University of Nebraska - Lincoln DigitalCommons@University of Nebraska - Lincoln US Department of Energy Publications U.S. Department of Energy 1999 Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms Gordon E. Brown Jr. Stanford University Victor Henrich Yale University William Casey University of California David Clark Los Alamos National Laboratory Carrick Eggleston University of Wyoming See next page for additional authors Follow this and additional works at: https://digitalcommons.unl.edu/usdoepub Part of the Bioresource and Agricultural Engineering Commons Brown, Gordon E. Jr.; Henrich, Victor; Casey, William; Clark, David; Eggleston, Carrick; Andrew Felmy, Andrew Felmy; Goodman, D. Wayne; Gratzel, Michael; Maciel, Gary; McCarthy, Maureen I.; Nealson, Kenneth H.; Sverjensky, Dimitri; Toney, Michael; and Zachara, John M., "Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms" (1999). US Department of Energy Publications. 197. https://digitalcommons.unl.edu/usdoepub/197 This Article is brought to you for free and open access by the U.S. Department of Energy at DigitalCommons@University of Nebraska - Lincoln. It has been accepted for inclusion in US Department of Energy Publications by an authorized administrator of DigitalCommons@University of Nebraska - Lincoln. Authors Gordon E. Brown Jr., Victor Henrich, William Casey, David Clark, Carrick Eggleston, Andrew Felmy Andrew Felmy, D. Wayne Goodman, Michael Gratzel, Gary Maciel, Maureen I. McCarthy, Kenneth H. Nealson, Dimitri Sverjensky, Michael Toney, and John M. Zachara This article is available at DigitalCommons@University of Nebraska - Lincoln: https://digitalcommons.unl.edu/ usdoepub/197 Chem. Rev. 1999, 99, 77−174 77 Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms Gordon E. Brown, Jr.* Surface and Aqueous Geochemistry Group, Department of Geological & Environmental Sciences, Stanford University, Stanford, California 94305-2115 Victor E. Henrich* Surface Science Laboratory, Department of Applied Physics, Yale University, New Haven, Connecticut 06520 William H. Casey Department of Land, Air, and Water Resources, University of California, Davis, Davis, California 95616 David L. Clark G.T. Seaborg Institute for Transactinium Science, Nuclear Materials Technology Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 Carrick Eggleston Department of Geology and Geophysics, University of Wyoming, Laramie, Wyoming 82071-3006 Andrew Felmy Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352 D. Wayne Goodman Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255 Michael Gra¨tzel Institute of Chemical Physics, EÄ cole Polytechnique Fe´de´rale de Lausanne, CH-1015 Lausanne, Switzerland Gary Maciel Department of Chemistry, Colorado State University, Ft. Collins, Colorado 80523 Maureen I. McCarthy Theory, Modeling and Simulation Group, Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352 Kenneth H. Nealson Jet Propulsion Laboratory-183-301, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, California 91109-8099 Dimitri A. Sverjensky Department of Earth and Planetary Sciences, The Johns Hopkins University, Baltimore, Maryland 21218 Michael F. Toney IBM Almaden Research Center, San Jose, California 95120 John M. Zachara Environmental Molecular Sciences, Laboratory Pacific Northwest National Laboratory, Richland, Washington 99352 Received February 27, 1998 (Revised Manuscript Received November 9, 1998) 10.1021/cr980011z CCC: $35.00 © 1999 American Chemical Society Published on Web 12/24/1998 78 Chemical Reviews, 1999, Vol. 99, No. 1 Brown et al. Contents 5. Dissolution and Growth of Metal (Hydr)oxides 141 5.1. Reactivities of Metal (Hydr)oxide Oligomers: 141 1. Introduction 78 Models for Surface Complexes 2. Characterization of Clean Metal Oxide Surfaces 83 5.2. Structural Similarities between Aqueous Oxo 141 2.1. The Nature of Defects on Metal Oxide 83 and Hydroxo Oligomers and Simple Surfaces Surfaces 5.3. Dissolution Rates of Metal (Hydr)oxides and 142 2.2. Overview of UHV Surface Science Methods 84 Depolymerization of Surface (Hydr)oxide Used To Study Clean Metal Oxide Surfaces Polymers 2.3. Geometric and Electronic Structure of Clean, 86 6. Biotic Processes in Metal Oxide Surface 144 Well-Ordered Surfaces Chemistry 2.3.1. Atomic Geometry 86 6.1. Surface Attachment and Biofilm Formation 144 2.3.2. Electronic Structure 89 6.2. Metal Oxide Dissolution (Reductive and 145 Nonreductive) 2.4. Imperfections on Oxide Surfaces 91 6.2.1. Nonreductive Dissolution of Metal Oxides 145 2.4.1. Bulk Point Defects 91 6.2.2. Reductive Dissolution of Metal Oxides 146 2.4.2. Steps, Kinks, and Point Defects 92 6.3. Metal Oxide Formation 