Structure of the Hydrated -Al2O3 (0001) Surface

Eng, P. J.; Trainor, Thomas P.; Brown, Jr., Gordon E.; Waychunas, Glenn A.; Newville, Matthew; Sutton, Stephen R.; Rivers, Mark L.

doi:10.1126/science.288.5468.1029

Title: Structure of the Hydrated -Al₂O₃ (0001) Surface

Journal Article · 12 May 2000 · Science

DOI: https://doi.org/10.1126/science.288.5468.1029 · OSTI ID:1508033

Eng, P. J. ^[1]; Trainor, Thomas P. ^[2]; Brown, Jr., Gordon E. ^[3]; Waychunas, Glenn A. ^[4]; Newville, Matthew ^[1]; Sutton, Stephen R. ^[1]; Rivers, Mark L. ^[1]

Univ. of Chicago, IL (United States)
Stanford Univ., CA (United States)
Stanford Univ., CA (United States); Stanford Synchrotron Radiation Lightsource, Stanford, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

The physical and chemical properties of the hydrated α-Al₂O₃ (0001) surface are important for understanding the reactivity of natural and synthetic aluminum-containing oxides. The structure of this surface was determined in the presence of water vapor at 300 kelvin by crystal truncation rod diffraction at a third-generation synchrotron x-ray source. The fully hydrated surface is oxygen terminated, with a 53% contracted double Al layer directly below. The structure is an intermediate between α-Al2O3 and γ-Al(OH)3, a fully hydroxylated form of alumina. A semiordered oxygen layer about 2.3 angstroms above the terminal oxygen layer is interpreted as adsorbed water. The clean α-Al₂O₃ (0001) surface, in contrast, is Al terminated and significantly relaxed relative to the bulk structure. These differences explain the different reactivities of the clean and hydroxylated surfaces.

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Research Organization:: Univ. of Chicago, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: FG02-94ER14466

OSTI ID:: 1508033

Report Number(s):: DOE-UCHICAGO-14466-3

Journal Information:: Science, Vol. 288, Issue 5468; ISSN 0036-8075

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 470 works

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References (30)

Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms Brown, Gordon E.; Henrich, Victor E.; Casey, William H. Chemical Reviews, Vol. 99, Issue 1 https://doi.org/10.1021/cr980011z	journal	January 1999
Catalytic Aluminas: Surface Models and Characterization of Surface Sites Knözinger, H.; Ratnasamy, P. Catalysis Reviews, Vol. 17, Issue 1 https://doi.org/10.1080/03602457808080878	journal	January 1978
The interaction of water with solid surfaces: Fundamental aspects Thiel, Patricia A.; Madey, Theodore E. Surface Science Reports, Vol. 7, Issue 6-8, p. 211-385 https://doi.org/10.1016/0167-5729(87)90001-X	journal	October 1987
Reaction of water vapor with α-Al2O3(0001) and α-Fe2O3(0001) surfaces: synchrotron X-ray photoemission studies and thermodynamic calculations Liu, Ping; Kendelewicz, Tom; Brown, Gordon E. Surface Science, Vol. 417, Issue 1 https://doi.org/10.1016/S0039-6028(98)00661-X	journal	November 1998
Adsorption of H ₂ O on a Single-Crystal α-Al ₂ O ₃ (0001) Surface Elam, J. W.; Nelson, C. E.; Cameron, M. A. The Journal of Physical Chemistry B, Vol. 102, Issue 36 https://doi.org/10.1021/jp981070j	journal	September 1998
Desorption of H2O from a hydroxylated single-crystal α-Al2O3(0001) surface Nelson, C. E.; Elam, J. W.; Cameron, M. A. Surface Science, Vol. 416, Issue 3 https://doi.org/10.1016/S0039-6028(98)00439-7	journal	October 1998
The Chemistry of Water on Alumina Surfaces: Reaction Dynamics from First Principles Hass, K. C. Science, Vol. 282, Issue 5387 https://doi.org/10.1126/science.282.5387.265	journal	October 1998
Ab Initio Study of the Interaction of Water with Cluster Models of the Aluminum Terminated (0001) α-Aluminum Oxide Surface Wittbrodt, J. M.; Hase, W. L.; Schlegel, H. B. The Journal of Physical Chemistry B, Vol. 102, Issue 34 https://doi.org/10.1021/jp981516w	journal	August 1998
Sapphire (0001) Surface, Clean and withd-Metal Overlayers Verdozzi, C.; Jennison, D. R.; Schultz, P. A. Physical Review Letters, Vol. 82, Issue 4 https://doi.org/10.1103/PhysRevLett.82.799	journal	January 1999
Atomic and electronic structure of the corundum (0001) surface: comparison with surface spectroscopies Puchin, V. E.; Gale, J. D.; Shluger, A. L. Surface Science, Vol. 370, Issue 2-3 https://doi.org/10.1016/S0039-6028(96)00971-5	journal	January 1997
Structure of the (0001) surface of α-Al2O3 from first principles calculations Manassidis, I.; De Vita, A.; Gillan, M. J. Surface Science, Vol. 285, Issue 3 https://doi.org/10.1016/0039-6028(93)90423-H	journal	April 1993
The termination of the α-Al2O3 (0001) surface: a LEED crystallography determination Toofan, J.; Watson, P. R. Surface Science, Vol. 401, Issue 2 https://doi.org/10.1016/S0039-6028(97)01031-5	journal	April 1998
Composition and structure of the Al2O3{0001}-(1 × 1) surface Ahn, J.; Rabalais, J. W. Surface Science, Vol. 388, Issue 1-3 https://doi.org/10.1016/S0039-6028(97)00383-X	journal	October 1997
Determination of the α-Ai ₂ O ₃ (0001) Surface Relaxation and Termination by Measurements of Crystal Truncation Rods Guénard, P.; Renaud, G.; Barbier, A. Surface Review and Letters, Vol. 05, Issue 01 https://doi.org/10.1142/S0218625X98000591	journal	February 1998
Interfacial Charging Phenomena of Aluminum (Hydr)oxides ^† Yong, Han; Van Riemsdijk, W. H. Langmuir, Vol. 15, Issue 18 https://doi.org/10.1021/la981301d	journal	August 1999
Theoretical prediction of single-site surface-protonation equilibrium constants for oxides and silicates in water Sverjensky, Dimitri A.; Sahai, Nita Geochimica et Cosmochimica Acta, Vol. 60, Issue 20 https://doi.org/10.1016/0016-7037(96)00207-4	journal	October 1996
Surface X-ray diffraction Robinson, I. K.; Tweet, D. J. Reports on Progress in Physics, Vol. 55, Issue 5 https://doi.org/10.1088/0034-4885/55/5/002	journal	May 1992
Oxide surfaces and metal/oxide interfaces studied by grazing incidence X-ray scattering Renaud, G. Surface Science Reports, Vol. 32, Issue 1-2 https://doi.org/10.1016/S0167-5729(98)00005-3	journal	January 1998
Accurate structure analysis with synchrotron radiation. The electron density in Al2O3 and Cu2O Kirfel, A.; Eichhorn, K. Acta Crystallographica Section A Foundations of Crystallography, Vol. 46, Issue 4 https://doi.org/10.1107/S0108767389012596	journal	April 1990
A structural investigation of α-Al ₂ O ₃ at 2170 K Ishizawa, N.; Miyata, T.; Minato, I. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 36, Issue 2 https://doi.org/10.1107/S0567740880002981	journal	February 1980
alpha-Al2O3 (0001) Surfaces: Atomic and Electronic Structure Gautier, Martine; Fenaud, Gilles; Pham Van, Laurent Journal of the American Ceramic Society, Vol. 77, Issue 2 https://doi.org/10.1111/j.1151-2916.1994.tb06999.x	journal	February 1994
High-resolution electron-energy-loss spectroscopy of isolated hydroxyl groups on α-Al2O3(0001) Coustet, Valérie; Jupille, Jacques Surface Science, Vol. 307-309 https://doi.org/10.1016/0039-6028(94)91557-1	journal	April 1994
Assignment of a surface vibrational mode by chemical means: Modification of the lattice modes of Al2O3 by a surface reaction with H2O Chen, J. G.; Crowell, J. E.; Yates, J. T. The Journal of Chemical Physics, Vol. 84, Issue 10 https://doi.org/10.1063/1.449902	journal	May 1986
Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database Brown, I. D.; Altermatt, D. Acta Crystallographica Section B Structural Science, Vol. 41, Issue 4 https://doi.org/10.1107/S0108768185002063	journal	August 1985
XAFS and Bond-Valence Determination of the Structures and Compositions of Surface Functional Groups and Pb(II) and Co(II) Sorption Products on Single-Crystal α-Al2O3 Bargar, J. R.; Towle, S. N.; Brown, G. E. Journal of Colloid and Interface Science, Vol. 185, Issue 2 https://doi.org/10.1006/jcis.1996.4574	journal	January 1997
An FTIR spectral investigation of the structural species found on alumina surfaces Lee, D. H.; Condrate, R. A. Materials Letters, Vol. 23, Issue 4-6 https://doi.org/10.1016/0167-577X(95)00039-9	journal	May 1995
Surface hydration of aqueous γ-Al2O3 studied by Fourier transform Raman and infrared spectroscopy—I. Initial results Dyer, Chris; Hendra, Patrick J.; Forsling, Willis Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 49, Issue 5-6 https://doi.org/10.1016/0584-8539(93)80092-O	journal	May 1993
Balance between Surface Complexation and Surface Phase Transformation at the Alumina/Water Interface Laiti, Erkki; Persson, Per; Öhman, Lars-Olof Langmuir, Vol. 14, Issue 4 https://doi.org/10.1021/la970383n	journal	January 1998
Sorption of Co(II) on Metal Oxide Surfaces Towle, Steven N.; Bargar, John R.; Brown, Gordon E. Journal of Colloid and Interface Science, Vol. 217, Issue 2 https://doi.org/10.1006/jcis.1999.6351	journal	September 1999
Copper wetting of α-Al2O3(0001): theory and experiment Kelber, J. A.; Niu, Chengyu; Shepherd, K. Surface Science, Vol. 446, Issue 1-2 https://doi.org/10.1016/S0039-6028(99)01089-4	journal	February 2000

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