Skip to main content Accessibility help
×
Home

Review of surface water interactions with metal oxide nanoparticles

  • Jason J. Calvin (a1), Peter F. Rosen (a1), Nancy L. Ross (a2), Alexandra Navrotsky (a3) and Brian F. Woodfield (a1)...

Abstract

Surface water can affect the properties of metal oxide nanoparticles. Investigations on several systems revealed that nanoparticles have different thermodynamic properties than their bulk counterparts due to adsorbed water on their surfaces. Some thermodynamically metastable phases of bulk metal oxides become stable when reduced to the nanoscale, partially due to interactions between high energy surfaces and surface water. Water adsorption microcalorimetry and high-temperature oxide melt solution calorimetry, low-temperature specific heat calorimetry, and inelastic neutron scattering are used to understand the interactions of surface water with metal oxide nanoparticles. Computational methods, such as molecular dynamics simulations and density functional theory calculations, have been used to study these interactions. Investigations on titania, cassiterite, and alumina illustrate the insights gained by these measurements. The energetics of water on metal oxide surfaces are different from those of either liquid water or hexagonal ice, and there is substantial variation in water interactions on different metal oxide surfaces.

Copyright

Corresponding author

a)Address all correspondence to this author. e-mail: brian_woodfield@byu.edu

Footnotes

Hide All

This section of Journal of Materials Research is reserved for papers that are reviews of literature in a given area.

Footnotes

References

Hide All
1.Heath, J.R., Shiang, J., and Alivisatos, A.: Germanium quantum dots: Optical properties and synthesis. J. Chem. Phys. 101, 16071615 (1994).
2.Alivisatos, A.P.: Semiconductor clusters, nanocrystals, and quantum dots. Science 271, 933937 (1996).
3.Dou, L., Wong, A.B., Yu, Y., Lai, M., Kornienko, N., Eaton, S.W., Fu, A., Bischak, C.G., Ma, J., and Ding, T.: Atomically thin two-dimensional organic-inorganic hybrid perovskites. Science 349, 15181521 (2015).
4.Huang, B., Schliesser, J., Olsen, R.E., Smith, S.J., and Woodfield, B.F.: Synthesis and thermodynamics of porous metal oxide nanomaterials. Curr. Inorg. Chem. 4, 4053 (2014).
5.Trueba, M. and Trasatti, S.P.: γ‐Alumina as a support for catalysts: A review of fundamental aspects. Eur. J. Inorg. Chem. 2005, 33933403 (2005).
6.Rahmati, M., Huang, B., Mortensen, M.K. Jr., Keyvanloo, K., Fletcher, T.H., Woodfield, B.F., Hecker, W.C., and Argyle, M.D.: Effect of different alumina supports on performance of cobalt Fischer–Tropsch catalysts. J. Catal. 359, 92100 (2018).
7.Smith, S.J., Huang, B., Liu, S., Liu, Q., Olsen, R.E., Boerio-Goates, J., and Woodfield, B.F.: Synthesis of metal oxide nanoparticles via a robust “solvent-deficient” method. Nanoscale 7, 144156 (2015).
8.Olsen, R.E., Bartholomew, C.H., Huang, B., Simmons, C., and Woodfield, B.F.: Synthesis and characterization of pure and stabilized mesoporous anatase titanias. Microporous Mesoporous Mater. 184, 714 (2014).
9.Mardkhe, M.K., Huang, B., Bartholomew, C.H., Alam, T.M., and Woodfield, B.F.: Synthesis and characterization of silica doped alumina catalyst support with superior thermal stability and unique pore properties. J. Porous Mater. 23, 475487 (2016).
10.Huang, B., Bartholomew, C.H., Smith, S.J., and Woodfield, B.F.: Facile solvent-deficient synthesis of mesoporous γ-alumina with controlled pore structures. Microporous Mesoporous Mater. 165, 7078 (2013).
11.Calvin, J.J., Asplund, M., Zhang, Y., Huang, B., and Woodfield, B.F.: Heat capacity and thermodynamic functions of γ-Al2O3. J. Chem. Thermodyn. 112, 7785 (2017).
12.Calvin, J.J., Asplund, M., Zhang, Y., Huang, B., and Woodfield, B.F.: Heat capacity and thermodynamic functions of boehmite (AlOOH) and silica-doped boehmite. J. Chem. Thermodyn. 118, 338345 (2018).
13.Asplund, M., Calvin, J.J., Zhang, Y., Huang, B., and Woodfield, B.F.: Heat capacity and thermodynamic functions of silica-doped γ-Al2O3. J. Chem. Thermodyn. 118, 165174 (2018).
14.Spencer, E.C., Huang, B., Parker, S.F., Kolesnikov, A.I., Ross, N.L., and Woodfield, B.F.: The thermodynamic properties of hydrated γ-Al2O3 nanoparticles. J. Chem. Phys. 139, 244705 (2013).
15.Navrotsky, A. and Kleppa, O.: Enthalpy of the anatase‐rutile transformation. J. Am. Ceram. Soc. 50, 626 (1967).
16.Smith, S.J., Stevens, R., Liu, S., Li, G., Navrotsky, A., Boerio-Goates, J., and Woodfield, B.F.: Heat capacities and thermodynamic functions of TiO2 anatase and rutile: Analysis of phase stability. Am. Mineral. 94, 236243 (2009).
17.Levchenko, A.A., Li, G., Boerio-Goates, J., Woodfield, B.F., and Navrotsky, A.: TiO2 stability landscape: Polymorphism, surface energy, and bound water energetics. Chem. Mater. 18, 63246332 (2006).
18.McHale, J., Auroux, A., Perrotta, A., and Navrotsky, A.: Surface energies and thermodynamic phase stability in nanocrystalline aluminas. Science 277, 788791 (1997).
19.McHale, J., Navrotsky, A., and Perrotta, A.: Effects of increased surface area and chemisorbed H2O on the relative stability of nanocrystalline γ-Al2O3 and α-Al2O3. J. Phys. Chem. B 101, 603613 (1997).
20.Wang, H-W., Wesolowski, D.J., Proffen, T.E., Vlcek, L., Wang, W., Allard, L.F., Kolesnikov, A.I., Feygenson, M., Anovitz, L.M., and Paul, R.L.: Structure and stability of SnO2 nanocrystals and surface-bound water species. J. Am. Chem. Soc. 135, 68856895 (2013).
21.Navrotsky, A.: Calorimetry of nanoparticles, surfaces, interfaces, thin films, and multilayers. J. Chem. Thermodyn. 39, 19 (2007).
22.Navrotsky, A.: Energetics of nanoparticle oxides: Interplay between surface energy and polymorphism. Geochem. Trans. 4, 3437 (2003).
23.Ushakov, S.V. and Navrotsky, A.: Direct measurements of water adsorption enthalpy on hafnia and zirconia. Appl. Phys. Lett. 87, 164103 (2005).
24.Drazin, J.W. and Castro, R.H.: Water adsorption microcalorimetry model: Deciphering surface energies and water chemical potentials of nanocrystalline oxides. J. Phys. Chem. C 118, 1013110142 (2014).
25.Castro, R.H. and Quach, D.V.: Analysis of anhydrous and hydrated surface energies of gamma-Al2O3 by water adsorption microcalorimetry. J. Phys. Chem. C 116, 2472624733 (2012).
26.Boerio-Goates, J., Li, G., Li, L., Walker, T.F., Parry, T., and Woodfield, B.F.: Surface water and the origin of the positive excess specific heat for 7 nm rutile and anatase nanoparticles. Nano Lett. 6, 750754 (2006).
27.Levchenko, A.A., Kolesnikov, A.I., Ross, N.L., Boerio-Goates, J., Woodfield, B.F., Li, G., and Navrotsky, A.: Dynamics of water confined on a TiO2 (anatase) surface. J. Phys. Chem. A 111, 1258412588 (2007).
28.Boerio-Goates, J., Smith, S.J., Liu, S., Lang, B.E., Li, G., Woodfield, B.F., and Navrotsky, A.: Characterization of surface defect sites on bulk and nanophase anatase and rutile TiO2 by low-temperature specific heat. J. Phys. Chem. C 117, 45444550 (2013).
29.Schliesser, J.M., Smith, S.J., Li, G., Li, L., Walker, T.F., Parry, T., Boerio-Goates, J., and Woodfield, B.F.: Heat capacity and thermodynamic functions of nano-TiO2 rutile in relation to bulk-TiO2 rutile. J. Chem. Thermodyn. 81, 311322 (2015).
30.Schliesser, J.M., Smith, S.J., Li, G., Li, L., Walker, T.F., Parry, T., Boerio-Goates, J., and Woodfield, B.F.: Heat capacity and thermodynamic functions of nano-TiO2 anatase in relation to bulk-TiO2 anatase. J. Chem. Thermodyn. 81, 298310 (2015).
31.Ma, Y., Castro, R.H., Zhou, W., and Navrotsky, A.: Surface enthalpy and enthalpy of water adsorption of nanocrystalline tin dioxide: Thermodynamic insight on the sensing activity. J. Mater. Res. 26, 848853 (2011).
32.Castro, R.H., Ushakov, S.V., Gengembre, L., Gouvêa, D., and Navrotsky, A.: Surface energy and thermodynamic stability of γ-alumina: Effect of dopants and water. Chem. Mater. 18, 18671872 (2006).
33.Navrotsky, A.: Progress and new directions in high temperature calorimetry. Phys. Chem. Miner. 2, 89104 (1977).
34.Navrotsky, A.: Progress and new directions in high temperature calorimetry revisited. Phys. Chem. Miner. 24, 222241 (1997).
35.Navrotsky, A.: Progress and new directions in calorimetry: A 2014 perspective. J. Am. Ceram. Soc. 97, 33493359 (2014).
36.Ranade, M., Navrotsky, A., Zhang, H., Banfield, J., Elder, S., Zaban, A., Borse, P., Kulkarni, S., Doran, G., and Whitfield, H.: Energetics of nanocrystalline TiO2. Proc. Natl. Acad. Sci. U. S. A. 99(Suppl. 2), 64766481 (2002).
37.White, G.K. and Collocott, S.: Heat capacity of reference materials: Cu and W. J. Phys. Chem. Ref. Data 13, 12511257 (1984).
38.Gopal, E.: Specific Heats at Low Temperatures (International Cryogenics Monograph Series) (Plenum Press, New York, 1966).
39.Calvin, J.J., Asplund, M., Akimbekov, Z., Ayoub, G., Katsenis, A.D., Navrotsky, A., Friščić, T., and Woodfield, B.F.: Heat capacity and thermodynamic functions of crystalline and amorphous forms of the metal organic framework zinc 2-ethylimidazolate, Zn(EtIm)2. J. Chem. Thermodyn. 116, 341351 (2018).
40.Smith, S.J., Lang, B.E., Liu, S., Boerio-Goates, J., and Woodfield, B.F.: Heat capacities and thermodynamic functions of hexagonal ice from T = 0.5 K to T = 38 K. J. Chem. Thermodyn. 39, 712716 (2007).
41.Lu, K.: Nanocrystalline metals crystallized from amorphous solids: Nanocrystallization, structure, and properties. Mater. Sci. Eng., R 16, 161221 (1996).
42.Zhang, H. and Banfield, J.F.: A model for exploring particle size and temperature dependence of excess heat capacities of nanocrystalline substances. Nanostruct. Mater. 10, 185194 (1998).
43.Shi, Q., Boerio-Goates, J., Woodfield, K., Rytting, M., Pulsipher, K., Spencer, E.C., Ross, N.L., Navrotsky, A., and Woodfield, B.F.: Heat capacity studies of surface water confined on cassiterite (SnO2) nanoparticles. J. Phys. Chem. C 116, 39103917 (2012).
44.Sears, V.F.: Neutron scattering lengths and cross sections. Neutron News 3, 2637 (1992).
45.Ross, N., Spencer, E., Levchenko, A., Kolesnikov, A., Wesolowski, D., Cole, D., Mamontov, E., and Vlcek, K.: Neutron scattering studies of surface water on metal oxide nanoparticles. In Neutron Applications in Earth, Energy and Environmental Sciences, L. Liyuan, R. Rinaldi, and H. Schober, eds. (Springer, New York, 2008); pp. 233254.
