Mossbauer spectroscopy applications in chemistry biology industry and nanotechnology

€
MOSSBAUER
SPECTROSCOPY



€
MOSSBAUER
SPECTROSCOPY
APPLICATIONS IN CHEMISTRY,
BIOLOGY, AND NANOTECHNOLOGY

Edited by
Virender K. Sharma, Ph.D.
Göstar Klingelhöfer
Tetsuaki Nishida


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Library of Congress Cataloging-in-Publication Data:
M€
ossbauer spectroscopy : applications in chemistry, biology, industry, and nanotechnology / [edited by] Virender K. Sharma, Ph.D.,
G€
ostar Klingelh€
ofer, Tetsuaki Nishida.
pages cm
Includes bibliographical references and index.
ISBN 978-1-118-05724-7 (hardback)
1. M€
ossbauer spectroscopy. I. Sharma, Virender K., editor of compilation. II. Klingelh€
ofer, G€
ostar, 1956- editor of compilation.
III. Nishida, Tetsuaki, 1950- editor of compilation.
QD96.M6M638 2014
2013011056
5430 .6–dc23
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1


We dedicate this book to the late Professor Attila Vertez,
E€otv€os Lorand University, Budapest, Hungary

Contents
Preface xix
Contributors xxi

Part I

Instrumentation 1

Chapter 1 | In Situ M€
ossbauer Spectroscopy with Synchrotron Radiation
on Thin Films

Svetoslav Stankov, Tomasz Sle˛zak, Marcin Zaja˛c, Michał Sle˛zak, Marcel Sladecek, Ralf R€ohlsberger,
Bogdan Sepiol, Gero Vogl, Nika Spiridis, Jan Ła_zewski, Krzysztof Parlinski, and Jozef Korecki

3

1.1
1.2

Introduction 3
Instrumentation 4
1.2.1 Nuclear Resonance Beamline ID18 at the ESRF 5
1.2.2 The UHV System for In Situ Nuclear Resonant Scattering Experiments
at ID18 of the ESRF 6
1.3
Synchrotron Radiation-Based M€

ossbauer Techniques 10
1.3.1 Coherent Elastic Nuclear Resonant Scattering 10
1.3.2 Coherent Quasielastic Nuclear Resonant Scattering 25
1.3.3 Incoherent Inelastic Nuclear Resonant Scattering 30
1.4
Conclusions 38
Acknowledgments 39
References 39

Chapter 2 | M€
ossbauer Spectroscopy in Studying Electronic Spin and Valence
States of Iron in the Earth’s Lower Mantle

43

Jung-Fu Lin, Zhu Mao, and Ercan E. Alp
2.1
2.2

Introduction 43
Synchrotron M€
ossbauer Spectroscopy at High Pressures and
Temperatures 44
2.3.1 Crystal Field Theory on the 3d Electronic States 46
2.3.2 Electronic Spin Transition of Fe2þ in Ferropericlase 47
2.3.3 Spin and Valence States of Iron in Silicate Perovskite 49
2.3.4 Spin and Valence States of Iron in Silicate Postperovskite 52
2.4
Conclusions 54
Acknowledgments 55

References 55

Chapter 3 | In-Beam M€
ossbauer Spectroscopy Using a Radioisotope Beam and
a Neutron Capture Reaction

58

Yoshio Kobayashi
3.1
3.2

Introduction 58
57
Mn (!57Fe) Implantation M€
ossbauer Spectroscopy 61
3.2.1 In-Beam M€
ossbauer Spectrometer 61
3.2.2 Detector for 14.4 keV M€
ossbauer g-Rays 62
3.2.3 Application to Materials Science—Ultratrace of Fe Atoms in Si
and Dynamic Jumping 62
vii


viii

CONTENTS

3.2.4 Application to Inorganic Chemistry 63

3.2.5 Development of M€
ossbauer g-Ray Detector 65
3.3
Neutron In-Beam M€
ossbauer Spectroscopy 66
3.4
Summary 66
References 67

Part II

Radionuclides 71

Chapter 4 | Lanthanides (151Eu and

155

Gd) M€
ossbauer Spectroscopic Study
of Defect-Fluorite Oxides Coupled with New Defect Crystal
Chemistry Model

73

Akio Nakamura, Naoki Igawa, Yoshihiro Okamoto, Yukio Hinatsu, Junhu Wang,
Masashi Takahashi, and Masuo Takeda
4.1
4.2
4.3

Introduction 73
Defect Crystal Chemistry (DCC) Lattice Parameter Model 76
Lns-M€
ossbauer and Lattice Parameter Data of DF Oxides 79
ossbauer and Lattice Parameter Data of M-Eus (M4þ ¼ Zr, Hf, Ce, U,
4.3.1 151Eu-M€
and Th) 79
ossbauer and Lattice Parameter Data of Zr1ÀyGdyO2Ày/2 80
4.3.2 155Gd-M€
4.4
DCC Model Lattice Parameter and Lns-M€
ossbauer Data Analysis 84
4.4.1 DCC Model Lattice Parameter Data Analysis of Ce–Eu and Th–Eu 85
4.4.2 Quantitative BL(Eu3þÀÀO)-Composition (y) Curves in Zr–Eu and Hf–Eu 88
4.4.3 Model Extension Attempt from Macroscopic Lattice Parameter Side 89
4.5
Conclusions 92
References 93

