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<p>Preface xi</p> <p><b>1 Application of Mössbauer Spectroscopy to Energy Materials 1<br /> </b><i>Pierre-Emmanuel Lippens, Jean-Claude Jumas, and Josette Olivier-Fourcade</i></p> <p>1.1 Introduction 1</p> <p>1.2 Mössbauer Spectroscopy for Li-ion and Na-ion Batteries 2</p> <p>1.2.1 Characterization of Electrode Materials and Electrochemical Reactions 2</p> <p>1.2.2 Tin-Based Negative Electrode Materials for Li-ion Batteries 3</p> <p>1.2.2.1 Electrochemical Reactions of Lithium with Tin 3</p> <p>1.2.2.2 Tin Oxides 7</p> <p>1.2.2.3 Tin Borophosphates 10</p> <p>1.2.2.4 Tin-Based Intermetallics 13</p> <p>1.2.3 Iron-Based Electrode Materials 17</p> <p>1.2.3.1 LiFePO₄ as Positive Electrode Material for Li-ion Batteries 17</p> <p>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</p> <p>1.2.3.3 Na 1.5 Fe _0.5 Ti _1.5 (PO₄) ₃ /C as Electrode Material for Na-ion Batteries 19</p> <p>1.3 Mössbauer Spectroscopy of Tin-Based Catalysts 21</p> <p>1.3.1 Reforming Catalysis 21</p> <p>1.3.2 Redox Properties of Pt-Sn Based Catalysts 22</p> <p>1.3.3 Trimetallic Pt-Sn-In Based Catalysts 24</p> <p>1.4 Conclusion 26</p> <p>Acknowledgments 27</p> <p>References 27</p> <p><b>2 Mössbauer Spectral Studies of Iron Phosphate Containing Minerals and Compounds 33<br /> </b><i>Gary J. Long and Fernande Grandjean</i></p> <p>2.1 Introduction 33</p> <p>2.2 Thermodynamic Properties of Iron Phosphate Containing Compounds 34</p> <p>2.3 Room Temperature Mössbauer Spectra of Iron Phosphate Containing Minerals 37</p> <p>2.4 Analysis of Magnetically Ordered Mössbauer Spectra 50</p> <p>2.5 Structural and Thermodynamic Properties of the Polymorphs of FePO₄ 53</p> <p>2.5.1 Polymorphs of FePO₄ 53</p> <p>2.6 Mössbauer Spectra of α-FePO₄ 55</p> <p>2.7 Magnetic Structure of α-FePO₄ , Obtained by Mössbauer Spectroscopy 57</p> <p>2.7.1 Magnetic Structure of α-FePO₄ 57</p> <p>2.8 Temperature Dependence of the α-FePO₄ Structure Tilt Angle 60</p> <p>2.9 Mössbauer Spectral Studies on Metastable Polymorphs of FePO₄ 62</p> <p>2.9.1 Crystallographic Structures of Two Polymorphs of FePO₄ ⋅2H₂ O 62</p> <p>2.9.2 Preparation and Crystallographic Structures of the Two Polymorphs, γ-FePO₄ and ζ-FePO₄ 62</p> <p>2.9.3 Mössbauer Spectral Studies of FePO₄ Metastable Polymorphs 64</p> <p>2.9.4 Preparation and Mössbauer Spectra of Synthetic Heterosite, (Fe,Mn)PO₄ 67</p> <p>2.9.5 Fits of the Magnetic Mössbauer Spectra of η-Fe _0.9 Mn _0.1 PO₄ 68</p> <p>2.10 Mössbauer Spectral Studies of Various Iron Phosphate Compounds 73</p> <p>2.10.1 Mössbauer Spectral Properties of α-Fe₂ (PO₄)O 74</p> <p>2.10.2 Mössbauer Spectral Properties of Fe₃ (PO₄)O₃ 79</p> <p>2.10.3 Preparation and Structural Properties of Fe₉ (PO₄)O₈ 