149 3. Water Vapor−Metal Oxide Interactions 92 6.3.1. Manganese Oxide Formation 149 3.1. Experimental Studies on Single-Crystal Metal 93 Oxides 6.3.2. Anaerobic Iron Oxide Formation 149 3.1.1. MgO and CaO 93 6.3.3. Magnetite Formation 150 7. Theory 150 3.1.2. R-Al2O3 95 7.1. Background 150 3.1.3. TiO2 (Rutile) 95 7.1.1. Thermodynamic Approaches 150 3.1.4. TiO2 (Anatase) 97 7.1.2. Molecular-Based Approaches 152 3.1.5. R-Fe2O3 97 3.2. NMR Studies of Amorphous and 98 7.2. Example Applications 154 Polycrystalline Samples under Ambient 7.2.1. Hydroxylation of MgO (100) and CaO 154 Conditions (100) 3.2.1. NMR Methods 98 7.2.2. Transferring Molecular Modeling Results 156 3.2.2. Cross-Polarization NMR as a 100 to Thermodynamic Models Surface-Selective Technique 7.2.3. Thermodynamic Modeling 157 3.2.3. NMR Applied to Metal Oxide Surfaces 100 8. Challenges and Future Directions 160 4. Aqueous Solution−Metal Oxide Interfaces 103 8.1. Surface Complexation Modeling Challenges 160 4.1. Metal Ions in Aqueous Solutions 103 8.2. Experimental Challenges 161 4.1.1. Complexation 104 8.2.1. Atomic-Scale Geometric and Electronic 161 4.1.2. Speciation 106 Structure 4.2. Solubility and Thermodynamics of Metal 108 8.2.2. Future Prospects for Experimental 162 Oxide Surfaces in Contact with Aqueous Studies of Interfacial Layers Solutions 8.2.3. Reaction Kinetics 163 4.2.1. Metal Oxide Dissolution/Solubility 108 8.2.4. Particles, Colloids, and Nanostructured 163 4.2.2. Thermodynamics of Surfaces in Contact 110 Materials with Aqueous Solution 8.2.5. Geomicrobiology 164 4.3. Experimental Studies of the Electrical Double 111 8.3. Theoretical Challenges 165 Layer 9. Acknowledgments 166 4.3.1. Experimental Issues Concerning the 111 10. References 166 Aqueous Solution−Metal Oxide Interface 4.3.2. Experimental Techniques 112 1. Introduction 4.3.3. The Electrical Double Layer 115 4.3.4. Geometric Structure of Metal Oxide 119 During the past decade, interest in chemical reac- Surfaces in Contact with Bulk Water tions occurring at metal oxide-aqueous solution 4.4. Chemical Reactions at Aqueous 120 interfaces has increased significantly because of their Solution−Metal Oxide Interfaces importance in a variety of fields, including atmo- 4.4.1. Conceptual Models of Sorption of 120 spheric chemistry, heterogeneous catalysis and pho- Aqueous Inorganic and Organic Species tocatalysis, chemical sensing, corrosion science, en- at Metal Oxide Surfaces vironmental chemistry and geochemistry, metallurgy 4.4.2. Experimental Studies of Metal Cation and 122 and ore beneficiation, metal oxide crystal growth, soil Oxoanion Sorption at Metal science, semiconductor manufacturing and cleaning, Oxide−Aqueous Solution Interfaces and tribology. The metal oxide-aqueous solution 4.4.3. Heterogeneous Redox Reactions at Metal 131 interface is reactive due to acid-base, ligand- Oxide−Aqueous Solution Interfaces exchange, and/or redox chemistry involving protons 4.4.4. Precipitation Reactions in the Interfacial 138 (hydronium ions), hydroxyl groups, aqueous metal Region ions, and aqueous organic species and also complexes 4.4.5. Catalysis and Photocatalysis 139 among these species. Interfacial localization of those 4.4.6. Photocatalytic Effects of Oxides in the 141 species (adsorption) may result from electrostatic, Atmosphere chemical complexation, and hydrophobic interactions Metal Oxide Surfaces and Their Interactions Chemical Reviews, 1999, Vol. 99, No. 1 79 Gordon E. Brown, Jr., received his B.S. in chemistry and geology in 1965 Carrick Eggleston graduated from Dartmouth College in 1983. He worked in from Millsaps College, Jackson, MS, and his M.S. and Ph.D. in mineralogy the oil field and at a ski area before graduate school, received a National and crystallography from Virginia Polytechnic Institute & State University in Science Foundation graduate fellowship, and received a Ph.D. from Stanford 1968 and 1970, respectively. He is currently the D. W. Kirby Professor of University in 1991. He is presently an Assistant Professor at the University of Earth Sciences at Stanford University and Professor and Chair of the Stanford Wyoming. Synchrotron Radiation Laboratory Faculty at SLAC. Andrew R. Felmy is a Staff Scientist in the Environmental Dynamics and Victor E. Henrich received his Ph.D. in physics from the University of Michigan Simulation Directorate in the Environmental Molecular Sciences Laboratory in 1967. He is currently the Eugene Higgins Professor of Applied Science at at PNNL. He obtained his Ph.D. in 1968 under Professor John H. Weare Yale, and a Professor in the Departments of Applied Physics and of Physics. from the Department