cases, J.M.: Surface heterogeneity studied by a quasi-equilibrium gas adsorption procedure. Langmuir 6, 677–681 (1990)

    Article  CAS  Google Scholar 

  • 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)

    Article  CAS  Google Scholar 

  • Petri, D.S., Wenz, G., Schunk, P., Schimmel, T.: An improved method for the assembly of amino-terminated monolayers on SiO2 and the vapor deposition of gold layers. Langmuir 15, 4520–4523 (1999)

    Article  CAS  Google Scholar 

  • 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)

    Article  CAS  Google Scholar 

  • 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)

    Article  CAS  Google Scholar 

  • Ruckriem, M., Inayat, A., Enke, D., Glaser, R., Einicke, W.D., Rockmann, R.: Inverse gas chromatography for determining the dispersive surface energy of porous silica. Colloids Surf. A 357, 21–26 (2010)

    Google Scholar 

  • Stephanovic, S., Ali Ahmad, M., Razafitianamaharavo, A., Villiéras, F., Barrès, O., 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)

    Article  Google Scholar 

  • Tanga, X., Li, J., Suna, L., Hao, J.: Origination of N2O from NO reduction by NH3 over β-MnO2 and α-Mn2O3. Appl. Catal. B 99, 156–162 (2010)

    Article  Google Scholar 

  • Ukaji, E., Furusawa, T., Sato, M., Suzuki, N.: The effect of surface modification with silane coupling agent on suppressing the photo-catalytic activity of fine TiO2 particles as inorganic UV filter. Appl. Surf. Sci. 254, 563–569 (2007)

    Article  CAS  Google Scholar 

  • Vandenberg, E.T., Bertilsson, L., Liedberg, B., Uvdal, K., Erlandsson, R., Elwing, H., Lundstroem, I.: Structure of 3-aminopropyl triethoxy silane on silicon oxide. J. Colloid Interf. Sci. 147, 103–118 (1991)

    Article  CAS  Google Scholar 

  • Villiéras, F., Cases, J.M., François, M., Michot, L.J., Thomas, F.: Texture and surface energetic heterogeneity of solid from modeling of low pressure gas adsorption isotherms. Langmuir 8, 1789–1795 (1992)

    Article  Google Scholar 

  • 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)

    Article  Google Scholar 

  • 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)

    Article  Google Scholar 

  • 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)

    Article  Google Scholar 

  • 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)

    Article  Google Scholar 

  • Wallart, X., Henry de Villeneuve, C., Allongue, P.: Truly quantitative XPS characterization of organic monolayers on silicon: study of alkyl and alkoxy monolayers on H-Si(111). J. Am. Chem. Soc. 127, 7871–7878 (2005)

    Article  CAS  Google Scholar 

  • Weigel, C., Kellner, R.: FTIR-ATR-spectroscopic investigation of the silanization of germanium surfaces with 3-aminopropyltriethoxysilane. Fresenius Z. Anal. Chem. 335, 663–668 (1989)

    Article  CAS  Google Scholar 

  • Wu, Y.L., Lin, J.J., Hsu, P.Y., Hsu, C.P.: Highly sensitive polysilicon wire sensor for DNA detection using silica nanoparticles/γ-APTES nanocomposite for surface modification. Sens. Actuators B 155, 709–715 (2011)

    Article  CAS  Google Scholar 

  • Yang, S.Q., Yuan, P., He, H.P., Qin, Z.H., Zhou, Q., Zhu, J.X., Liu, D.: Effect of reaction temperature on grafting of γ-aminopropyl triethoxysilane (APTES) onto kaolinite. Appl. Clay Sci. 62, 8–14 (2012)

    Article  Google Scholar 

  • Zhao, J., Milanova, M., Warmoeskerken, M.M.C.G., Dutschk, V.: Surface modification of TiO2 nanoparticles with silane coupling agents. Colloids Surf. A 413, 273–279 (2011)

    Article  Google Scholar 

  • Zheng, J.W., Zhu, Z.H., Chen, H.F., Liu, Z.F.: Nanopatterned assembling of colloidal gold nanoparticles on silicon. Langmuir 16, 4409–4412 (2000)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We express our gratitude to Dr. Aurélien Renard and Martine Mallet (LCPME, Université de Lorraine, CNRS) for acquiring the XPS spectra.

Author information

Authors and Affiliations

  1. Laboratoire Interdisciplinaire des Environnements Continentaux, Université de Lorraine, UMR 7360, CNRS, 15 Avenue du Charmois, 54500, Vandœuvre-lès-Nancy, France

    Mounir Kassir, Angelina Razafitianamaharavo & Frédéric Villiéras

  2. Laboratory of Materials, Catalysis, Environment and Analytical Methods, Faculty of Sciences I, Lebanese University, Campus Rafic Hariri, Beyrouth, Lebanon

    Mounir Kassir, Tayssir Hamieh & Joumana Toufaily

  3. GeoRessources, Université de Lorraine, UMR 7359, CNRS, CREGU, Faculté des Sciences et Techniques, Rue Jacques Callot, 54506, Vandœuvre-lès-Nancy, France

    Odile Barres

  4. Laboratoire Réactions et Génie des Procédés, Université de Lorraine, UPR 3349, CNRS, 1 rue Grandville, 54001, Nancy Cedex, France

    Thibault Roques-Carmes

Authors
  1. Mounir Kassir
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Thibault Roques-Carmes
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Tayssir Hamieh
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Angelina Razafitianamaharavo
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Odile Barres
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Joumana Toufaily
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Frédéric Villiéras
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Thibault Roques-Carmes.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 101 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Kassir, M., Roques-Carmes, T., Hamieh, T. et al. Surface modification of TiO2 nanoparticles with AHAPS aminosilane: distinction between physisorption and chemisorption. Adsorption 19, 1197–1209 (2013). https://doi.org/10.1007/s10450-013-9555-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10450-013-9555-y

Keywords

Search

Navigation