46.Spencer, E.C., Ross, N.L., Parker, S.F., Kolesnikov, A.I., Woodfield, B.F., Woodfield, K., Rytting, M., Boerio-Goates, J., and Navrotksy, A.: Influence of particle size and water coverage on the thermodynamic properties of water confined on the surface of SnO2 cassiterite nanoparticles. J. Phys. Chem. C 115, 2110521112 (2011).
47.Ross, N.L., Spencer, E.C., Levchenko, A.A., Kolesnikov, A.I., Wesolowski, D.J., Cole, D.R., Mamontov, E., and Vlcek, L.: Studies of mineral-water surfaces. In Neutron Applications in Earth, Energy and Environmental Sciences, Liyuan, L., Rinaldi, R., and Schober, H., eds. (Springer, New York, 2009); pp. 235256.
48.Spencer, E.C., Levchenko, A.A., Ross, N.L., Kolesnikov, A.I., Boerio-Goates, J., Woodfield, B.F., Navrotsky, A., and Li, G.: Inelastic neutron scattering study of confined surface water on rutile nanoparticles. J. Phys. Chem. A 113, 27962800 (2009).
49.Morterra, C.: An infrared spectroscopic study of anatase properties. Part 6—Surface hydration and strong Lewis acidity of pure and sulphate-doped preparations. J. Chem. Soc., Faraday Trans. 1 84, 16171637 (1988).
50.Bezrodna, T., Puchkovska, G., Shymanovska, V., Baran, J., and Ratajczak, H.: IR-analysis of H-bonded H2O on the pure TiO2 surface. J. Mol. Struct. 700, 175181 (2004).
51.Ionescu, A., Allouche, A., Aycard, J-P., Rajzmann, M., and Hutschka, F.: Study of γ-alumina surface reactivity: Adsorption of water and hydrogen sulfide on octahedral aluminum sites. J. Phys. Chem. B 106, 93599366 (2002).
52.Mamontov, E., Vlcek, L., Wesolowski, D.J., Cummings, P.T., Wang, W., Anovitz, L., Rosenqvist, J., Brown, C., and Garcia Sakai, V.: Dynamics and structure of hydration water on rutile and cassiterite nanopowders studied by quasielastic neutron scattering and molecular dynamics simulations. J. Phys. Chem. C 111, 43284341 (2007).
53.Mamontov, E., Wesolowski, D.J., Vlcek, L., Cummings, P.T., Rosenqvist, J., Wang, W., and Cole, D.R.: Dynamics of hydration water on rutile studied by backscattering neutron spectroscopy and molecular dynamics simulation. J. Phys. Chem. C 112, 1233412341 (2008).
54.Mamontov, E., Vlcek, L., Wesolowski, D.J., Cummings, P.T., Rosenqvist, J., Wang, W., Cole, D.R., Anovitz, L.M., and Gasparovic, G.: Suppression of the dynamic transition in surface water at low hydration levels: A study of water on rutile. Phys. Rev. E 79, 051504 (2009).
55.Koparde, V.N. and Cummings, P.T.: Molecular dynamics study of water adsorption on TiO2 nanoparticles. J. Phys. Chem. C 111, 69206926 (2007).
56.Vlček, L. and Cummings, P.T.: Adsorption of water on TiO2 and SnO2 surfaces: Molecular dynamics study. Collect. Czech. Chem. Commun. 73, 575589 (2008).
57.Redfern, P., Zapol, P., Curtiss, L., Rajh, T., and Thurnauer, M.: Computational studies of catechol and water interactions with titanium oxide nanoparticles. J. Phys. Chem. B 107, 1141911427 (2003).
58.Salameh, S., Schneider, J., Laube, J., Alessandrini, A., Facci, P., Seo, J.W., Ciacchi, L.C., and Mädler, L.: Adhesion mechanisms of the contact interface of TiO2 nanoparticles in films and aggregates. Langmuir 28, 1145711464 (2012).
59.Laube, J., Salameh, S., Kappl, M., Mädler, L., and Colombi Ciacchi, L.: Contact forces between TiO2 nanoparticles governed by an interplay of adsorbed water layers and roughness. Langmuir 31, 1128811295 (2015).
60.Gercher, V.A. and Cox, D.F.: Water adsorption on stoichiometric and defective SnO2(110) surfaces. Surf. Sci. 322, 177184 (1995).
61.Kumar, N., Kent, P.R., Bandura, A.V., Kubicki, J.D., Wesolowski, D.J., Cole, D.R., and Sofo, J.O.: Faster proton transfer dynamics of water on SnO2 compared to TiO2. J. Chem. Phys. 134, 044706 (2011).
62.Arrouvel, C., Digne, M., Breysse, M., Toulhoat, H., and Raybaud, P.: Effects of morphology on surface hydroxyl concentration: A DFT comparison of anatase–TiO2 and γ-alumina catalytic supports. J. Catal. 222, 152166 (2004).
63.Digne, M., Sautet, P., Raybaud, P., Euzen, P., and Toulhoat, H.: Use of DFT to achieve a rational understanding of acid–basic properties of γ-alumina surfaces. J. Catal. 226, 5468 (2004).
64.Asplund, M., Calvin, J.J., Zhang, Y., Huang, B., and Woodfield, B.F.: Heat capacity and thermodynamic functions of γ-Al2O3 synthesized from Al(NO3)3. J. Chem. Thermodyn. 132, 295305 (2019).

Keywords

Metrics

Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed