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

Structure of the Hydrated -Al₂O₃ (0001) Surface

Journal Article · Fri May 12 00:00:00 EDT 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 ^[5]; Sutton, Stephen R. ^[5]; Rivers, Mark L. ^[5]

Univ. of Chicago, IL (United States); The University of Chicago
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)
Univ. of Chicago, IL (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.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: FG02-94ER14466

OSTI ID:: 1508033

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

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

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (31)

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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
Atomic and electronic structure of the corundum (α-alumina) (0001) surface Godin, T. J.; LaFemina, John P. Physical Review B, Vol. 49, Issue 11 https://doi.org/10.1103/PhysRevB.49.7691	journal	March 1994
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
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
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
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
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
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

Cited By (40)

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy Kumar, N.; Andersson, M. P.; van den Ende, D. Langmuir, Vol. 33, Issue 50 https://doi.org/10.1021/acs.langmuir.7b03153	journal	December 2017
Adsorption of dissolved aluminum on sapphire-c and kaolinite: Implications for points of zero charge of clay minerals Lützenkirchen, J.; Abdelmonem, A.; Weerasooriya, R. Karlsruhe https://doi.org/10.5445/ir/1000046385	text	January 2014
Paving the Path toward Reliable Cathode Materials for Aluminum-Ion Batteries Wu, Feng; Yang, Haoyi; Bai, Ying Advanced Materials, Vol. 31, Issue 16 https://doi.org/10.1002/adma.201806510	journal	February 2019
Controlled Growth of Single‐Crystal Graphene Films Zhang, Jincan; Lin, Li; Jia, Kaicheng Advanced Materials, Vol. 32, Issue 1 https://doi.org/10.1002/adma.201903266	journal	October 2019
Generation of Hydrogen through the Reaction between Plasma-Modified Aluminum and Water Urbonavicius, Marius; Varnagiris, Sarunas; Milcius, Darius Energy Technology, Vol. 5, Issue 12 https://doi.org/10.1002/ente.201700344	journal	October 2017
Overview of the Relationship Between Aluminum Exposure and Health of Human Being Niu, Qiao Neurotoxicity of Aluminum, p. 1-31 https://doi.org/10.1007/978-981-13-1370-7_1	book	October 2018
TitaniQ recrystallized: experimental confirmation of the original Ti-in-quartz calibrations Thomas, Jay B.; Watson, E. Bruce; Spear, Frank S. Contributions to Mineralogy and Petrology, Vol. 169, Issue 3 https://doi.org/10.1007/s00410-015-1120-0	journal	February 2015
Towards Realistic Surface Science Models of Heterogeneous Catalysts: Influence of Support Hydroxylation and Catalyst Preparation Method Sterrer, Martin; Freund, Hans-Joachim Catalysis Letters, Vol. 143, Issue 5 https://doi.org/10.1007/s10562-013-0987-5	journal	March 2013
Nanoparticulate Iron Oxide Minerals in Soils and Sediments: Unique Properties and Contaminant Scavenging Mechanisms Waychunas, Glenn A.; Kim, Christopher S.; Banfield, Jillian F. Journal of Nanoparticle Research, Vol. 7, Issue 4-5 https://doi.org/10.1007/s11051-005-6931-x	journal	October 2005
Dechlorinating transformation of propachlor through nucleophilic substitution by dithionite on the surface of alumina Liu, Chengshuai; Shih, Kaimin; Gao, Yuanxue Journal of Soils and Sediments, Vol. 12, Issue 5 https://doi.org/10.1007/s11368-012-0506-0	journal	March 2012
Aluminum Pitting Corrosion in Halide Media: A Quantum Model and Empirical Evidence Lashgari, Mohsen; Kianpour, Effat; Mohammadi, Esmaeil Journal of Materials Engineering and Performance, Vol. 22, Issue 12 https://doi.org/10.1007/s11665-013-0669-x	journal	August 2013
