Skip to main content Accessibility help
×
Home

Surface enthalpy and enthalpy of water adsorption of nanocrystalline tin dioxide: Thermodynamic insight on the sensing activity

  • Yuanyuan Ma (a1), Ricardo H.R. Castro (a1), Wei Zhou (a1) and Alexandra Navrotsky (a1)

Abstract

Tin dioxide (SnO2) is an important base material for a variety of gas sensors and catalysts. However, there is a lack of experimental data on the energetics of SnO2 surfaces and their water adsorption. In this work, the surface energies of anhydrous and hydrated SnO2 nanoparticles were measured by combining high-temperature oxide melt solution calorimetry and water adsorption calorimetry. The SnO2 nanoparticles were synthesized through oxidation of metallic tin using nitric acid followed by heat treatment at different temperatures to achieve surface areas ranging from 4000 to 10,000 m2·mol−1(25–65 m2·g−1). The enthalpy of the anhydrous surface is 1.72 ± 0.01 J·m−2, and that of the hydrated surface is 1.49 ± 0.01 J·m−2. The integral heat of water adsorption is −75 kJ·mol−1, with a chemisorbed maximum coverage of ∼5 H2O·nm−2. SnO2 has a lower surface energy and less exothermic enthalpy of water adsorption than the isostructural TiO2 (rutile) reported previously. This comparison suggests that the excellent sensing properties of SnO2 may be a consequence of its relatively low affinity for surface H2O molecules that compete with other gases for adsorption.

