Hostname: page-component-78c5997874-ndw9j Total loading time: 0 Render date: 2024-11-20T05:23:06.772Z Has data issue: false hasContentIssue false

Morphology and mesopores in photoelectrochemically active LaTiO2N single crystals

Published online by Cambridge University Press:  02 February 2016

Simone Pokrant*
Affiliation:
Laboratory Materials for Energy Conversion, Empa, 8600 Dübendorf, Switzerland
Stefan Dilger
Affiliation:
Laboratory Materials for Energy Conversion, Empa, 8600 Dübendorf, Switzerland
Steve Landsmann
Affiliation:
Laboratory Materials for Energy Conversion, Empa, 8600 Dübendorf, Switzerland
*
a)Address all correspondence to this author. e-mail: [email protected]
Get access

Abstract

The mesoporous network within photocatalytically and photoelectrochemically active LaTiO2N (LTON) single crystals was investigated by electron microscopy techniques including electron diffraction and scanning transmission electron microscopy imaging. The perovskite-related oxynitride particles were obtained by thermal ammonolysis from monocrystalline micrometer-sized La2Ti2O7 (LTO) particles grown by flux-assisted solid state synthesis. Special attention was paid to the crystal transformation from the monoclinic layered LTO to the orthorhombic perovskite-related LTON within the monocrystalline particles. A detailed analysis of pore directions and pore sizes with respect to the LTON particle shape was performed. The pore formation mechanism taking place during thermal ammonolysis was discussed. Based on the mechanistic understanding of the transformation from the oxide to the oxynitride, a further extension of the mesoporous network toward higher surface areas was proposed for improved photoelectrochemical activity of oxynitride particles, while high crystallinity and particle sizes in the micrometer range continue to enable efficient charge transport.

Type
Articles
Copyright
Copyright © Materials Research Society 2016 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

