Structural Chemistry of Inorganic Actinide Compounds (eBook)

Cover 1
Copyright Page 5
Table of Contents 6
Foreword 8
Preface 10
Chapter 1. Crystal chemistry of uranium oxocompounds: an overview 12
1. Introduction 12
2. Coordination Polyhedra and Polyhedral Linkages 13
3. Structural Hierarchy of Inorganic Uranyl Compounds 16
4. Bond-Valence Approach to Uranyl Structures 19
5. Uranyl Oxide Hydrates 19
6. Uranyl Silicates 30
7. Uranyl Carbonates 35
References 39
Chapter 2. Some features of stereochemistry of U(VI) 42
1. Introduction 42
2. Basic principles of stereoatomic model of crystal structures 47
3. Voronoi-Dirichlet polyhedra of the U(VI) atoms in oxygen-containing compounds 51
4. The 18-electron rule for the U(VI) oxocompounds 58
5. Uranyl aqua-complexes 61
6. Carbonate and nitrate uranyl complexes 63
7. Sulfate uranyl complexes 66
8. Structure of the [UO2.O4]z- complexes (.= Si, P ... S) 71
9. Conclusions 74
References 75
Chapter 3. Hydrated oxides, hydroxides and peroxides of transuranium elements 78
1. Introduction 78
2. Transuranium element(III) hydroxides 79
3. Transuranium element (IV) hydroxides 81
4. Transuranium elements(V) hydroxides 88
5. Transuranium elements(VI) hydroxides 98
6. Peroxides 100
References 101
Chapter 4. Actinide compounds containing hexavalent cations of the VI group elements (S, Se, Mo, Cr, W) 106
1. Introduction 106
2. Tri- and tetravalent actinide compounds 107
3. Actinyl compounds 121
4. Flexibility of structural units with corner-sharing UO7 pentagonal bipyramids and TO4 tetrahedra (T = S, Cr, Se, Mo) 184
5. Concluding remarks 186
References 186
Chapter 5. Actinide compounds with heavy oxoanions containing a stereochemically active lone-pair of electrons 194
1. Introduction 194
2. Some Tellurites of Interest 201
3. Some Iodates of Interest 207
4. Transplutonium Iodates 216
5. Underdeveloped actinide oxoanions: antimonites and bismuthites 221
6. Summary 222
References 224
Chapter 6. Crystal chemistry of actinide phosphates and arsenates 228
1. Introduction 228
2. Trivalent and Tetravalent Actinides 229
3. Hexavalent Actinides 252
References 284
Chapter 7. Structural chemistry of uranium vanadates: from 2-D to 3-D networks 290
1. Introduction 290
2. 2-D polymerization of U polyhedra 291
3. 1-D polymerization of U polyhedra 299
4. 2-D and 3-D arrangements of mutually perpendicular [[7]U]e chains 308
5. 2-D polymerization of VO5 square pyramids or VO6 octahedra 312
6. Copolymerization of the U and V polyhedra 317
7. Mobility of the alkaline ions in the 2-D networks and 3-D frameworks 319
8. Conclusions 320
References 322
Chapter 8. Chemistry and structural chemistry of anhydrous tri- and tetravalent actinide orthophosphates 326
1. Introduction 326
2. The tetravalent actinide orthophosphates: M – thorium, uranium, neptunium, plutonium 328
3. Trivalent actinide orthophosphates: plutonium, americium, curium, berkelium, californium, einsteinium 340
4. Structural investigations of tetra- and trivalent actinide orthophosphates 341
5. Conclusions 347
References 348
Chapter 9. Structural chemistry of actinide polyoxometalates 352
1. Introduction 352
2. Molybdates 354
3. Tungstates 356
4. Solution equilibria btween actinide cations and polyoxometalate anions 368
5. Conclusions 369
Acknowledgment 369
References 370
Chapter 10. Coordination interaction of transuranium elements with N-donor ligands 374
1. Introduction 374
2. Trivalent transuranium elements 377
3. Tetravalent transuranium elements 383
4. Pentavalent transuranium elements 388
5. Hexavalent transuranium elements 407
6. Conclusion 411
References 414
Chapter 11. U(VI)-containing metal-organic frameworks and coordination polymers 420
1. Introduction 420
2. Structural Systematics for U-MOFs and U-CPs 423
3. Specific Examples 427
4. Miscellaneous structures 446
5. Conclusions and outlook 450
Acknowledgements 450
References 451
Chapter 12. Nanostructured actinide compounds: an introduction 454
1. Introduction 454
2. 0D structures: actinide peroxide nanospheres 455
3. 1D structures: uranyl selenate nanotubules 458
4. 2D structures: organic-inorganic nanocomposites 460
5. Conclusions 466
References 467
Chapter 13. Actinide host phases as radioactive waste forms 468
1. Introduction 468
2. Actinide-bearing waste streams 470
3. Major requirements for actinide waste forms 471
4. Determination of durability and radiation resistance of HLW forms 472
5. Types and design of the HLW and actinide waste forms 474
6. Production of the HLW and actinide waste forms 475
7. Vitreous actinide waste forms 477
8. Crystalline actinide waste forms 478
9. Glass-ceramic actinide waste forms 492
10. Conclusion 493
Acknowledgements 494
References 495
Subject Index 502