Preface xi
1 Application of Mossbauer Spectroscopy to Energy Materials 1
Pierre-Emmanuel Lippens, Jean-Claude Jumas, and Josette Olivier-Fourcade
1.1 Introduction 1
1.2 Mossbauer Spectroscopy for Li-ion and Na-ion Batteries 2
1.2.1 Characterization of Electrode Materials and Electrochemical Reactions 2
1.2.2 Tin-Based Negative Electrode Materials for Li-ion Batteries 3
1.2.2.1 Electrochemical Reactions of Lithium with Tin 3
1.2.2.2 Tin Oxides 7
1.2.2.3 Tin Borophosphates 10
1.2.2.4 Tin-Based Intermetallics 13
1.2.3 Iron-Based Electrode Materials 17
1.2.3.1 LiFePO4 as Positive Electrode Material for Li-ion Batteries 17
1.2.3.2 Fe 1.19 PO4 (OH) 0.57 (H2 O) 0.43 /C as Positive Electrode Material for Li-ion Batteries 18
1.2.3.3 Na 1.5 Fe 0.5 Ti 1.5 (PO4) 3 /C as Electrode Material for Na-ion Batteries 19
1.3 Mossbauer Spectroscopy of Tin-Based Catalysts 21
1.3.1 Reforming Catalysis 21
1.3.2 Redox Properties of Pt-Sn Based Catalysts 22
1.3.3 Trimetallic Pt-Sn-In Based Catalysts 24
1.4 Conclusion 26
Acknowledgments 27
References 27
2 Mossbauer Spectral Studies of Iron Phosphate Containing Minerals and Compounds 33
Gary J. Long and Fernande Grandjean
2.1 Introduction 33
2.2 Thermodynamic Properties of Iron Phosphate Containing Compounds 34
2.3 Room Temperature Mossbauer Spectra of Iron Phosphate Containing Minerals 37
2.4 Analysis of Magnetically Ordered Mossbauer Spectra 50
2.5 Structural and Thermodynamic Properties of the Polymorphs of FePO4 53
2.5.1 Polymorphs of FePO4 53
2.6 Mossbauer Spectra of α-FePO4 55
2.7 Magnetic Structure of α-FePO4 , Obtained by Mossbauer Spectroscopy 57
2.7.1 Magnetic Structure of α-FePO4 57
2.8 Temperature Dependence of the α-FePO4 Structure Tilt Angle 60
2.9 Mossbauer Spectral Studies on Metastable Polymorphs of FePO4 62
2.9.1 Crystallographic Structures of Two Polymorphs of FePO4 ⋅2H2 O 62
2.9.2 Preparation and Crystallographic Structures of the Two Polymorphs, γ-FePO4 and ζ-FePO4 62
2.9.3 Mossbauer Spectral Studies of FePO4 Metastable Polymorphs 64
2.9.4 Preparation and Mossbauer Spectra of Synthetic Heterosite, (Fe,Mn)PO4 67
2.9.5 Fits of the Magnetic Mossbauer Spectra of η-Fe 0.9 Mn 0.1 PO4 68
2.10 Mossbauer Spectral Studies of Various Iron Phosphate Compounds 73
2.10.1 Mossbauer Spectral Properties of α-Fe2 (PO4)O 74
2.10.2 Mossbauer Spectral Properties of Fe3 (PO4)O3 79
2.10.3 Preparation and Structural Properties of Fe9 (PO4)O8 80
2.10.4 Mossbauer Spectral Properties of Fe9 (PO4)O8 81
Acknowledgments 85
References and Notes 85
3 Mossbauer Spectroscopic Investigation of Fe-Based Silicides 93
Xiao Chen, Junhu Wang, and Changhai Liang
3.1 Introduction 93
3.2 Mossbauer Spectroscopic Investigation of Iron Silicides Prepared By Mechanical Alloying and Heat Treatment 95
3.3 Mossbauer Spectra of Iron Silicide on Silica Prepared by Pyrolysis of Ferrocene-Polydimethylsilane Composites 99
3.4 Synthesis and Mossbauer Spectra of Iron Silicides by Temperature-Programmed Silicification 102
3.5 Mossbauer Spectroscopic Investigation of Doped Iron Silicides 104
3.6 Conclusion and Perspective 107
References 108
4 Mossbauer Spectroscopy of Catalysts 113
Karoly Lazar
4.1 Introduction 113
4.2 Principles of the Mossbauer Effect and Outlook of Its Application for Catalyst Studies 116
4.2.1 Brief Overview of the Basics of Mossbauer Spectroscopy 116