Chapter 5 | M€
ossbauer and Magnetic Study of Neptunyl(þ1) Complexes

95

Tadahiro Nakamoto, Akio Nakamura, and Masuo Takeda
5.1
5.2
5.3
5.4

Introduction 95
237
Np M€
ossbauer Spectroscopy 96
Magnetic Property of Neptunyl Monocation (NpO2þ) 97
M€
ossbauer and Magnetic Study of Neptunyl(þ1) Complexes 98
5.4.1 (NH4)[NpO2(O2CH)2] (1) 98
5.4.2 [NpO2(O2CCH2OH)(H2O)] (2) 100
5.4.3 [NpO2(O2CH)(H2O)] (3) 101
5.4.4 [(NpO2)2((O2C)2C6H4)(H2O)3]ÁH2O (4) 104
5.5
Discussion 106
ossbauer Relaxation Spectra 106
5.5.1 237 Np M€
5.5.2 Magnetic Susceptibility and Saturation Moment: Averaged Powder Magnetization
for the Ground jJz ¼ Æ4i Doublet 107
5.6
Conclusion 113
Acknowledgment 113
References 113

Chapter 6 | M€
ossbauer Spectroscopy of

161

Dy in Dysprosium Dicarboxylates

Masashi Takahashi, Clive I. Wynter, Barbara R. Hillery, Virender K. Sharma, Duncan Quarless,

Leopold May, Toshiyuki Misu, Sabrina G. Sobel, Masuo Takeda, and Edward Brown
6.1
Introduction 116
6.2
Experimental Methods 117
6.3
Results and Discussion 117
Acknowledgment 122
References 122

116


ix

CONTENTS

Chapter 7 | Study of Exotic Uranium Compounds Using

238

U M€
ossbauer

Spectroscopy

123

Satoshi Tsutsui and Masami Nakada
7.1

7.2

Introduction 123
Determination of Nuclear g-Factor in the Excited State of 238U Nuclei 125
ossbauer Spectroscopy and Its Application
7.2.1 Background of 238 U M€
to Magnetism in Uranium Compounds 125
ossbauer and 235 U NMR Measurements of UO2 in the
7.2.2 238 U M€
Antiferromagnetic State 125
7.2.3 Determination of the Nuclear g-Factor in the First Excited
State of 238 U 127
ossbauer Spectroscopy to Heavy Fermion
7.3
Application of 238U M€
Superconductors 127
7.3.1 Introduction of Uranium-Based Heavy Fermion Superconductors 127
7.3.2 Magnetic Ordering and Paramagnetic Relaxation in Heavy Fermion
Superconductors 129
ossbauer Spectroscopy of Uranium-Based
7.3.3 Summary of 238 U M€
Heavy Fermion Superconductors 133
7.4
Application to Two-Dimensional (2D) Fermi Surface System of Uranium
Dipnictides 134
7.4.1 Introduction of Uranium Dipnictides 134
7.4.2 Hyperfine Interactions Correlated with the Magnetic Structures in Uranium
Dipnictides 135
ossbauer Spectroscopy of Uranium Dipnictides 137
7.4.3 Summary of 238 U M€

7.5
Summary 137
Acknowledgments 138
References 138

Part III

Spin Dynamics 141

Chapter 8 | Reversible Spin-State Switching Involving a Structural Change

143

Satoru Nakashima
8.1
8.2

Introduction 143
Three Assembled Structures of Fe(NCX)2(bpa)2 (X ¼ S, Se) and Their
Structural Change by Desorption of Propanol Molecules [23] 144
8.3
Occurrence of Spin-Crossover Phenomenon in Assembled
Complexes Fe(NCX)2(bpa)2 (X ¼ S, Se, BH3) by Enclathrating
Guest Molecules [25–27] 145
8.4
Reversible Structural Change of Host Framework of Fe(NCS)2(bpp)2Á2
(Benzene) Triggered by Sorption of Benzene Molecules [29] 147
8.5
Reversible Spin-State Switching Involving a Structural Change
of Fe(NCX)2(bpp)2Á2(Benzene) (X ¼ Se, BH3) Triggered by Sorption

of Benzene Molecules [30] 149
8.6
Conclusions 150
References 151

Chapter 9 | Spin-Crossover and Related Phenomena Coupled with Spin,
Photon, and Charge
Norimichi Kojima and Akira Sugahara
9.1
9.2

Introduction 152
Photoinduced Spin-Crossover Phenomena 153
9.2.1 LIESST for Fe(II) Complexes 153

152


x

CONTENTS

9.2.2 LIESST for Fe(III) Complexes 157
9.2.3 Recent Topics of Photoinduced Spin-Crossover Phenomena 160
9.3
Charge Transfer Phase Transition 161
9.3.1 Thermally Induced Charge Transfer Phase Transition 161
9.3.2 Photoinduced Charge Transfer Phase Transition 164
9.4
Spin Equilibrium and Succeeding Phenomena 168

9.4.1 Rapid Spin Equilibrium in Solid State 168
9.4.2 Concerted Phenomenon Coupled with Spin Equilibrium and Valence
Fluctuation 173
References 175

Chapter 10

| Spin Crossover in Iron(III) Porphyrins Involving the
Intermediate-Spin State

177

Mikio Nakamura and Masashi Takahashi
10.1
10.2

Introduction 177
Methodology to Obtain Pure Intermediate-Spin Complexes 178
10.2.1 Saddled Deformation 178
10.2.2 Ruffled Deformation 182
10.2.3 Core Modification 184
10.3 Spin Crossover Involving the Intermediate-Spin State 189
10.3.1 Spin Crossover Between S ¼ 3/2 and S ¼ 1/2 189
10.3.2 Spin Crossover Between S ¼ 3/2 and S ¼ 5/2 192
10.4 Spin-Crossover Triangle in Iron(III) Porphyrin Complexes 195
10.5 Conclusions 198
Acknowledgments 198
References 199

Chapter 11

| Tin(II) Lone Pair Stereoactivity: Influence on Structures and
Properties and M€
ossbauer Spectroscopic Properties
Georges Denes, Abdualhafed Muntasar, M. Cecilia Madamba, and Hocine Merazig
11.1
11.2
11.3