Control of electronic conduction at an oxide heterointerface using surface polar adsorbates Xie, Yanwu; Hikita, Yasuyuki; Bell, Christopher Nature Communications, Vol. 2, Issue 1 https://doi.org/10.1038/ncomms1501	journal	September 2011
A negative surface energy for alumina Łodziana, Zbigniew; Topsøe, Nan-Yu; Nørskov, Jens K. Nature Materials, Vol. 3, Issue 5 https://doi.org/10.1038/nmat1106	journal	April 2004
Electronic interactions and charge transfers of metal atoms and clusters on oxide surfaces Pacchioni, Gianfranco Physical Chemistry Chemical Physics, Vol. 15, Issue 6 https://doi.org/10.1039/c2cp43731g	journal	January 2013
Comparative DFT study of inner-sphere As(iii) complexes on hydrated α-Fe2O3(0001) surface models Goffinet, Christoffer J.; Mason, Sara E. Journal of Environmental Monitoring, Vol. 14, Issue 7 https://doi.org/10.1039/c2em30355h	journal	January 2012
Naturally occurring iron oxide nanoparticles: morphology, surface chemistry and environmental stability Guo, Haibo; Barnard, Amanda S. J. Mater. Chem. A, Vol. 1, Issue 1 https://doi.org/10.1039/c2ta00523a	journal	January 2013
Role(s) of adsorbed water in the surface chemistry of environmental interfaces Rubasinghege, Gayan; Grassian, Vicki H. Chemical Communications, Vol. 49, Issue 30 https://doi.org/10.1039/c3cc38872g	journal	January 2013
Oxygen adsorption onto pure and doped Al surfaces – the role of surface dopants Lousada, Cláudio M.; Korzhavyi, Pavel A. Physical Chemistry Chemical Physics, Vol. 17, Issue 3 https://doi.org/10.1039/c4cp04277h	journal	January 2015
Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis Hong, Wesley T.; Risch, Marcel; Stoerzinger, Kelsey A. Energy & Environmental Science, Vol. 8, Issue 5 https://doi.org/10.1039/c4ee03869j	journal	January 2015
Morphology-dependent interplay of reduction behaviors, oxygen vacancies and hydroxyl reactivity of CeO ₂ nanocrystals Gao, Yuxian; Li, Rongtan; Chen, Shilong Physical Chemistry Chemical Physics, Vol. 17, Issue 47 https://doi.org/10.1039/c5cp04570c	journal	January 2015
The atomistic origin of interface confinement and enhanced conversion efficiency in Si nanowire solar cells He, Yan; Quan, Jun; Ouyang, Gang Physical Chemistry Chemical Physics, Vol. 18, Issue 10 https://doi.org/10.1039/c5cp08035e	journal	January 2016
Phase dependent thermal and spectroscopic responses of Al ₂ O ₃ nanostructures with different morphogenesis Gangwar, Jitendra; Gupta, Bipin Kumar; Tripathi, Surya Kant Nanoscale, Vol. 7, Issue 32 https://doi.org/10.1039/c5nr02369f	journal	January 2015
Molecular structure of octadecylphosphonic acids during their self-assembly on α-Al ₂ O ₃ (0001) Meltzer, Christian; Yu, Hui; Peukert, Wolfgang Physical Chemistry Chemical Physics, Vol. 20, Issue 29 https://doi.org/10.1039/c8cp02391c	journal	January 2018
The stability of the hydroxylated (0001) surface of α-Al2O3 Łodziana, Z.; Nørskov, J. K.; Stoltze, P. The Journal of Chemical Physics, Vol. 118, Issue 24 https://doi.org/10.1063/1.1574798	journal	June 2003
Vibrational spectra of dissociatively adsorbed D ₂ O on Al-terminated α-Al ₂ O ₃ (0001) surfaces from ab initio molecular dynamics Melani, Giacomo; Nagata, Yuki; Campen, R. Kramer The Journal of Chemical Physics, Vol. 150, Issue 24 https://doi.org/10.1063/1.5099895	journal	June 2019
Pt ₈ cluster on alumina under a pressure of hydrogen: Support-dependent reconstruction from first-principles global optimization Sun, Geng; Alexandrova, Anastassia N.; Sautet, Philippe The Journal of Chemical Physics, Vol. 151, Issue 19 https://doi.org/10.1063/1.5129296	journal	November 2019
Probing equilibrium of molecular and deprotonated water on TiO ₂ (110) Wang, Zhi-Tao; Wang, Yang-Gang; Mu, Rentao Proceedings of the National Academy of Sciences, Vol. 114, Issue 8 https://doi.org/10.1073/pnas.1613756114	journal	February 2017