80</p> <p>2.10.4 Mössbauer Spectral Properties of Fe₉ (PO₄)O₈ 81</p> <p>Acknowledgments 85</p> <p>References and Notes 85</p> <p><b>3 Mössbauer Spectroscopic Investigation of Fe-Based Silicides 93<br /> </b><i>Xiao Chen, Junhu Wang, and Changhai Liang</i></p> <p>3.1 Introduction 93</p> <p>3.2 Mössbauer Spectroscopic Investigation of Iron Silicides Prepared By Mechanical Alloying and Heat Treatment 95</p> <p>3.3 Mössbauer Spectra of Iron Silicide on Silica Prepared by Pyrolysis of Ferrocene-Polydimethylsilane Composites 99</p> <p>3.4 Synthesis and Mössbauer Spectra of Iron Silicides by Temperature-Programmed Silicification 102</p> <p>3.5 Mössbauer Spectroscopic Investigation of Doped Iron Silicides 104</p> <p>3.6 Conclusion and Perspective 107</p> <p>References 108</p> <p><b>4 Mössbauer Spectroscopy of Catalysts 113<br /> </b><i>Károly Lázár</i></p> <p>4.1 Introduction 113</p> <p>4.2 Principles of the Mössbauer Effect and Outlook of Its Application for Catalyst Studies 116</p> <p>4.2.1 Brief Overview of the Basics of Mössbauer Spectroscopy 116</p> <p>4.2.2 Mössbauer Spectroscopy from the Point of View of Catalyst Studies – Particular Features 117</p> <p>4.2.3 The Probability of the Mössbauer Effect – f-Factor and Size Effects 118</p> <p>4.2.4 Variants of the Technique 120</p> <p>4.2.4.1 ⁵⁷Co Emission Spectroscopy 120</p> <p>4.2.4.2 Synchrotron-Based NFS (Nuclear Forward Scattering) 122</p> <p>4.2.4.3 Conversion Electron Mössbauer Spectroscopy 122</p> <p>4.2.5 Technical Implementations – Experimental Conditions 123</p> <p>4.3 Heterogeneous Catalysts 124</p> <p>4.3.1 Sites on Supported Particles with Different Participation in Catalytic Processes 124</p> <p>4.3.2 Collective Effects in Particles (Magnetism) 125</p> <p>4.3.3 Case Studies 126</p> <p>4.3.3.1 Metals and Alloys 126</p> <p>4.3.3.2 Oxide Catalysts 130</p> <p>4.3.3.3 Catalysts with Fe–N, Fe–C, and Fe–N–C Centers 133</p> <p>4.4 Biocatalysts – Enzymes 135</p> <p>4.5 Homogeneous Catalysts – Frozen Solutions 135</p> <p>4.5.1 Studies on Reaction Intermediates – Time-Resolved Freeze-Quenched Spectra 136</p> <p>4.6 Conclusions 137</p> <p>Acknowledgment 137</p> <p>References 138</p> <p><b>5 Application of Mössbauer Spectroscopy in Studying Catalysts for CO Oxidation and Preferential Oxidation of CO in H₂<br /> <i>145<br /> </i></b><i>Kuo Liu, Junhu Wang, and Tao Zhang</i></p> <p>5.1 Introduction 145</p> <p>5.2 Application of Mössbauer Spectroscopy in CO Oxidation 147</p> <p>5.2.1 ⁵⁷ Fe Mössbauer Spectroscopy 147</p> <p>5.2.2 ¹¹⁹ Sn Mössbauer Spectroscopy 150</p> <p>5.2.3 ¹⁹⁷ Au Mössbauer Spectroscopy 151</p> <p>5.2.4 ¹⁹³ Ir Mössbauer spectroscopy 152</p> <p>5.3 Application of Mössbauer Spectroscopy in PROX 153</p> <p>5.3.1 PtFe-Containing Catalysts 153</p> <p>5.3.2 Au-Based Catalysts 155</p> <p>5.3.3 IrFe-Containing Catalysts 158</p> <p>5.3.3.1 Porous Carbon Supported IrFe Catalysts 158</p> <p>5.3.3.2 SiO₂ and Al₂ O₃ Supported IrFe Catalysts 159</p> <p>5.3.4 CuO/CeO₂ with Fe₂O₃ Additive 165</p> <p>5.4 Concluding Remarks 165</p> <p>Acknowledgments 166</p> <p>References 166</p> <p><b>6 Application of ⁵⁷ Fe Mössbauer Spectroscopy in Studying Fe–N–C Catalysts for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells 171<br /> </b><i>Xinlong Xu, Junhu Wang, Suli Wang, and Gongquan Sun</i></p> <p>6.1 Introduction 171</p> <p>6.2 Advanced ⁵⁷Fe Mössbauer Spectroscopy Technique 173</p> <p>6.2.1 Room Temperature ⁵⁷Fe Mössbauer Spectroscopy 173</p> <p>6.2.2 Low Temperature and Computational ⁵⁷Fe Mössbauer Spectroscopy 174</p> <p>6.2.3 In Situ Electrochemical ⁵⁷Fe Mössbauer Spectroscopy 175</p> <p>6.3 Characterization of Fe–N–C Using ⁵⁷Fe Mössbauer Spectroscopy 177</p> <p>6.3.1 Identification of Active Sites 177</p> <p>6.3.2 Investigation of Degradation Mechanism 180</p> <p>6.3.3 Optimization for Synthesis of Fe–N–C 184</p> <p>6.3.3.1 Precursor Composition 184</p> <p>6.3.3.2 Heat Treatment 185</p> <p>6.4 Summary and Perspective 187</p> <p>Acknowledgments 188</p> <p>References 188</p> <p><b>7 ¹⁹⁷ Au Mössbauer Spectroscopy of Thiolate-protected Gold Clusters 195<br /> </b><i>Norimichi Kojima, Yasuhiro Kobaqyashi, and Makoto Seto</i></p> <p>7.1 Introduction 195</p> <p>7.2 Synthesis of Thiolate Protected Gold Clusters 197</p> <p>7.3 197 Au Mössbauer Spectroscopy of Gold Nano-clusters 198</p> <p>7.3.1 Experimental Procedure of ¹⁹⁷ Au Mössbauer Spectroscopy 198</p> <p>7.3.2 197 Au Mössbauer Spectra of Au_n (SG)_m(n = 10∼55) 198</p> <p>7.3.3 Molecular Structure and ¹⁹⁷ Au Mössbauer Spectra of Au₁₀ (SG)₁₀ 198</p> <p>7.3.4 Molecular Structure and ¹⁹⁷ Au Mössbauer Spectra of Au₂₅ (SG)₁₈ 200</p> <p>7.3.5 Structural Evolution of Au_n (SG)_m(n = 10∼55) Based on ¹⁹⁷Au Mössbauer Spectroscopy 201</p> <p>7.3.6 197 Au Mössbauer Spectra of Au₂₄ Pd₁ (SC₁₂ H₂₅)₁₈ 204</p> <p>7.3.7 197 Au Mössbauer Spectra of Au_n (SC₁₂ H₂₅)_m 205</p> <p>7.4 Conclusion 208</p> <p>Acknowledgments 208</p> <p>References 209</p> <p><b>8 ¹⁹⁷ Au Mössbauer Spectroscopy of Gold Mixed-Valence Complexes, Cs₂ [Au^I X₂ ][Au^III Y₄ ](X, Y = Cl, Br, I) and [NH₃ (CH₂)_n NH₃ ]₂[(Au^I I₂)(Au^III I₄)(I₃)₂](n= 7, 8) 213<br /> </b><i>Norimichi Kojima, Yasuhiro Kobaqyashi, and Makoto Seto</i></p> <p>8.1 Introduction 213</p> <p>8.2 Experimental Procedure 216</p> <p>8.2.1 Synthesis and Characterization 216</p> <p>8.2.1.1 Cs₂ [Au^I X₂][Au^IIIY₄ ](X,Y= Cl, Br, I) 216</p> <p>8.2.1.2 [NH₃ (CH₂)_n NH₃ ]₂ [(Au^II₂)(Au^III I₄)(I₃)₂ ](n= 7, 8) 217</p> <p>8.2.2 197 Au Mössbauer Spectroscopy 217</p> <p>8.3 Crystal Structure of Cs₂ [Au^I X₂][ Au^III X₄](X,Y= Cl, Br, I) 218</p> <p>8.4 Chemical Bond of Au−Xin[Au^I X₂] − and [Au^III X₄] − 221</p> <p>8.5 Mössbauer Parameters of ¹⁹⁷ Au in [Au^I X₂] − and [Au^III X₄ ] − 223</p> <p>8.5.1 Mössbauer Parameters of ¹⁹⁷ Au in (C₄ H₉)₄ N[Au^I X₂] and (C₄ H₉)₄ N[Au^III Y₄] 224</p> <p>8.5.1.1 Isomer Shift 224</p> <p>8.5.1.2 Quadrupole Splitting 224</p> <p>8.5.2 Mössbauer Parameters of ¹⁹⁷ Au in Cs₂ [Au^I X₂] [ Au^III Y₄] (X = Cl, Br, I) 225</p> <p>8.5.2.1 Isomer Shift 225</p> <p>8.5.2.2 Quadrupole Splitting 226</p> <p>8.5.2.3 Analysis of ¹⁹⁷ Au Mössbauer Parameters for Cs₂ [Au^I X₂] [ Au^III Y₄] 226</p> <p>8.6 Charge Transfer Interaction in Cs₂ [Au^I X₂] [ Au^III Y₄](X= Cl, Br, I) 227</p> <p>8.7 ¹⁹⁷ Au Mössbauer Spectra of Cs₂ [Au^I X₂] [ Au^III Y₄](X,Y= Cl, Br, I) 228</p> <p>8.7.1 Isomer Shift of Au^I in Cs₂ [Au^I X₂] [ Au^III Y₄] 228</p> <p>8.7.2 Isomer Shift of Au^III in Cs₂ [Au^I X₂] [ Au^III Y₄] 230</p> <p>8.7.3 Quadrupole Splitting of Au^I in Cs₂ [Au^I X₂ ] [Au^III Y₄ ] 230</p> <p>8.7.4 Quadrupole Splitting of Au^III in Cs₂ [Au^I X₂] [Au^III Y₄ ] 231</p> <p>8.8 Single Crystal ¹⁹⁷ Au Mössbauer Spectra of Cs₂ [Au^I I₂ ] [Au^III I₄ ] 231</p> <p>8.8.1 Comparison of ¹⁹⁷ Au Mössbauer Spectra Between Single Crystal and Powder Crystal 231</p> <p>8.8.2 Sign of EFG for Au^I in [Au^I I₂ ] − and Au^IIIin [Au^III X₄] − 234</p> <p>8.9 ¹⁹⁷ Au Mössbauer Spectra of Cs₂ [Au^I X ₂ ] [Au^III X₄ ](X= Cl, I) Under High Pressures 235</p> <p>8.9.1 Phase Diagram of Cs₂ [Au^I X₂ ] [Au^III X₄ ](X= Cl, Br, I) 235</p> <p>8.9.2 Origin of Metallic Mixed-Valence State in Cs₂ [Au^I Cl² ] [Au^III Cl₄ ] 236</p> <p>8.9.3 Au Valence Transition in Cs₂ [Au ^II₂ ] [Au^III I₄ ] 239</p> <p>8.10 ¹⁹⁷ Au Mössbauer Spectra of [NH₃ (CH₂)_n NH₃ ]₂ [(Au ^II₂)(Au^III I₄)(I₃)₂ ] (n = 7, 8) 241</p> <p>8.11 Conclusion 243</p> <p>Acknowledgments 244  </p> <p>References 245</p> <p><b>9 Temperature- and Photo-Induced Spin-Crossover in Molecule-Based Magnets 251<br /> </b><i>Hiroko Tokoro, Kenta Imoto, and Shin-ichi Ohkoshi</i></p> <p>9.1 Introduction 251</p> <p>9.2 Spin-Crossover Phenomena in Cesium Iron Hexacyanidochromate Prussian Blue Analog 252</p> <p>9.3 Light-Induced Spin-Crossover Magnet in Iron Octacyanidoniobate Bimetal Assembly 254</p> <p>9.4 Chiral Photomagnetism and Light-Controllable Second Harmonic Light in Iron Octacyanidoniobate Bimetal Assembly 258</p> <p>9.5 Conclusion and Perspective 265</p> <p>References 265</p> <p><b>10 Developing a Methodology to Obtain New Photoswitchable Fe(II) Spin Crossover Complexes 271<br /> </b><i>Varun Kumar and Yann Garcia</i></p> <p>10.1 Introduction and Context 271</p> <p>10.2 Introduction to a New Photo-responsive Anion: psca 275</p> <p>10.3 Combining Fe(II) and psca