11.4

11.5

11.6

Introduction 202
Experimental Aspects 203
11.2.1 Sample Preparation 203
Crystal Structures 204
11.3.1 The Fluorite-Type Structure: A Typically Ionic Structure 204
11.3.2 Tin(II) Fluoride: Covalent Bonding and Polymeric Structure 205
11.3.3 The a-PbSnF4 Structure: The Unexpected Combination of Ionic
Bonding and Covalent Bonding 207
11.3.4 The PbClF-Type Structure: An Ionic Structure and a Tetragonal Distortion
of the Fluorite Type 207
Tin Electronic Structure and M€
ossbauer Spectroscopy 208
11.4.1 Tin Electronic Structure, Bonding Type, and Coordination 208
11.4.2 Using M€
ossbauer Spectroscopy to Probe the Tin Electronic Structure

and Bonding Mode 211
Application to the Structural Determination of a-SnF2 213
11.5.1 History 213
ossbauer Spectroscopy to Determine that the Tin Positions
11.5.2 Using 119Sn M€
Used by Bergerhoff Were Incorrect 214
Application to the Structural Determination of the Highly Layered
Structures of a-PbSnF4 and BaSnF4 216
11.6.1 History 216
11.6.2 Unit Cell of MSnF4 and Relationships with the Fluorite-Type MF2 217

202


xi

CONTENTS

11.6.3 M€
ossbauer Spectroscopy, Bonding Type, Crystal Symmetry, and Preferred
Orientation 220
11.6.4 Combining All the Results: The a-PbSnF4 Structural Type 225
11.7 Application to the Structural Study of Disordered Phases 226
11.7.1 Disordered Fluoride Phases 226
11.7.2 Disordered Chloride Fluoride Phases 232
11.8 Lone Pair Stereoactivity and Material Properties 241
11.9 Conclusions 242
Acknowledgments 243
References 243

Part IV

Biological Applications 247

Chapter 12

| Synchrotron Radiation-Based Nuclear Resonant Scattering:
Applications to Bioinorganic Chemistry

249

Yisong Guo, Yoshitaka Yoda, Xiaowei Zhang, Yuming Xiao, and Stephen P. Cramer
12.1
12.2

Introduction 249
Technical Background 250
12.2.1 Theoretical Aspects of NFS 250
12.2.2 Theoretical Aspects of SRPAC 252
12.2.3 Experimental Aspects of NFS and SRPAC 255
12.3 Applications in Bioinorganic Chemistry 258
12.3.1 Nuclear Forward Scattering 258
12.3.2 SRPAC 264
12.4 Summary and Prospects 269
Acknowledgments 269
References 269

Chapter 13

| M€

ossbauer Spectroscopy in Biological and Biomedical Research

272

Alexander A. Kamnev, Krisztina Kovacs, Irina V. Alenkina, and Michael I. Oshtrakh
13.1 Introduction 272
13.2 Microorganisms-Related Studies 273
13.3 Plants 276
13.4 Enzymes 280
13.5 Hemoglobin 281
13.6 Ferritin and Hemosiderin 283
13.7 Tissues 284
13.8 Pharmaceutical Products 286
13.9 Conclusions 286
Acknowledgments 287
References 287

Chapter 14

| Controlled Spontaneous Decay of M€
ossbauer Nuclei
(Theory and Experiments)

292

Vladimir I. Vysotskii and Alla A. Kornilova
14.1
14.2

Introduction to the Problem of Controlled Spontaneous Gamma Decay 292

The Theory of Controlled Radiative Gamma Decay 293
14.2.1 General Consideration 293
14.3 Controlled Spontaneous Gamma Decay of Excited Nucleus in the System
of Mutually Uncorrelated Modes of Electromagnetic Vacuum 295
14.3.1 Spontaneous Gamma Decay in the Case of Free Space 296
14.3.2 Spontaneous Gamma Decay of Excited Nuclei in the Case of Screen
Presence 298


xii

CONTENTS

14.4

Spontaneous Gamma Decay in the System of Synchronized
Modes of Electromagnetic Vacuum 302
14.5 Experimental Study of the Phenomenon of Controlled Gamma Decay
of M€
ossbauer Nuclei 303
14.5.1 Investigation of the Phenomenon of Controlled Gamma Decay by Analysis of
Deformation of M€
ossbauer Gamma Spectrum 303
14.6 Experimental Study of the Phenomenon of Controlled Gamma Decay
by Investigation of Space Anisotropy and Self-Focusing of
M€
ossbauer Radiation 309
14.7 Direct Experimental Observation and Study of the Process of Controlled
Radioactive and Excited Nuclei Radiative Gamma Decay by the Delayed
Gamma–Gamma Coincidence Method 311

14.8 Conclusions 314
References 314

Chapter 15

| Nature’s Strategy for Oxidizing Tryptophan: EPR and M€
ossbauer
Characterization of the Unusual High-Valent Heme Fe Intermediates

315

Kednerlin Dornevil and Aimin Liu
15.1 Two Oxidizing Equivalents Stored at a Ferric Heme 315
15.2 Oxidation of L-Tryptophan by Heme-Based Enzymes 316
15.3 The Chemical Reaction Catalyzed by MauG 318
15.4 A High-Valent Bis-Fe(IV) Intermediate in MauG 319
15.5 A High-Valent Fe Intermediate of Tryptophan 2,3-Dioxygenase 320
15.6 Concluding Remarks 321
References 322

Chapter 16

| Iron in Neurodegeneration

Jolanta Gała˛zka-Friedman, Erika R. Bauminger, and Andrzej Friedman

324

16.1
16.2

16.3
16.4
16.5

Introduction 324
Neurodegeneration and Oxidative Stress 324
M€
ossbauer Studies of Healthy Brain Tissue 325
Properties of Ferritin and Hemosiderin Present in Healthy Brain Tissue 327
Concentration of Iron Present in Healthy and Diseased Brain Tissue:
Labile Iron 328
16.6 Asymmetry of the M€
ossbauer Spectra of Healthy and Diseased
Brain Tissue 330
16.7 Conclusion: The Possible Role of Iron in Neurodegeneration 331
References 331

Chapter 17

| Emission (57Co) M€
ossbauer Spectroscopy: Biology-Related Applications,
Potentials, and Prospects

333

Alexander A. Kamnev
17.1
17.2
17.3
17.4

Introduction 333
Methodology 334
Microbiological Applications 336
Enzymological Applications 340
17.4.1 Choosing a Test Object 340
17.4.2 Prerequisites for Using the 57 Co EMS Technique 342
17.4.3 Experimental 57 Co EMS Studies 342
17.4.4 Two-Metal-Ion Catalysis: Competitive Metal Binding at the Active Centers 344
17.4.5 Possibilities of 57 Co Substitution for Other Cations in Metalloproteins 345
17.5 Conclusions and Outlook 345
Acknowledgments 345
References 346


xiii

CONTENTS

Part V

Iron Oxides 349

Chapter 18

| M€
ossbauer Spectroscopy in Study of Nanocrystalline Iron Oxides
from Thermal Processes

Ji9rı Tu9cek, Libor Machala, Ji9rı Frydrych, Ji9rı Pechou9sek, and Radek Zbo9ril

351

18.1
18.2

Introduction 351
Polymorphs of Iron(III) Oxide, Their Crystal Structures, Magnetic
Properties, and Polymorphous Phase Transformations 352
18.2.1 a-Fe2O3 353
18.2.2 b-Fe2O3 358
18.2.3 g-Fe2O3 360
18.2.4 e-Fe2O3 364
18.2.5 Amorphous Fe2O3 369
ossbauer Spectroscopy in Monitoring Solid-State
18.3 Use of 57Fe M€
Reaction Mechanisms Toward Iron Oxides 371
18.3.1 Thermal Decomposition of Ammonium Ferrocyanide—A Valence Change
Mechanism 371
18.3.2 Thermal Decomposition of Prussian Blue in Air 374
18.3.3 Thermal Conversion of Fe2(SO4)3 in Air—Polymorphous Exhibition of Fe2O3 376
18.3.4 Nanocrystalline Fe2O3 Catalyst from FeC2O4Á2H2O 376
18.4 Various M€
ossbauer Spectroscopy Techniques in Study of Applications
Related to Nanocrystalline Iron Oxides 378
ossbauer Spectroscopy at Various Temperatures 378
18.4.1 57Fe Transmission M€
ossbauer Spectroscopy 379
18.4.2 In-Field 57Fe Transmission M€
ossbauer Spectroscopy 381

18.4.3 In Situ High-Temperature 57Fe Transmission M€
ossbauer Spectroscopy 383
18.4.4 57Fe Conversion Electron and Conversion X-Ray M€
18.5 Conclusions 389
Acknowledgments 389
References 389

Chapter 19

| Transmission and Emission

57

Fe M€
ossbauer Studies on Perovskites

and Related Oxide Systems

393

Zoltan Homonnay and Zoltan Nemeth
19.1
19.2

Introduction 393
Study of High-TC Superconductors 394
19.2.1 Study of 57 Co-Doped YBa2Cu3O7Àd 395
19.2.2 Study of 57 Co-Doped Y1ÀxPrxBa2Cu3O7Àd 397
19.3 Study of Strontium Ferrate and Its Substituted Analogues 401
19.3.1 Study of Sr0.95Ca0.05Co0.5Fe0.5O3Àd and Sr0.5Ca0.5Co0.5Fe0.5O3Àd 401

19.4 Pursuing Colossal Magnetoresistance in Doped Lanthanum Cobaltates 407
19.4.1 Emission M€
ossbauer Study of La0.8Sr0.2CoO3Àd Perovskites 408
19.4.2 Emission and Transmission M€
ossbauer Study of Iron-Doped
La0.8Sr0.2FeyCo1ÀyO3Àd Perovskites 411
References 413

Chapter 20

| Enhancing the Possibilities of

57

Fe M€
ossbauer Spectrometry
to Study the Inherent Properties of Rust Layers
Karen E. Garcıa, Cesar A. Barrero, Alvaro L. Morales, and Jean-Marc Greneche

20.1
20.2

Introduction 415
M€
ossbauer Characterization of Some Iron Phases Presented in the Rust
Layers 416
20.2.1 Akaganeite 416

415

xiv

CONTENTS

20.2.2 Goethite 418
20.2.3 Magnetite/Maghemite 420
20.3 Determining Inherent Properties of Rust Layers by M€
ossbauer
Spectrometry 421
20.3.1 Rust Layers in Steels Submitted to Total Immersion Tests 421
20.3.2 Rust Layers in Steels Submitted to Dry–Wet Cycles 424
20.3.3 Rust Layers in Steels Submitted to Outdoor Tests 426
20.4 Final Remarks 426
Acknowledgments 426
References 426

Chapter 21

| Application of M€
ossbauer Spectroscopy to Nanomagnetics

429

Lakshmi Nambakkat
21.1
21.2

Introduction 429
Spinel Ferrites 430

21.2.1 Microstructure Determination 430
21.2.2 Elucidation of Bulk Magnetic Properties in Nanoferrites Using In-Field M€
ossbauer
Spectroscopy 434
21.2.3 Core–Shell Effect on the Magnetic Properties in Superparamagnetic
Nanosystems 436
21.3 Nanosized Fe–Al Alloys Synthesized by High-Energy Ball Milling 441
21.3.1 Nanosized Al–1 at% Fe 442
21.4 Magnetic Thin Films/Multilayer Systems: 57Fe/AI MLS 446
21.4.1 Structural Characterization 447
21.4.2 DC Magnetization Studies 448
21.4.3 M€
ossbauer (CEMS) Study 451
21.5 Conclusions 452
Acknowledgments 453
References 453

Chapter 22

| M€
ossbauer Spectroscopy and Surface Analysis

455

Jose F. Marco, Jose Ramon Gancedo, Matteo Monti, and Juan de La Figuera
22.1
22.2

Introduction 455
The Physical Basis: How and Why Electrons Appear in M€

ossbauer
Spectroscopy 456
22.3 Increasing Surface Sensitivity in Electron M€
ossbauer Spectroscopy 458
22.4 The Practical Way: Experimental Low-Energy Electron M€
ossbauer
Spectroscopy 460
22.5 M€
ossbauer Surface Imaging Techniques 465
22.6 Recent Surface M€
ossbauer Studies in an “Ancient” Material:
Fe3O4 466
Acknowledgment 468
References 468

Chapter 23

|

57

Fe M€
ossbauer Spectroscopy in the Investigation of the
Precipitation of Iron Oxides
Svetozar Music, Mira Ristic, and Stjepko Krehula
23.1
23.2
23.3
23.4

Introduction 470
Complexation of Iron Ions by Hydrolysis 470
Precipitation of Iron Oxides by Hydrolysis Reactions 472
Precipitation of Iron Oxides from Dense b-FeOOH
Suspensions 480

470


xv

CONTENTS

23.5

Precipitation and Properties of Some Other Iron Oxides 483
23.5.1 Ferrihydrite 483
23.5.2 Lepidocrocite (g-FeOOH) 485
23.5.3 Magnetite (Fe3O4) and Maghemite (g-Fe2O3) 487
23.6 Influence of Cations on the Precipitation of Iron Oxides 490
23.6.1 Goethite 490
23.6.2 Hematite 495
23.6.3 Magnetite and Maghemite 496
Acknowledgment 496
References 497

Chapter 24

| Ferrates(IV, V, and VI): M€
ossbauer Spectroscopy Characterization

505

Virender K. Sharma, Yurii D. Perfiliev, Radek Zbo9ril, Libor Machala, and Clive I. Wynter
24.1
24.2
24.3

Introduction 505
Spectroscopic Characterization 506
M€
ossbauer Spectroscopy Characterization 508
24.3.1 Ferryl(IV) Ion 508
24.3.2 Ferrates(IV, V, and VI) 510
24.3.3 Case Studies 513
Acknowledgments 517
References 517

Chapter 25

| Characterization of Dilute Iron-Doped Yttrium Aluminum
Garnets by M€
ossbauer Spectrometry

521

Kiyoshi Nomura and Zoltan Nemeth
25.1 Introduction 521
25.2 Sample Preparations by the Sol–Gel Method 523
25.3 X-Ray Diffraction and EXAFS Analysis 523

25.4 Magnetic Properties 525
25.5 M€
ossbauer Analysis of YAG Doped with Dilute Iron 526
25.6 Microdischarge Treatment of Iron-Doped YAG 528
25.7 Conclusions 531
Acknowledgments 532
References 532

Part VI

Industrial Applications 533

Chapter 26

| Some M€
ossbauer Studies of Fe–As-Based
High-Temperature Superconductors

535

Amar Nath and Airat Khasanov
26.1
26.2
26.3
26.4

Introduction 535
Experimental Procedure 535
Where Do the Injected Electrons Go? 537
New Electron-Rich Species in Ni-Doped Single Crystals: Is It

Superconducting? 538
26.5 Can O2 Play an Important Role? 539
Acknowledgment 541
References 541

Chapter 27

| M€
ossbauer Study of New Electrically Conductive Oxide Glass
Tetsuaki Nishida and Shiro Kubuki
27.1

Introduction 542
27.1.1 Electrically Conductive Oxide Glass 542
27.1.2 Cathode Active Material for Lithium-Ion Battery (LIB) 543

542


xvi

CONTENTS

27.2

Structural Relaxation of Electrically Conductive Vanadate Glass 544
27.2.1 Increase in the Electrically Conductivity of Vanadate Glass 544
27.2.2 Cathode Active Material for Li-Ion Battery (LIB) 547
27.3 Summary 551
Acknowledgments 551

References 551

Chapter 28

| Applications of M€
ossbauer Spectroscopy in the Study of Lithium
Battery Materials

552

Ricardo Alcantara, Pedro Lavela, Carlos Perez Vicente, and Jose L. Tirado
28.1
28.2

Introduction 552
Cathode Materials for Li-Ion Batteries 554
28.2.1 Layered Intercalation Electrodes 554
28.2.2 Phosphate Electrodes with Olivine Structure 554
28.2.3 Insertion Silicate Electrodes 555
28.3 Anode Materials for Li-Ion Batteries 556
28.3.1 Conversion Oxides 556
28.3.2 Tin Alloys and Intermetallic Compounds 558
28.3.3 Antimony Alloys and Intermetallic Compounds 560
28.4 Conclusions 561
Acknowledgments 561
References 562

Chapter 29

| M€

ossbauer Spectroscopic Investigations of Novel Bimetal Catalysts
for Preferential CO Oxidation in H2

564

Wansheng Zhang, Junhu Wang, Kuo Liu, Jie Jin, and Tao Zhang
29.1
29.2

Introduction 564
Experimental Section 564
29.2.1 Catalyst Preparation 564
29.2.2 Catalytic Activity Test 565
29.2.3 M€
ossbauer Spectra Characterization 565
29.3 Results and Discussion 565
29.3.1 PtFe Alloy Nanoparticles Catalyst 565
29.3.2 Ir–Fe/SiO2 Catalyst 567
29.4 Conclusions 574
Acknowledgments 574
References 575

Chapter 30

| The Use of M€
ossbauer Spectroscopy in Coal Research: Is It Relevant
or Not?
Frans B. Waanders
30.1
30.2

Introduction 576
Experimental Procedures 577
30.2.1 M€
ossbauer Spectroscopy 577
30.2.2 SEM Analyses 577
30.2.3 XRD Analyses 577
30.2.4 Samples and Sample Preparation 577
30.3 Results and Discussion 578
30.3.1 M€
ossbauer Analyses of the As-Mined Samples 578
30.3.2 Weathering of Coal 578
30.3.3 Corrosion of Mild Steel Due to the Presence of Compacted Fine Coal 583
30.3.4 Coal Combustion 584
30.3.5 Coal Gasification and Resultant Products 587

576


xvii

CONTENTS

30.4 Conclusions 590
Acknowledgments 591
References 591

Part VII
Chapter 31

Environmental Applications 593

| Water Purification and Characterization of Recycled
Iron-Silicate Glass

595

Shiro Kubuki and Tetsuaki Nishida
31.1

Introduction 595
31.1.1 Water-Purifying Ability of Recycled Iron Silicate Glass 595
31.1.2 Iron Silicate Glass Prepared by Recycling Coal Ash 596
31.2 Properties and Structure of Recycled Silicate Glasses 596
31.2.1 Water-Purifying Ability of Recycled Silicate Glasses 596
31.2.2 Electromagnetic Property of Recycled Silicate Glasses 601
31.3 Summary 605
31.3.1 Water-Purifying Ability of Recycled Silicate Glasses 605
31.3.2 Electromagnetic Property of Recycled Silicate Glasses 606
References 606

Chapter 32

| M€
ossbauer Spectroscopy in the Study of Laterite Mineral Processing
Eamonn Devlin, Michail Samouhos, and Charalabos Zografidis
32.1 Introduction 608
32.2 Conventional Processing 609
32.3 Microwave Processing 612
References 619

Index 621

608



Preface
Five decades ago, the M€ossbauer concept was invented. Since then the M€
ossbauer spectroscopy has been applied in a wide
range of fields including physics, chemistry, biology, and nanotechnology. The M€
ossbauer spectroscopy is still being
applied vigorously in understanding the hyperfine interactions of electromagnetic nature. This is evident from a similar
number of publications on the M€
ossbauer concept (14,000/decade) in the last three decades. This book presents the
current knowledge on the applications of M€
ossbauer spectroscopy. With this theme in the minds of editors, many
experts were invited to contribute to the book on the use of the M€ossbauer effect in a number of subject areas. The
editors also made sure that the contributors were from almost every region of the world (i.e., North America, South
America, Europe, Africa, and Asia) in order to cover different aspects of the M€
ossbauer spectroscopy.
In Chapters 1 and 2, an introduction is made to the synchrotron M€
ossbauer spectroscopy with examples. Examples
include the in situ M€
ossbauer spectroscopy with synchrotron radiation on thin films and the study of deep-earth minerals.
Investigations of in-beam M€
ossbauer spectroscopy using a 57 Mn beam at the RIKEN RIBF is presented in Chapter 3. This
chapter demonstrates innovative experimental setup for online M€
ossbauer spectroscopy using the thermal neutron
ossbauer spectroscopy of radionuclides is described in Chapters 4–7. Chapter 4

capture reaction, 56 Fe (n, g) 57 Fe. The M€
ossbauer structure and powder X-ray
gives full description of the latest analysis results of lanthanides (151 Eu and 155 Gd) M€
diffraction (XRD) lattice parameter (a0) data of defect fluorite (DF) oxides with the new defect crystal chemistry (DCC)
ossbauer and magnetic study of neptunyl(þ1) complexes, while Chapter 6
a0 model. Chapter 5 reviews the 237 Np M€
ossbauer spectrosdescribes the M€
ossbauer spectroscopy of organic complexes of europium and dysprosium. 238 U M€
copy is presented in Chapter 7. There are three chapters on spin-state switching/spin-crossover phenomena (Chapter 8–
10). Examples in these chapters are mainly on iron compounds, such as iron(III) porphyrins. The use of M€
ossbauer
spectroscopy of physical properties of Sn(II) is discussed in Chapter 11.
Chapters 12–17 are devoted to applications of the M€
ossbauer spectroscopy to the biological chemistry. Chapter 12
details the recent progress on the application of 57 Fe NFS, 57 Fe SRPAC, and 61 Ni SRPAC to bioinorganic chemistry. The
future prospect of these techniques is also given. The role of M€
ossbauer spectroscopy in biological and biomedical
research is described in Chapters 13 and 17. These chapters demonstrate how M€
ossbauer spectroscopy can be applied
to study microorganisms, plants, tissues, enzymes, hemoglobin, ferritin, and hemosiderin. Chapter 15 deals with the
M€
ossbauer characterization of high-valent iron intermediates in the oxidation of L-tryptophan by heme-based enzymes.
Chapter 16 is focused on the use of M€
ossbauer spectroscopy to study iron in neurodegenerative diseases.
Recent advances on studying iron and iron oxides using M€
ossbauer spectroscopy are described in Chapters 18–25.
Chapter 18 discusses the nanocrystalline iron oxides, while Chapter 19 presents perovskite-related systems where
emission M€
ossbauer spectroscopy contributes to exploring the structure and electronic or magnetic behavior of these
ossbauer spectrometry to study iron phases in rust layers is described in Chapter 20. The

materials. The use of 57 Fe M€
progress made on understanding bulk magnetic properties of nanosized powders of ferrites, mechanically alloyed/milled
Fe–Cr–Al intermetallics, and a Fe–Al multilayer system is presented in Chapter 21. The application of surface M€
ossbauer
spectroscopy to study very thin layers (a few atomic layers thick) of iron oxides is discussed in Chapter 22. Chapter 23
describes in detail the precipitation of iron oxides from aqueous iron salt solutions using M€
ossbauer spectroscopy.
Chapter 24 is focused on the spectroscopic characterization of ferrates in high-valent oxidation states (þ4, þ5, and þ6).
Chapter 25 deals with dilute iron-doped yttrium aluminum garnets.
M€
ossbauer spectroscopy of materials of industrial interest is discussed in Chapters 26–30. Chapter 26 deals with Fe–
As-based high-temperature superconductors. M€
ossbauer study of cathode active material for lithium-ion battery (LIB)
and electrically conductive vanadate glass is presented in Chapter 27. More details on the applications of M€
ossbauer
spectroscopy to LIB are given in Chapter 28. Chapter 29 is the example of applying M€
ossbauer spectroscopy to develop
novel bimetal heterogeneous catalysts for preferential CO oxidation in H2. Chapter 30 shows the successful use of
M€
ossbauer spectroscopy to identify and quantify the iron mineral phases of South African coal fractions. The last two
chapters are mainly on the applications of M€
ossbauer spectroscopy to the environmental field, for example, describing
the recycling process of iron-containing “waste” of silicate glasses, which is related to purification of polluted water
xix


xx

PREFACE

(Chapter 31). The variables control in the laterite mineral processing using M€
ossbauer spectroscopy is another example
(Chapter 32).
Finally, the editors of the book would like to acknowledge contributions by late Professor Attila Vertez, E€
otv€
os
Lorand University. In addition to studying fundamentals of M€
ossbauer spectroscopy, Attila applied the M€
ossbauer effect
to various fields. One of the coeditors, Virender K. Sharma, met Attila in fall 2002 when he was visiting Budapest under
the sustainability grant, received by Florida Tech, from the U.S. Department of States. During the visit, Attila was very
kind to accept him in his group. Since then Virender had several interactions in Budapest and on one occasion in
Melbourne, Florida. Because of the admiration for Attila, the M€
ossbauer community organized a special symposium titled
“Chemical Applications of M€
ossbauer Spectroscopy,” honoring him at the American Chemical Society Spring Meeting at
San Francisco in March 2010. In the summer 2010, Virender traveled to Budapest to present the “Salute of Excellence”
from the American Chemical Society. It was heartening to see that leading chemists from Hungary, including the
president of the chemistry division of the Hungarian Academy of Science and president of E€
otv€
os Lorand University, were
present at that occasion. Attila will always be known as a great scientist with a gentleman touch and we will miss him
dearly. This book is dedicated to late Professor Attila Vertez for his many accomplishments in M€
ossbauer spectroscopy.

VIRENDER K. SHARMA
€STAR KLINGELHo
€FER
Go
TETSUAKI NISHIDA

Contributors
Ricardo Alc
antara, Laboratorio de Quımica Inorganica, Universidad de C
ordoba, C
ordoba, Spain
Irina V. Alenkina, Faculty of Physical Techniques and Devices for Quality Control, Institute of Physics and Technology,
Ural Federal University, Ekaterinburg, Russian Federation
Ercan E. Alp, Advanced Photon Source, Argonne National Laboratory, Argonne, IL, USA
C
esar A. Barrero, Grupo de Estado S
olido, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia,
Medellın, Colombia
Erika R. Bauminger, Racah Institute of Physics, Hebrew University of Jerusalem, Jerusalem, Israel
Edward Brown, Chemistry Department, Nassau Community College, Garden City, NY
Stephen P. Cramer, Department of Applied Science, University of California-Davis, Davis, CA, USA
Juan de la Figuera, Instituto de Quımica Fısica “Rocasolano”, CSIC, Madrid, Spain
Georges D
en
es, Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec, Canada
Eamonn Devlin, Institute of Materials Science, N.C.S.R. “Demokritos”, Attiki, Athens, Greece
Kednerlin Dornevil, Department of Chemistry, Georgia State University, Atlanta, GA, USA
Andrzej Friedman, Department of Neurology, Faculty of Health Science, Medical University of Warsaw, Warsaw,
Poland
Ji9rı Frydrych, Regional Center of Advanced Technologies and Materials, Olomouc, Czech Republic
Jolanta Gała˛zka-Friedman, Faculty of Physics, Warsaw University of Technology, Warsaw, Poland
Jos
e Ram
on Gancedo, Instituto de Quımica Fısica “Rocasolano”, CSIC, Madrid, Spain

Karen E. Garcıa, Grupo de Estado S
olido, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia,
Medellın, Colombia
Jean-Marc Greneche, LUNAM, Universite du Maine, Institut des Molecules et Materiaux du Mans, Le Mans Cedex,
France
Yisong Guo, Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA, USA
Barbara R. Hillery, Chemistry Department, Nassau Community College, Garden City, NY
Yukio Hinatsu, Department of Chemistry, Hokkaido University, Sapporo, Hokkaido, Japan
Zolt
an Homonnay, Faculty of Science, Eotvos Lorand University, Budapest, Hungary
Naoki Igawa, Quantum Bean Science Directorate, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki, Japan
Jie Jin, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
Alexander A. Kamnev, Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and Microorganisms, Russian Academy of Sciences, Saratov, Russian Federation
Airat Khasanov, Department of Chemistry, University of North Carolina at Asheville, Asheville, NC, USA
Yoshio Kobayashi, Department of Engineering Science, The University of Electro-Communications, Tokyo, Japan
xxi


xxii

CONTRIBUTORS

Norimichi Kojima, Graduate School of Arts and Sciences, The University of Tokyo, Meguro-ku, Tokyo, Japan
J
ozef Korecki, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,
Karlsruhe, Germany
Alla A. Kornilova, Moscow State University, Moscow, Russia
Krisztina Kov
acs, Laboratory of Nuclear Chemistry, Institute of Chemistry, E€
otv€