Ducati, C.: Porosity in a single crystal. Nature 495, 180 (2013).Google Scholar
Walter, M.G., Warren, E.L., McKone, J.R., Boettcher, S.W., Mi, Q., Santori, E.A., and Lewis, N.S.: Solar water splitting cells. Chem. Rev. 110, 6446 (2010).CrossRefGoogle ScholarPubMed
Hisatomi, T., Kubota, J., and Domen, K.: Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting. Chem. Soc. Rev. 43, 7520 (2014).CrossRefGoogle ScholarPubMed
Kay, A., Cesar, I., and Grätzel, M.: New benchmark for water photooxidation by nanostructured α-Fe2O3 films. J. Am. Chem. Soc. 128, 15714 (2006).Google Scholar
Osterloh, F.E.: Inorganic nanostructures for photoelectrochemical and photocatalytic water splitting. Chem. Soc. Rev. 42, 2294 (2013).Google Scholar
Tilley, S.D., Cornuz, M., Sivula, K., and Grätzel, M.: Light-induced water splitting with hematite: Improved nanostructure and iridium oxide catalysis. Angew. Chem. Int. Ed. 49, 6405 (2010).CrossRefGoogle ScholarPubMed
Landsmann, S., Maegli, A.E., Trottmann, M., Battaglia, C., Weidenkaff, A., and Pokrant, S.: Design guidelines for high-performance particle-based photoanodes for water splitting: Lanthanum titanium oxynitride as a model. ChemSusChem 8, 3451 (2015).CrossRefGoogle ScholarPubMed
Crossland, E.J.W., Noel, N., Sivaram, V., Leijtens, T., Alexander-Webber, J.A., and Snaith, H.J.: Mesoporous TiO2 single crystals delivering enhanced mobility and optoelectronic device performance. Nature 495, 215 (2013).Google Scholar
Maeda, K.: (Oxy)nitrides with d0-electronic configuration as photocatalysts and photoanodes that operate under a wide range of visible light for overall water splitting. Phys. Chem. Chem. Phys. 15, 10537 (2013).Google Scholar
Ebbinghaus, S.G., Abicht, H-P., Dronskowski, R., Müller, T., Reller, A., and Weidenkaff, A.: Perovskite-related oxynitrides—Recent developments in synthesis, characterisation and investigations of physical properties. Prog. Solid State Chem. 37, 173 (2009).Google Scholar
Park, N-Y. and Kim, Y-I.: Morphology and band gap variations of oxynitride LaTaON2 depending on the ammonolysis temperature and precursor. J. Mater. Sci. 47, 5333 (2012).Google Scholar
Sagarna, L., Rushchanskii, K.Z., Maegli, A., Yoon, S., Populoh, S., Shkabko, A., Pokrant, S., Lezaic, M., Waser, R., and Weidenkaff, A.: Structure and thermoelectric properties of EuTi(O,N)3±δ . J. Appl. Phys. 114, 033701 (2013).Google Scholar
Higashi, M., Domen, K., and Abe, R.: Fabrication of efficient TaON and Ta3N5 photoanodes for water splitting under visible light irradiation. Energy Environ. Sci. 4, 4138 (2011).CrossRefGoogle Scholar
Zhang, F., Yamakata, A., Maeda, K., Moriya, Y., Takata, T., Kubota, J., Teshima, K., Oishi, S., and Domen, K.: Cobalt-modified porous single-crystalline LaTiO2N for highly efficient water oxidation under visible light. J. Am. Chem. Soc. 134, 8348 (2012).Google Scholar
Maegli, A.E., Pokrant, S., Hisatomi, T., Trottmann, M., Domen, K., and Weidenkaff, A.: Enhancement of photocatalytic water oxidation by the morphological control of LaTiO2N and cobalt oxide catalysts. J. Phys. Chem. C 118, 16344 (2014).Google Scholar
Feng, J., Luo, W., Fang, T., Lv, H., Wang, Z., Gao, J., Liu, W., Yu, T., Li, Z., and Zou, Z.: Highly photo-responsive LaTiO2N photoanodes by improvement of charge carrier transport among film particles. Adv. Funct. Mater. 24, 3535 (2014).Google Scholar
Maegli, A.E., Hisatomi, T., Otal, E.H., Yoon, S., Pokrant, S., Graetzel, M., and Weidenkaff, A.: Structural and photocatalytic properties of perovskite-type (La,Ca)Ti(O,N)3 prepared from A-site deficient precursors. J. Mater. Chem. 22, 17906 (2012).Google Scholar
Wagata, H., Zettsu, N., Yamaguchi, A., Nishikiori, H., Yubuta, K., Oishi, S., and Teshima, K.: Chloride flux growth of La2Ti2O7 crystals and subsequent nitridation to form LaTiO2N crystals. Cryst. Growth Des. 15, 124 (2015).Google Scholar
Pokrant, S., Cheynet, M.C., Irsen, S., Maegli, A.E., and Erni, R.: Mesoporosity in photocatalytically active oxynitride single crystals. J. Phys. Chem. C 118, 20940 (2014).Google Scholar
Yashima, M., Saito, M., Nakano, H., Takata, T., Ogisu, K., and Domen, K.: Imma perovskite-type oxynitride LaTiO2N: Structure and electron density. Chem. Commun. 46, 4704 (2010).Google Scholar
Stadelmann, P.: JEMS. http://www.jems-saas.ch/ (accessed January 04, 2016).Google Scholar
Gasperin, M.: Lanthanum dititanate. Acta Crystallogr., Sect. B B31, 2129 (1975).Google Scholar
Momma, K. and Izumi, F.: Vesta 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272 (2011).Google Scholar
Ebbinghaus, S.G., Aguiar, R., Weidenkaff, A., Gsell, S., and Reller, A.: Topotactical growth of thick perovskite oxynitride layers by nitridation of single crystalline oxides. Solid State Sci. 10, 709 (2008).Google Scholar
Supplementary material: PDF

Pokrant supplementary material

Pokrant supplementary material 1

Download Pokrant supplementary material(PDF)
PDF 301.6 KB
Supplementary material: Image

Pokrant supplementary material

Figure S1

Download Pokrant supplementary material(Image)
Image 346.5 KB
Supplementary material: Image

Pokrant supplementary material

Figure S2

Download Pokrant supplementary material(Image)
Image 1.4 MB
Supplementary material: Image

Pokrant supplementary material

Figure S3

Download Pokrant supplementary material(Image)
Image 2.6 MB
Supplementary material: Image

Pokrant supplementary material

Figure S4

Download Pokrant supplementary material(Image)
Image 1.5 MB