Copyright

Corresponding author

a)Address all correspondence to this author. e-mail: anavrotsky@ucdavis.edu

References

Hide All
1.Barsan, N., Schweizer-Berberich, M., and Gopel, W.: Fundamental and practical aspects in the design of nanoscaled SnO2 gas sensors: A status report. Fresenius J. Anal. Chem. 365, 287 (1999).
2.Batzill, M. and Diebold, U.: The surface and materials science of tin oxide. Prog. Surf. Sci. 79, 47 (2005).
3.Batzill, M.: Surface science studies of gas sensing materials: SnO2. Sensors. 6, 1345 (2006).
4.Franke, M.E., Koplin, T.J., and Simon, U.: Metal and metal oxide nanoparticles in chemiresistors: Does the nanoscale matter? Small. 2, 36 (2006).
5.Huang, J. and Wan, Q.: Gas sensors based on semiconducting metal oxide one-dimensional nanostructures. Sensors. 9, 9903 (2009).
6.Basu, S. and Basu, P.K.: Nanocrystalline metal oxides for methane sensors: Role of noble metals. J. Sens. 2009, 861968 (2009).
7.Zhang, J., Liu, X.H., Wu, S.H., Xu, M.J., Guo, X.Z., and Wang, S.R.: Au nanoparticle-decorated porous SnO2 hollow spheres: A new model for a chemical sensor. J. Mater. Chem. 20, 6453 (2010).
8.Qian, L.H., Wang, K., Li, Y., Fang, H.T., Lu, Q.H., and Ma, X.L.: CO sensor based on Au-decorated SnO2 nanobelt. Mater. Chem. Phys. 100, 82 (2006).
9.Epifani, M., Arbiol, J., Pellicer, E., Comini, E., Siciliano, P., Faglia, G., and Morante, J.R.: Synthesis and gas-sensing properties of Pd-doped SnO2 nanocrystals: A case study of a general methodology for doping metal oxide nanocrystals. Cryst. Growth Des. 8, 1774 (2008).
10.Gong, J.W., Chen, Q.F., Lian, M.R., Liu, N.C., Stevenson, R.G., and Adami, F.: Micromachined nanocrystalline silver doped SnO2 H2S sensor. Sens. Actuators, B 114, 32 (2006).
11.Kolmakov, A., Klenov, D.O., Lilach, Y., Stemmer, S., and Moskovits, M.: Enhanced gas sensing by individual SnO2 nanowires and nanobelts functionalized with Pd catalyst particles. Nano Lett. 5, 667 (2005).
12.Kong, X.H. and Li, Y.D.: High sensitivity of CuO modified SnO2 nanoribbons to H2S at room temperature. Sens. Actuators, B 105, 449 (2005).
13.Oldfield, G., Ung, T., and Mulvaney, P.: Au@SnO2 core-shell nanocapacitors. Adv. Mater. 12, 1519 (2000).
14.Choi, U.S., Sakai, G., Shimanoe, K., and Yamazoe, N.: Sensing properties of Au-loaded SnO2-Co3O4 composites to CO and H2. Sens. Actuators, B 107, 397 (2005).
15.Castro, R.H.R., Hidalgo, P., Perez, H.E.M., Ramirez-Fernandez, F.J., and Gouvea, D.: Relationship between surface segregation and rapid propane electrical response in Cd-doped SnO2 nanornaterials. Sens. Actuators, B 133, 263 (2008).
16.Hidalgo, P., Castro, R.H.R., Coelho, A.C.V., and Gouvea, D.: Surface segregation and consequent SO2 sensor response in SnO2-NiO. Chem. Mater. 17, 4149 (2005).
17.Boyle, J.F. and Jones, K.A.: Effect of CO, water-vapor and surface-temperature on conductivity of a SnO2 gas sensor. J. Electron. Mater. 6, 717 (1977).
18.Mulheran, P.A. and Harding, J.H.: The stability of SnO2 surfaces. Modell. Simul.Mater. Sci. Eng. 1, 39 (1992).
19.Oviedo, J. and Gillan, M.J.: Energetics and structure of stoichiometric SnO2 surfaces studied by first-principles calculations. Surf. Sci. 463, 93 (2000).
20.Yamaguchi, Y., Tabata, K., and Yashima, T.: First-principles calculations on the surface electronic and reactive properties of M/SnO2 (M = Ge, Mn) (110). J. Mol. Struct. 714, 221 (2005).
21.Evarestov, R.A., Bandura, A.V., and Proskurov, E.V.: Plain DFT and hybrid HF-DFT LCAO calculations of SnO2 (110) and (100) bare and hydroxylated surfaces. Phys. Status Solidi. 243, 1823 (2006) (b).
22.Batzill, M., Diebold, U., Bergermayer, W., and Tanaka, I.: Tuning the chemical functionality of a gas sensitive material: Water adsorption on SnO2(101). Surf. Sci. 600, 29 (2006).
23.Zhang, P., Xu, F., Navrotsky, A., Lee, J.S., Kim, S.T., and Liu, J.: Surface enthalpies of nanophase ZnO with different morphologies. Chem. Mater. 19, 5687 (2007).
24.Levchenko, A.A., Li, G.S., Boerio-Goates, J., Woodfield, B.F., and Navrotsky, A.: TiO2 stability landscape: Polymorphism, surface energy, and bound water energetics. Chem. Mater. 18, 6324 (2006).
25.Zhou, W., Ushakov, S.V., Wang, T., Ekerdt, J.G., Demkov, A.A., and Navrotsky, A.: Hafnia: Energetics of thin films and nanoparticles. J. Appl. Phys. 107, 123514 (2010).
26.Radha, A.V., Bomati-Miguel, O., Ushakov, S.V., Navrotsky, A., and Tartaj, P.: Surface enthalpy, enthalpy of water adsorption, and phase stability in nanocrystalline monoclinic zirconia. J. Am. Ceram. Soc. 92, 133 (2009).
27.Navrotsky, A.: Progress and new directions in high-temperature calorimetry. Phys. Chem. Miner. 2, 89 (1977).
28.Navrotsky, A.: Progress and new directions in high-temperature calorimetry revisited. Phys. Chem. Miner. 24, 222 (1997).
29.Ushakov, S.V. and Navrotsky, A.: Direct measurements of water adsorption enthalpy on hafnia and zirconia. Appl. Phys. Lett. 87, 164103 (2005).
30.Costa, G.C.C., Ushakov, S.V., Castro, R.H.R., Navrotsky, A., and Muccillo, R.: Calorimetric measurement of surface and interface enthalpies of yttria-stabilized zirconia (YSZ). Chem. Mater. 22, 2937 (2010).
31.Robie, R.A. and Hemingway, B.S.: Thermodynamic properties of minerals and related substrate at 298.15 K and 1 bar (105 Pascals) pressure and at higher temperature. U.S. Geol. Surv. Bull. 2131, 461 (1995).

Keywords

Surface enthalpy and enthalpy of water adsorption of nanocrystalline tin dioxide: Thermodynamic insight on the sensing activity

  • Yuanyuan Ma (a1), Ricardo H.R. Castro (a1), Wei Zhou (a1) and Alexandra Navrotsky (a1)

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