os Lorand University, Budapest,
Hungary
Stjepko Krehula, Division of Materials Chemistry, Rudjer Bo9skovic Institute, Zagreb, Croatia
Shiro Kubuki, Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University,
Hachioji, Japan
Pedro Lavela, Laboratorio de Quımica Inorganica, Universidad de C
ordoba, C
ordoba, Spain
_
Jan Łazewski,
Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,
Karlsruhe, Germany
Jung-Fu Lin, Department of Geological Sciences, Jackson School of Geosciences, The University of Texas at Austin,
Austin, TX, USA
Aimin Liu, Department of Chemistry, Georgia State University, Atlanta, GA, USA
Kuo Liu, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
Libor Machala, Regional Center of Advanced Technologies and Materials, Olomouc, Czech Republic
M. Cecilia Madamba, Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec, Canada
Zhu Mao, Department of Geological Sciences, Jackson School of Geosciences, The University of Texas at Austin,
Austin, TX, USA
Jos
e F. Marco, Instituto de Quımica Fısica “Rocasolano”, CSIC, Madrid, Spain
Leopold May, Chemistry Department, Nassau Community College, Garden City, NY
Hocine Merazig, Laboratoire de Chimie Moleculaire, du Contr^
ole de l’Environnement et de Mesures PhysicoChimiques, Departement de Chimie, Faculte des Sciences, Universite Mentouri, Constantine, Algeria
Toshiyuki Misu, Department of Chemistry, Faculty of Science, Toho University, Funabashi, Chiba, Japan
Matteo Monti, Instituto de Quımica Fısica “Rocasolano”, CSIC, Madrid, Spain
Alvaro L. Morales, Grupo de Estado S
olido, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia,
Medellın, Colombia

Abdualhafed Muntasar, Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec,
Canada
Svetozar Musi
c, Division of Materials Chemistry, Rugjer Bo9skovic Institute, Zagreb, Croatia
Masami Nakada, Advanced Science Research Center, Japan Atomic Energy Agency, Ibaraki, Japan
Tadahiro Nakamoto, Department of Materials Characterization, Toray Research Center, Inc., Otsu, Shiga, Japan
Akio Nakamura, Advanced Science Research Center, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki,
Japan
Mikio Nakamura, Department of Chemistry, Faculty of Science, Toho University, Funabashi, Chiba, Japan
Satoru Nakashima, Natural Science Center for Basic Research and Development, Hiroshima University,
Higashi-Hiroshima, Japan
Lakshmi Nambakkat, Department of Physics, University College of Science, Mohanlal Sukhadia University, Udaipur,
Rajasthan, India


CONTRIBUTORS

xxiii

Amar Nath, Department of Chemistry, University of North Carolina at Asheville, Asheville, NC, USA
Zolt
an N
emeth, Faculty of Science, Eotvos Lorand University, Budapest, Hungary
Tetsuaki Nishida, Department of Biological and Environmental Chemistry, Faculty of Humanity-Oriented Science and
Engineering, Kinki University, Iizuka, Japan
Kiyoshi Nomura, School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo, Japan
Yoshihiro Okamoto, Quantum Beam Science Directorate, Japan Atomic Energy Agency, Tokai-mura, Naka-gun,
Ibaraki, Japan
Michael I. Oshtrakh, Faculty of Physical Techniques and Devices for Quality Control, Institute of Physics and
Technology, Ural Federal University, Ekaterinburg, Russian Federation

Krzysztof Parli
nski, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), EggensteinLeopoldshafen, Karlsruhe, Germany
Ji9rı Pechou9sek, Regional Center of Advanced Technologies and Materials, Olomouc, Czech Republic
Carlos P
erez Vicente, Laboratorio de Quımica Inorganica, Universidad de C
ordoba, C
ordoba, Spain
Yurii D. Perfiliev, Chemistry Department, Florida Institute of Technology, Melbourne, FL, USA
Duncan Quarless, Chemistry Department, Nassau Community College, Garden City, NY
Mira Risti
c, Division of Materials Chemistry, Rugjer Bo9skovic Institute, Zagreb, Croatia
Ralf R€
ohlsberger, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), EggensteinLeopoldshafen, Karlsruhe, Germany
Michail Samouhos, School of Mining and Metallurgical Engineering, National Technical University of Athens,
Athens, Greece
Bogdan Sepiol, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,
Karlsruhe, Germany
Virender K. Sharma, Chemistry Department, Florida Institute of Technology, Melbourne, Florida, USA
Marcel Sladecek, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), EggensteinLeopoldshafen, Karlsruhe, Germany
 ˛zak, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,
Michał Sle
Karlsruhe, Germany
 ˛zak, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,
Tomasz Sle
Karlsruhe, Germany
Sabrina G. Sobel, Chemistry Department, Nassau Community College, Garden City, NY
Nika Spiridis, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,
Karlsruhe, Germany
Svetoslav Stankov, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), EggensteinLeopoldshafen, Karlsruhe, Germany
Akira Sugahara, Graduate School of Arts and Sciences, The University of Tokyo, Meguro-ku, Tokyo, Japan

Masashi Takahashi, Department of Chemistry, Faculty of Science, Toho University, Funabashi, Chiba, Japan
Masuo Takeda, Department of Chemistry, Faculty of Science, Toho University, Funabashi, Chiba, Japan
ordoba, C
ordoba, Spain
Jos
e L. Tirado, Laboratorio de Quımica Inorganica, Universidad de C
Satoshi Tsutsui, Research and Utilization Division, SPring-8/JASRI, Sayo-cho, Sayo-gun, Hyogo, Japan; Advanced
Science Research Center, Japan Atomic Energy Agency, Ibaraki, Japan