Human Health Risk Assessment for Aluminium, Aluminium Oxide, and Aluminium Hydroxide Krewski, Daniel; Yokel, Robert A.; Nieboer, Evert Journal of Toxicology and Environmental Health, Part B, Vol. 10, Issue sup1 https://doi.org/10.1080/10937400701597766	journal	November 2007
Polarity of oxide surfaces and nanostructures Goniakowski, Jacek; Finocchi, Fabio; Noguera, Claudine Reports on Progress in Physics, Vol. 71, Issue 1 https://doi.org/10.1088/0034-4885/71/1/016501	journal	December 2007
X-ray truncation rod analysis of the reversible temperature-dependent [001] surface structure of LaAlO3 Francis, R.; Moss, S.; Jacobson, A. Physical Review B, Vol. 64, Issue 23 https://doi.org/10.1103/physrevb.64.235425	journal	November 2001
Adhesion, atomic structure, and bonding at the Al ( 111 ) / α − Al 2 O 3 ( 0001 ) interface: A first principles study Siegel, Donald J.; Hector, Louis G.; Adams, James B. Physical Review B, Vol. 65, Issue 8 https://doi.org/10.1103/physrevb.65.085415	journal	February 2002
Layer intermixing during metal/metal oxide adsorption: Ti/sapphire(0001) Verdozzi, C.; Schultz, P. A.; Wu, Ruqian Physical Review B, Vol. 66, Issue 12 https://doi.org/10.1103/physrevb.66.125408	journal	September 2002
Direct Identification of Dilute Surface Spins on Al 2 O 3 : Origin of Flux Noise in Quantum Circuits de Graaf, S. E.; Adamyan, A. A.; Lindström, T. Physical Review Letters, Vol. 118, Issue 5 https://doi.org/10.1103/physrevlett.118.057703	journal	January 2017
Unveiling the influence of interfacial bonding and dynamics on solid/liquid interfacial structures: An ab initio molecular dynamics study of (0001) sapphire-liquid Al interfaces Ma, Sida; Yan, Rui; Zong, Nanfu Physical Review Materials, Vol. 4, Issue 2 https://doi.org/10.1103/physrevmaterials.4.023401	journal	February 2020
Optimizing a flow-through X-ray transmission cell for studies of temporal and spatial variations of ion distributions at mineral–water interfaces Lee, Sang Soo; Fenter, Paul; Park, Changyong Journal of Synchrotron Radiation, Vol. 20, Issue 1 https://doi.org/10.1107/s0909049512041568	journal	November 2012
Microwave Plasma Synthesis of Nanostructured γ-Al ₂ O ₃ Powders Fu, L.; Johnson, D. Lynn; Zheng, Jian G. Journal of the American Ceramic Society, Vol. 86, Issue 9 https://doi.org/10.1111/j.1151-2916.2003.tb03532.x	journal	September 2003
Hydroxylation of the surface of PbS nanocrystals passivated with oleic acid Zherebetskyy, D.; Scheele, M.; Zhang, Y. Science, Vol. 344, Issue 6190 https://doi.org/10.1126/science.1252727	journal	May 2014
SURFACE STRUCTURES OF α- Fe 2 O 3 (0001) PHASES DETERMINED BY LEED CRYSTALLOGRAPHY Ketteler, Guido; Weiss, Werner; Ranke, Wolfgang Surface Review and Letters, Vol. 08, Issue 06 https://doi.org/10.1142/s0218625x01001610	journal	December 2001
Zinc and Cadmium Adsorption to Aluminum Oxide Nanoparticles Affected by Naturally Occurring Ligands Stietiya, M. Hashem; Wang, Jim J. Journal of Environmental Quality, Vol. 43, Issue 2 https://doi.org/10.2134/jeq2013.07.0263	journal	March 2014
Heterogeneous chemistry of monocarboxylic acids on α-Al ₂ O ₃ at different relative humidities Tong, S. R.; Wu, L. Y.; Ge, M. F. Atmospheric Chemistry and Physics, Vol. 10, Issue 16 https://doi.org/10.5194/acp-10-7561-2010	journal	January 2010

Figures / Tables (3)

Table 1(p. 7)

Fig. 1(p. 9)

Fig. 2(p. 10)

Similar Records

Molecular water adsorption and reactions on (alpha)-Al2O3(0001) and (alpha)-Alumina Particles

Journal Article · Thu May 03 00:00:00 EDT 2018 · Journal of Physical Chemistry C · OSTI ID:1582577

Electron-stimulated reactions in nanoscale water films adsorbed on α-Al₂O₃ (0001)

Journal Article · Sun Dec 31 23:00:00 EST 2017 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1439011

Related Subjects

58 GEOSCIENCES
Synchrotron radiation