4.2.2 Mossbauer Spectroscopy from the Point of View of Catalyst Studies – Particular Features 117
4.2.3 The Probability of the Mossbauer Effect – f-Factor and Size Effects 118
4.2.4 Variants of the Technique 120
4.2.4.1 57Co Emission Spectroscopy 120
4.2.4.2 Synchrotron-Based NFS (Nuclear Forward Scattering) 122
4.2.4.3 Conversion Electron Mossbauer Spectroscopy 122
4.2.5 Technical Implementations – Experimental Conditions 123
4.3 Heterogeneous Catalysts 124
4.3.1 Sites on Supported Particles with Different Participation in Catalytic Processes 124
4.3.2 Collective Effects in Particles (Magnetism) 125
4.3.3 Case Studies 126
4.3.3.1 Metals and Alloys 126
4.3.3.2 Oxide Catalysts 130
4.3.3.3 Catalysts with Fe–N, Fe–C, and Fe–N–C Centers 133
4.4 Biocatalysts – Enzymes 135
4.5 Homogeneous Catalysts – Frozen Solutions 135
4.5.1 Studies on Reaction Intermediates – Time-Resolved Freeze-Quenched Spectra 136
4.6 Conclusions 137
Acknowledgment 137
References 138
5 Application of Mossbauer Spectroscopy in Studying Catalysts for CO Oxidation and Preferential Oxidation of CO in H2
145
Kuo Liu, Junhu Wang, and Tao Zhang
5.1 Introduction 145
5.2 Application of Mossbauer Spectroscopy in CO Oxidation 147
5.2.1 57 Fe Mossbauer Spectroscopy 147
5.2.2 119 Sn Mossbauer Spectroscopy 150
5.2.3 197 Au Mossbauer Spectroscopy 151
5.2.4 193 Ir Mossbauer spectroscopy 152
5.3 Application of Mossbauer Spectroscopy in PROX 153
5.3.1 PtFe-Containing Catalysts 153
5.3.2 Au-Based Catalysts 155
5.3.3 IrFe-Containing Catalysts 158
5.3.3.1 Porous Carbon Supported IrFe Catalysts 158
5.3.3.2 SiO2 and Al2 O3 Supported IrFe Catalysts 159
5.3.4 CuO/CeO2 with Fe2 O3 Additive 165
5.4 Concluding Remarks 165
Acknowledgments 166
References 166
6 Application of 57 Fe Mossbauer Spectroscopy in Studying Fe–N–C Catalysts for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells 171
Xinlong Xu, Junhu Wang, Suli Wang, and Gongquan Sun
6.1 Introduction 171
6.2 Advanced 57Fe Mossbauer Spectroscopy Technique 173
6.2.1 Room Temperature 57Fe Mossbauer Spectroscopy 173
6.2.2 Low Temperature and Computational 57Fe Mossbauer Spectroscopy 174
6.2.3 In Situ Electrochemical 57Fe Mossbauer Spectroscopy 175
6.3 Characterization of Fe–N–C Using 57Fe Mossbauer Spectroscopy 177
6.3.1 Identification of Active Sites 177
6.3.2 Investigation of Degradation Mechanism 180
6.3.3 Optimization for Synthesis of Fe–N–C 184
6.3.3.1 Precursor Composition 184
6.3.3.2 Heat Treatment 185
6.4 Summary and Perspective 187
Acknowledgments 188
References 188
7 197 Au Mossbauer Spectroscopy of Thiolate-protected Gold Clusters 195
Norimichi Kojima, Yasuhiro Kobaqyashi, and Makoto Seto
7.1 Introduction 195
7.2 Synthesis of Thiolate Protected Gold Clusters 197
7.3 197 Au Mossbauer Spectroscopy of Gold Nano-clusters 198
7.3.1 Experimental Procedure of 197 Au Mossbauer Spectroscopy 198
7.3.2 197 Au Mossbauer Spectra of Aun (SG)m(n = 10∼55) 198
7.3.3 Molecular Structure and 197 Au Mossbauer Spectra of Au10 (SG)10 198
7.3.4 Molecular Structure and 197 Au Mossbauer Spectra of Au25 (SG)18 200
7.3.5 Structural Evolution of Aun (SG)m(n = 10∼55) Based on 197 Au Mossbauer Spectroscopy 201
7.3.6 197 Au Mossbauer Spectra of Au24 Pd1 (SC12 H25)18 204
7.3.7 197 Au Mossbauer Spectra of Aun (SC12 H25)m 205
7.4 Conclusion 208
Acknowledgments 208
References 209
8 197 Au Mossbauer Spectroscopy of Gold Mixed-Valence Complexes, Cs2 [AuI X2 ][AuIII Y4 ](X, Y = Cl, Br, I) and [NH3 (CH2)n NH3 ]2[(AuI I2)(AuIII I4)(I3)2](n= 7, 8) 213
