Skip to main content
×
Home
    • Aa
    • Aa

Interaction of Oxide Surfaces with Water: Environmental Transmission Electron Microscopy of MgO Hydroxylation

  • Marija Gajdardziska-Josifovska (a1) and Renu Sharma (a2)
Abstract

Environmental transmission electron microscopy (ETEM) is opening an important window for in situ studies of interaction of water with oxides. Studies of MgO smoke nanocrystals under partial pressures of water ranging from 10 mTorr to 10 Torr found their {100} neutral surfaces to be extremely resistant to dissociative adsorption of water and hydroxylation, in agreement with recent theoretical predictions. ETEM observations of electron irradiation driven MgO smoke nanocrystal hydroxylation displayed the anticipated volume expansion, but revealed complex shape changes with elongations toward oxide corners. The reaction rate was found to increase with electron flux at constant water pressure. In situ selected area diffraction studies of MgO single crystals showed that the hydroxide grows with its basal (0001) plane parallel to the polar MgO (111) planes. This is the same crystallographic relationship as in dehydroxylation experiments, but with four variants. Electron energy loss spectroscopy found oxygen K-edge changes consistent with bulk hydroxylation.

Copyright
Corresponding author
Corresponding author. E-mail: mgj@csd.uwm.edu
Linked references
Hide All

This list contains references from the content that can be linked to their source. For a full set of references and notes please see the PDF or HTML where available.

Abriou, D. & Jupille, J. (1999). Self-inhibition of water dissociation on magnesium oxide surfaces. Surf Sci430, L527532.

Béarat, H., McKelvy, M.J., Chizmeshya, A.V.G., Sharma, R., & Carpenter, R.W. (2002). Magnesium hydroxide dehydroxylation/carbonation reaction processes: Implications for carbon dioxide mineral sequestration. J Am Ceram Soc85, 742748.

Dahmen, U., Kim, M.G., & Searcy, A.W. (1987). Microstructural evolution during the decomposition of Mg(OH)2. Ultramicroscopy23, 365370.

Eggkvist, O. & Stone, A.J. (1999). Adsorption of water on the MgO(001) surface. Surf Sci437, 239248.

Ferry, D., Glebov, A., Senz, V., Suzanne, J., Toennies, J.P., & Weiss, H. (1996). Observation of the second ordered phase of water on the MgO(100) surface: Low energy electron diffraction and helium atom scattering studies. J Chem Phys105, 16971701.

Finocchi, F., Barbier, A., Jupille, J., & Noguera, C. (2004). Stability of rocksalt (111) polar surfaces: Beyond the octopole. Phys Rev Lett92, Art. No. 136101.

Gajdardziska-Josifovska, M., Crozier, P.A., & Cowley, J.M. (1991). A ([SQUARE ROOT 3] ×[SQUARE ROOT 3])R30° reconstruction on annealed (111) surfaces of MgO. Surf Sci Lett248, L259L264.

Gajdardziska-Josifovska, M., Crozier, P.A., McCartney, M.R., & Cowley, J.M. (1993). Ca segregation and step modifications on cleaved and annealed MgO (100) surfaces. Surf Sci284, 186199.

Gajdardziska-Josifovska, M., Plass, R., Schofield, M.A., Giese, D.R., & Sharma, R. (2002). In situ and ex situ electron microscopy studies of polar oxide surfaces with rock salt structure. J Electron Microsc51, S13S25.

Giordano, L., Goniakowski, J., & Suzanne, J. (1998). Partial dissociation of water molecules in the (3 × 2) water monolayer deposited on the MgO (100) surface. Phys Rev Lett81, 12711273.

Hansen, T.W., Wagner, J.B., Hansen, P.L., Dahl, S., Topsoe, H., & Jacobsen, C.J.H. (2001). Atomic-resolution in situ transmission electron microscopy of a promoter of a heterogeneous catalyst. Science294, 15081510.

Jones, C.F., Reeve, R.A., Rigg, R., Segall, R.L., Smart, R. St. C., & Turner, P.S. (1984). Surface area and the mechanism of hydroxylation of ionic oxide surfaces. J Chem Soc Faraday Trans80, 26092617.

Langel, W. & Parrinello, M. (1994). Hydrolysis at stepped MgO surfaces. Phys Rev Lett73, 504507.

Langel, W. & Parrinello, M. (1995). Ab-initio molecular-dynamics of H2O adsorbed on solid MgO. J Chem Phys103, 32403252.

Lazarov, V.K., Plass, R., Poon, H.-C., Saldin, D.K., Weinert, M., Chambers, S.A., & Gajdardziska-Josifovska, M. (2005). Structure of the hydrogen stabilized MgO(111)-(1×1) polar surface: Integrated experimental and theoretical studies. Phys Rev B71, 115434 (19).

Liu, P., Kendelewicz, T., & Brown, G.E., Jr. (1998a). Reaction of water with MgO(100) surfaces. Part II: Synchrotron photoemission studies of defective surfaces. Surf Sci412/413, 315332.

Liu, P., Kendelewicz, T., Brown, G.E., Jr., & Parks, G.A. (1998b). Reaction of water with MgO(100) surfaces. Part I: Synchrotron X-ray photoemission studies of low-defect surfaces. Surf Sci412/413, 287314.

McKelvy, M.J., Sharma, R., Chizmeshya, A.V.G., Carpenter, R.W., & Streib, K. (2001). Magnesium hydroxide dehydroxylation: In situ nanoscale observation of lamellar nucleation and growth. Chem Mater13, 921926.

Noguera, C. (2000). Polar oxide surfaces. J Phys Condens Matter12, R367R410.

Odelius, M. (1999). Mixed molecular and dissociative water adsorption on MgO[100]. Phys Rev Lett82, 39193922.

Plass, R., Egan, K., Collazo-Davila, C., Grozea, D., Landree, E., Marks, L.D., & Gajdardziska-Josifovska, M. (1998). Cyclic ozone identified in magnesium oxide (111) surface reconstructions. Phys Rev Lett81, 48914894.

Refson, K., Wogelius, R.A., & Fraser, D.G. (1995). Water chemisorption and reconstruction of the MgO surface. Phys Rev B52, 1082310826.

Russo, S. & Noguera, C. (1992). Acido-basic properties of simple oxide surfaces. 1. Magnesium-oxide. Surf Sci262, 245258.

Sharma, R., McKelvy, M.J., Béarat, H., Chizmeshya, A.V.G., & Carpenter, R.W. (2004). In situ observation of nano-materials formation processes during Mg(OH)2 dehydroxylation and rehydroxylation. Philos Mag84, 27112729.

Sharma, R. & Weiss, K. (1998). Development of a TEM to study in situ structural and chemical changes at atomic level during gas solid interaction at elevated temperatures. Micros Res Tech42, 270280.

Subramanian, A., Marks, L.D., Warschkow, O., & Ellis, D.E. (2004). Direct observation of charge transfer at a MgO(111) surface. Phys Rev Lett92, Art. No. 026101.

Tasker, P.W. (1979). The stability of ionic crystal surfaces. J Phys C Solid State Phys12, 49774984.

Recommend this journal

Email your librarian or administrator to recommend adding this journal to your organisation's collection.

Microscopy and Microanalysis
  • ISSN: 1431-9276
  • EISSN: 1435-8115
  • URL: /core/journals/microscopy-and-microanalysis
Please enter your name
Please enter a valid email address
Who would you like to send this to? *
×

Keywords: