Aqueous Aluminum Polynuclear Complexes and Nanoclusters: A Review

Most undergraduate students of aqueous geochemistry are told that polynuclear aqueous complexes can largely be ignored because they form only from concentrated metal solutions that are rare at the Earth’s surface. However, these polynuclear complexes can serve as models for more-complicated surface structures and are the precursors to nanometric and colloidal solids and solutes. There are many reasons why polynuclear complexes should be foremost in the minds of geochemists, and particularly those geochemists who are interested in molecular information and reaction pathways: 1. Polynuclear complexes contain many of the structural features that are present at mineral surfaces, including a shell of structured water molecules. Because aqueous nanoclusters tumble rapidly in an aqueous solution, one can use solution NMR spectroscopy to determine the structure and the atomic dynamics in these clusters in ways that are impossible for mineral surfaces. 2. Some polynuclear complexes are metastable for long periods of time and may represent an important vector for the dispersal of metal contaminants from hazardous waste. The chemical conditions found in many polluted soils: high metal concentrations, elevated temperatures, and either highly acidic or highly alkaline solutions with a large pH-gradient, are needed to synthesize many polynuclear complexes. It is easy to make a solution that is 5 M in dissolved aluminum at 4 < pH < 6, composed of nanometer-sized clusters that are stable for months or years. 3. Polynuclear complexes lie at the core of many biomolecules, including metalloproteins such as ferritin and enzymes such as nitrogenase. Recent work has suggested that they are present in natural waters (e.g., Rozan et al. 2000) and serve as nuclei for crystal growth. 4. Aqueous clusters are sufficiently small that they can serve as experimental models for ab initio computer simulations that relate bonding to reactivity. In this chapter we discuss polynuclear complexes of aluminum. There is …

[1]  W. Casey,et al.  Water exchange in fluoroaluminate complexes in aqueous solution: a variable temperature multinuclear NMR study. , 2001, Inorganic chemistry.

[2]  F. Taulelle,et al.  3QMAS of three aluminum polycations: space group consistency between NMR and XRD , 2001 .

[3]  W. Casey,et al.  Synthesis and characterization of the GeO(4)Al(12)(OH)(24)(OH2)(12)(8+) polyoxocation. , 2001, Inorganic chemistry.

[4]  W. Casey,et al.  Kinetics of oxygen exchange between sites in the GaO , 2001 .

[5]  W. Casey,et al.  Rates and mechanisms of oxygen exchanges between sites in the AlO4Al12(OH)24(H2O)127+(aq) complex and water: implications for mineral surface chemistry , 2000 .

[6]  Michael E. Lassman,et al.  Evidence for iron, copper and zinc complexation as multinuclear sulphide clusters in oxic rivers , 2000, Nature.

[7]  J. Banfield,et al.  Aggregation-based crystal growth and microstructure development in natural iron oxyhydroxide biomineralization products. , 2000, Science.

[8]  V. Briois,et al.  Formation Mechanism of the Ga13 Keggin Ion: A Combined EXAFS and NMR Study , 2000 .

[9]  L. Nazar,et al.  Speciation and Thermal Transformation in Alumina Sols: Structures of the Polyhydroxyoxoaluminum Cluster [Al30O8(OH)56(H2O)26]18+ and Its δ-Keggin Moieté , 2000 .

[10]  W. Casey,et al.  Bonding and reactivity at oxide mineral surfaces from model aqueous complexes , 2000, Nature.

[11]  A. Amirbahman,et al.  Kinetics and mechanism of ligand-promoted decomposition of the Keggin Al13 polymer , 2000 .

[12]  F. Taulelle,et al.  Al(30): A Giant Aluminum Polycation. , 2000, Angewandte Chemie.

[13]  W. Casey,et al.  Mechanisms for fluoride-promoted dissolution of bayerite [β-Al(OH)3(s)] and boehmite [γ-AlOOH]: 19F-NMR spectroscopy and aqueous surface chemistry , 1999 .

[14]  B. Wehrli,et al.  On the chemistry of the keggin Al13 polymer: kinetics of proton-promoted decomposition , 1999 .

[15]  O. Kamishima,et al.  Local structure and mean-square relative displacement in SiO2 and GeO2 polymorphs , 1999 .

[16]  S. Pennycook,et al.  Hydrogen and the Structure of the Transition Aluminas , 1999 .

[17]  W. Casey,et al.  The rates of water exchange in AI(III)-salicylate and AI(III)-sulfosalicylate complexes , 1999 .

[18]  T. Yokoyama,et al.  ^13C and ^27Al NMR Study on the Interaction between Aluminium Ion and Iminodiacetic Acid in Acidic Aqueous Solutions , 1999 .

[19]  A. Salifoglou,et al.  Synthesis, Structural Characterization, and Solution Behavior of the First Mononuclear, Aqueous Aluminum Citrate Complex , 1999 .

[20]  L. Öhman,et al.  Coordination of acetate to Al(III) in aqueous solution and at the water-aluminum hydroxide interface: A potentiometric and attenuated total reflectance FTIR study , 1998 .

[21]  W. Casey,et al.  AN 17O-NMR STUDY OF THE EXCHANGE OF WATER ON ALOH(H2O)52+(AQ) , 1998 .

[22]  W. Casey,et al.  The rates of exchange of water molecules from Al(III)-methylmalonate complexes: The effect of chelate ring size , 1998 .

[23]  H. Mögel,et al.  Crystal Structure and Formation of the Aluminium Hydroxide Chloride [Al13(OH)24(H2O)24]Cl15 · 13 H2O , 1998 .

[24]  W. Casey,et al.  Rate of water exchange between Al(C2O4)(H2O)4+(aq) complexes and aqueous solutions determined by 17O-NMR spectroscopy , 1997 .

[25]  A. Barron,et al.  Aqueous Synthesis of Water-Soluble Alumoxanes: Environmentally Benign Precursors to Alumina and Aluminum-Based Ceramics , 1997 .

[26]  W. Casey,et al.  Solvent exchange in AlFx (H2O 6−x3−x (aq) complexes: Ligand-directed labilization of water as an analogue for ligand-induced dissolution of oxide minerals , 1997 .

[27]  Barbara Lothenbach,et al.  Immobilization of Heavy Metals by Polynuclear Aluminium and Montmorillonite Compounds , 1997 .

[28]  I. Kiricsi,et al.  Metal Substitution in Keggin-Type Tridecameric Aluminum-Oxo-Hydroxy Clusters. , 1997, Inorganic chemistry.

[29]  A. Barron,et al.  Structural Characterization of Dialkylaluminum Carboxylates: Models for Carboxylate Alumoxanes , 1997 .

[30]  G. Svensson,et al.  A Reinvestigation of β-Gallium Oxide , 1996 .

[31]  A. Powell,et al.  Defining speciation profiles of Al3+ complexed with small organic ligands: the A13+-heidi system , 1996 .

[32]  A. Powell,et al.  Comparative x-ray and 27Al NMR spectroscopic studies of the speciation of aluminum in aqueous systems: Al(III) complexes of N(CH2CO2H)2 (CH2CH2OH) , 1995 .

[33]  A. Bacchi,et al.  Synthesis and New Reactions of Alkynylcobalt Complexes: Preparation and Structure of [Co{η2:η1-C6H4P(OEt)2C(H)C(H)Ph}(CO){PPh(OEt)2}2]BPh4 , 1995 .

[34]  L. Michot,et al.  Intercalation of Al13-Polyethyleneoxide Complexes into Montmorillonite Clay , 1995 .

[35]  I. Kiricsi,et al.  Aluminum complexes in partially hydrolyzed aqueous A1C13 solutions used to prepare pillared clay catalysts , 1995 .

[36]  Wei-Zi Wang,et al.  The Nature of Polynuclear Oh-Al Complexes in Laboratory-Hydrolyzed and Commercial Hydroxyaluminum Solutions , 1994 .

[37]  K. Kawano,et al.  A 9 GHz cw‐electron‐paramagnetic resonance study of the sulphate salts of tridecameric [MnxAl13−xO4(OH)24(H2O)12](7−x)+ , 1993 .

[38]  R. Howe,et al.  The Structure of Al Gels Formed through the Base Hydrolysis of Al3+ Aqueous Solutions , 1993 .

[39]  G. V. Rao,et al.  Evidence for a hydroxy‐aluminium polymer (Al13) in synaptosomes , 1992, FEBS letters.

[40]  G. Furrer,et al.  The formation of polynuclear Al13 under simulated natural conditions , 1992 .

[41]  C. Fyfe,et al.  Characterization of the galloaluminate GaO4Al12(OH)24(H2O)127+ polyoxocation by MAS NMR and infrared spectroscopies and powder x-ray diffraction , 1992 .

[42]  C. Ludwig,et al.  On the chemistry of the Keggin Al13 polymer , 1992 .

[43]  R. Snyder,et al.  Structures and transformation mechanisms of the η, γ and θ transition aluminas , 1991 .

[44]  A. D. Bain,et al.  Aging processes of alumina sol-gels: characterization of new aluminum polyoxycations by aluminum-27 NMR spectroscopy , 1991 .

[45]  D. Hunter,et al.  Evidence for a Phytotoxic Hydroxy-Aluminum Polymer in Organic Soil Horizons , 1991, Science.

[46]  S. Bradley,et al.  Study of the hydrolysis of combined Al3+ and Ga3+ aqueous solutions: Formation of an extremely stable GaO4Al12(OH)24(H2O)  127+ polyoxycation , 1990 .

[47]  G. Valle,et al.  The speciation of aluminum in aqueous solutions of aluminum carboxylates. Part I. X-ray molecular structure of Al[OC(O)CH(OH)CH3]3 , 1990 .

[48]  P. Gurian,et al.  Aluminum citrate: isolation and structural characterization of a stable trinuclear complex , 1990 .

[49]  G. Valle,et al.  Crystal and Molecular Structures of Diaqua(nitrilotriacetato)aluminum(III) and Di-μ-hydroxo-bis(nitrilotriacetato)dialuminate(III) Dianion , 1989 .

[50]  J. W. Akitt.  Multinuclear Studies of Aluminum Compounds , 1989 .

[51]  L. Golič,et al.  The structure of sodium bis(tetraethylammonium) tris(oxalato)aluminate(III) monohydrate , 1989 .

[52]  H. Bilinski,et al.  Equilibrium and structural studies of silicon (IV) and aluminum (III) in aqueous solution. 16. Complexation and precipitation reactions in the proton-aluminum(3+)-phthalate system , 1988 .

[53]  P. Bertsch.  Conditions for Al13 polymer formation in partially neutralized aluminum solutions , 1987 .

[54]  C. Baes,et al.  The hydrolysis of cations , 1986 .

[55]  L. Helm,et al.  Variable-Temperature and Variable-Pressure 17O-NMR Study of Water Exchange of Hexaaquaaluminium(III)†‡ , 1985 .

[56]  S. Schönherr,et al.  Darstellung und Eigenschaften von Heteropolykationenverbindungen. I. Über das Dodekaaluminogermaniumsulfat [GeO4Al12(OH)24(H2O)12](SO4)4 · xH2O , 1983 .

[57]  J. W. Akitt,et al.  ALUMINUM-27 NUCLEAR MAGNETIC RESONANCE STUDIES OF THE HYDROLYSIS OF ALUMINUM(III). PART 4. HYDROLYSIS USING SODIUM CARBONATE , 1981 .

[58]  A. Frueh,et al.  The crystal structure of dawsonite NaAl(CO 3 )(OH) 2 , 1967 .

[59]  J. Bruce,et al.  Oxygen coordinates of compounds with garnet structure , 1965 .

[60]  M. Vicente,et al.  Al-pillared saponites Part 4. Pillaring with a new Al13 oligomer containing organic ligands , 1999 .

[61]  I. Kiricsi,et al.  XPS investigations on the feasibility of isomorphous substitution of octahedral Al3+ for Fe3+ in Keggin ion salts , 1999 .

[62]  L. Öhman,et al.  Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. 34. A crystal structure determination of the Al(methylmalonate)(2)(CH3OH)(2)(-) complex with Na+ as counter-ion , 1998 .

[63]  Gérard Férey,et al.  Crystal structure of κ-alumina: an X-ray powder diffraction,TEM and NMR study , 1997 .

[64]  A. Powell,et al.  Crystal structure and solution-state study of K[Al(mal)2(H2O)2]·2H2O (H2mal = malonic acid) , 1996 .

[65]  A. Barron,et al.  From minerals to materials: synthesis of alumoxanes from the reaction of boehmite with carboxylic acids , 1995 .

[66]  S. Bradley,et al.  Comparison of the species formed upon base hydrolyses of gallium(III) and iron(III) aqueous solutions : the possibility of existence of an [FeO4Fe12(OH)24(H2O)12]7+ polyoxocation , 1993 .

[67]  J. T. Kloprogge,et al.  A 27Al nuclear magnetic resonance study on the optimalization of the development of the Al13 polymer , 1992 .

[68]  L. Öhman,et al.  Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. XXVII, Al3+ complexation to monocarboxylic acids , 1991 .

[69]  D. Aksnes,et al.  Equilibrium and Structural Studies of Silicon(IV) and Aluminium(III) in Aqueous Solution. 24. A Potentiometric and 27Al NMR Study of Polynuclear Aluminium(III) Hydroxo Complexes with Lactic Acid. , 1990 .

[70]  S. Bradley,et al.  Detection of a new polymeric species formed through the hydrolysis of gallium(III) salt solutions , 1990 .

[71]  J. W. Akitt.  Multinuclear studies of aluminium compounds , 1989 .

[72]  G. Valle,et al.  Crystal and molecular structures of diaqua(nitrilotriacetato)aluminium(III) and di-µ-hydroxo-bis(nitrilotriacetato)dialuminate(III) dianion , 1989 .

[73]  J. Springborg.  Hydroxo-Bridged Complexes of Chromium (III), Cobalt (III), Rhodium (III), and Iridium (III) , 1988 .

[74]  P. Huang.  Ionic Factors Affecting Aluminum Transformations and the Impact on Soil and Environmental Sciences , 1988 .

[75]  D. Bish,et al.  Crystal structures and cation sites of the rock-forming minerals , 1988 .

[76]  J. W. Akitt,et al.  Multinuclear magnetic resonance studies of the hydrolysis of aluminium(III). Part 8. Base hydrolysis monitored at very high magnetic field , 1988 .

[77]  L. Öhman,et al.  Equilibrium and Structural Studies of Silicon(IV) and Aluminium(III) in Aqueous Solution. 15. A Potentiometric Study of Speciation and Equilibria in the Al(3+)-CO2(g)-OH- System. , 1987 .

[78]  L. Öhman,et al.  Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. Part 13. A potentiometric and 27Al nuclear magnetic resonance study of speciation and equilibria in the aluminium(III)-oxalic acid-hydroxide system , 1985 .

[79]  L. Öhman,et al.  Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution—10. A potentiometric study of aluminium(III) pyrocatecholates and aluminium(III) hydroxo pyrocatecholates in 0.6 M Na(Cl) , 1983 .

[80]  H. Flood,et al.  The Crystal Structures of [Al2(OH)2(H2O)8](SO4)2.2H2O and [Al2(OH)2(H2O)8](SeO4)2.2H2O. , 1962 .

[81]  A. Kjekshus,et al.  On the Crystal Structure of Some Basic Aluminium Salts. , 1960 .

[82]  L. G. Sillén,et al.  On the Crystal Structure of a Basic Aluminium Sulfate and the Corresponding Selenate. , 1960 .