Norimichi Kojima, Yasuhiro Kobaqyashi, and Makoto Seto
8.1 Introduction 213
8.2 Experimental Procedure 216
8.2.1 Synthesis and Characterization 216
8.2.1.1 Cs2 [AuI X2][AuIII Y4 ](X,Y= Cl, Br, I) 216
8.2.1.2 [NH3 (CH2)n NH3 ]2 [(AuI I2)(AuIII I4)(I3)2 ](n= 7, 8) 217
8.2.2 197 Au Mossbauer Spectroscopy 217
8.3 Crystal Structure of Cs2 [AuI X2][ AuIII X4](X,Y= Cl, Br, I) 218
8.4 Chemical Bond of Au−Xin[AuI X2] − and [AuIII X4] − 221
8.5 Mossbauer Parameters of 197 Au in [AuI X2] − and [AuIII X4 ] − 223
8.5.1 Mossbauer Parameters of 197 Au in (C4 H9)4 N[AuI X2] and (C4 H9)4 N[AuIII Y4] 224
8.5.1.1 Isomer Shift 224
8.5.1.2 Quadrupole Splitting 224
8.5.2 Mossbauer Parameters of 197 Au in Cs2 [AuI X2] [ AuIII Y4] (X = Cl, Br, I) 225
8.5.2.1 Isomer Shift 225
8.5.2.2 Quadrupole Splitting 226
8.5.2.3 Analysis of 197 Au Mossbauer Parameters for Cs2 [AuI X2] [ AuIII Y4] 226
8.6 Charge Transfer Interaction in Cs2 [AuI X2] [ AuIII Y4](X= Cl, Br, I) 227
8.7 197 Au Mossbauer Spectra of Cs2 [AuI X2] [ AuIII Y4](X,Y= Cl, Br, I) 228
8.7.1 Isomer Shift of AuI in Cs2 [AuI X2] [ AuIII Y4] 228
8.7.2 Isomer Shift of AuIII in Cs2 [AuI X2] [ AuIII Y4] 230
8.7.3 Quadrupole Splitting of AuI in Cs2 [AuI X2 ] [AuIII Y4 ] 230
8.7.4 Quadrupole Splitting of AuIII in Cs2 [AuI X2] [AuIII Y4 ] 231
8.8 Single Crystal 197 Au Mossbauer Spectra of Cs2 [AuI I2 ] [AuIII I4 ] 231
8.8.1 Comparison of 197 Au Mossbauer Spectra Between Single Crystal and Powder Crystal 231
8.8.2 Sign of EFG for AuI in [AuI I2 ] − and AuIII in [AuIII X4 ] − 234
8.9 197 Au Mossbauer Spectra of Cs2 [AuI X 2 ] [AuIII X4 ](X= Cl, I) Under High Pressures 235
8.9.1 Phase Diagram of Cs2 [AuI X2 ] [AuIII X4 ](X= Cl, Br, I) 235
8.9.2 Origin of Metallic Mixed-Valence State in Cs2 [AuI Cl2 ] [AuIII Cl4 ] 236
8.9.3 Au Valence Transition in Cs2 [Au II2 ] [AuIII I4 ] 239
8.10 197 Au Mossbauer Spectra of [NH3 (CH2)n NH3 ]2 [(Au II2)(AuIII I4)(I3)2 ] (n = 7, 8) 241
8.11 Conclusion 243
Acknowledgments 244
References 245
9 Temperature- and Photo-Induced Spin-Crossover in Molecule-Based Magnets 251
Hiroko Tokoro, Kenta Imoto, and Shin-ichi Ohkoshi
9.1 Introduction 251
9.2 Spin-Crossover Phenomena in Cesium Iron Hexacyanidochromate Prussian Blue Analog 252
9.3 Light-Induced Spin-Crossover Magnet in Iron Octacyanidoniobate Bimetal Assembly 254
9.4 Chiral Photomagnetism and Light-Controllable Second Harmonic Light in Iron Octacyanidoniobate Bimetal Assembly 258
9.5 Conclusion and Perspective 265
References 265
10 Developing a Methodology to Obtain New Photoswitchable Fe(II) Spin Crossover Complexes 271
Varun Kumar and Yann Garcia
10.1 Introduction and Context 271
10.2 Introduction to a New Photo-responsive Anion: psca 275
10.3 Combining Fe(II) and psca Together in a Single Compound 276
10.4 Fe(II) Mononuclear Complexes with DMPP and psca Ligands 278
10.5 1D Fe(II) Coordination Polymer with psca as Non-Coordinated Anions 281
10.6 Conclusions and Perspectives 284
References 285
11 57 Fe Mossbauer Spectroscopy as a Prime Tool to Explore a New Family of Colorimetric Sensors 291
li Sun, Weiyang li, and Yann Garcia
11.1 Introduction and General Context 291
11.2 Colorimetric Gas Sensors Based on Fe(II) Complexes 292
11.3 Conclusions and Perspectives 306
References 306
Index 311
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