Together in a Single Compound 276</p> <p>10.4 Fe(II) Mononuclear Complexes with DMPP and psca Ligands 278</p> <p>10.5 1D Fe(II) Coordination Polymer with psca as Non-Coordinated Anions 281</p> <p>10.6 Conclusions and Perspectives 284</p> <p>References 285</p> <p><b>11 ⁵⁷ Fe Mössbauer Spectroscopy as a Prime Tool to Explore a New Family of Colorimetric Sensors 291<br /> </b><i>li Sun, Weiyang li, and Yann Garcia</i></p> <p>11.1 Introduction and General Context 291</p> <p>11.2 Colorimetric Gas Sensors Based on Fe(II) Complexes 292</p> <p>11.3 Conclusions and Perspectives 306</p> <p>References 306</p> <p>Index 311</p>

<p><b>Yann Garcia</b> is Professor of Analytical Chemistry at UCLouvain, IBAME vice-chair and GFSM president.</p> <p><b>Junhu Wang</b> is Professor & Group Leader at Dalian Institute of Chemical Physics, Chinese Academy of Sciences and Secretary General of Mössbauer Effect Data Center.</p> <p><b>Tao Zhang</b> is Vice President at the Chinese Academy of Sciences and Director of Mössbauer Effect Data Center.</p>

<p><b>Unique and comprehensive overview of versatile applications of Mössbauer spectroscopy in chemistry and material sciences</b> <p><i>Mössbauer Spectroscopy</i> provides a comprehensive overview of relevant applications of this physical analysis method in chemistry and material sciences. <p>The book shows the versatility of Mössbauer spectroscopy in finding useful information on electronic structure, structural insights, and solid-state effects of chemical systems. A wide range of chemical applications and applied concepts are covered as well as numerous examples, selected from recent literature. <p>To aid in reader comprehension and accessibility, contents are well-structured and divided in different sections covering energy, catalysis, coordination chemistry, spin crossover, sensing, photomagnetism. <p>Edited by prominent scientists in the field and authored by a group of international experts, <i>Mössbauer Spectroscopy</i> covers sample topics such as: <ul><li>Li-ion batteries, catalysts, fuel cells, Fe based silicides and iron phosphates containing minerals</li> <li>Gold clusters and gold mixed valence complexes</li> <li>Molecule based magnets, photoswitchable spin crossover coordination polymers and molecular sensors for meat freshness control</li></ul> <p>With comprehensive coverage of the developments in the technique, <i>Mössbauer Spectroscopy</i> is a beneficial resource for researchers, professionals, and academics in chemistry related fields, such as material science, sustainable environment, and molecular electronics. It can be used by newcomers as well as for educational purposes at the master and PhD levels.

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