Kroto / Laureate / Cataldo Fulleranes

The Hydrogenated Fullerenes
1. Auflage 2010
ISBN: 978-1-4020-9887-1
Verlag: Springer-Verlag
Format: PDF
Kopierschutz: Wasserzeichen (»Systemvoraussetzungen)

E-Book, Englisch, 350 Seiten

Fulleranes are a special class of carbon molecules derived from fullerenes whose double bonds are partially or at least theoretically fully saturated by hydrogen. The hydrogenation changes the chemical properties of fullerenes which can become susceptible to substitution reactions as opposed to addition reactions to the double bonds (present in common fullerenes). One of the most intriguing aspects of fulleranes is the fact that they have been thought to exist in the interstellar medium or even in certain circumstellar media. 'Fulleranes: The Hydrogenated Fullerenes' presents the state of the art research, synthesis and properties of these molecules.This book also includes astrophysicists' and astrochemists' expectations regarding the presence of these molecules in space.

Autoren/Hrsg.

Kroto, Harry

Laureate, Nobel

Cataldo, Franco

Iglesias-Groth, Susana

Inhaltsverzeichnis

1;Foreword;6
2;Preface;9
3;Contents;12
4;Chapter 1;14
4.1;Fulleranes and Carbon Nanostructures in the Interstellar Medium;14
4.1.1;1.1 Introduction;15
4.1.2;1.2 General Properties of Fullerenes;16
4.1.2.1;1.2.1 Icosahedric Fullerenes;16
4.1.2.1.1;1.2.1.1 Photoabsorption Spectra;16
4.1.2.2;1.2.2 Fullerenes with Multiple Spheric Layers: Buckyonions;18
4.1.2.3;1.2.3 Fulleranes: Hydrogenated Fullerenes;20
4.1.3;1.3 Formation of Fullerenes and Fulleranes in Astrophysical Environments;20
4.1.3.1;1.3.1 Meteorites;20
4.1.3.2;1.3.2 Carbon Stars and Planetary Nebulae;21
4.1.3.3;1.3.3 Formation of Fullerenes and Buckyonions;22
4.1.4;1.4 Fullerenes in the Interstellar Medium;23
4.1.4.1;1.4.1 Interstellar Extintion and the UV Bump;23
4.1.4.2;1.4.2 Theoretical Spectra and the 2,175 Å Band;24
4.1.4.3;1.4.3 Carbon Fraction in Fullerenes and Buckyonions;25
4.1.4.4;1.4.4 Diffuse Interstellar Bands;26
4.1.4.5;1.4.5 The Hydrogenation of Fullerenes in the Interstellar Medium;30
4.1.5;1.5 Anomalous Microwave Emission and Hydrogenated Fullerenes;31
4.1.5.1;1.5.1 Electric Dipole and Inertia Moment of Fulleranes;31
4.1.5.2;1.5.2 Rotation and Electric Dipole Emisivity from Fulleranes;32
4.1.5.3;1.5.3 Electric Dipole Emissivity from Fulleranes;34
4.1.6;1.6 Conclusions;36
4.2;References;36
5;Chapter 2;39
5.1;Infrared and Ultraviolet Spectra of Fulleranes: HREELS Studies and Implications for the Interstellar Medium;39
5.1.1;2.1 Introduction;39
5.1.2;2.2 The Unidentified Infrared Emission Problem;40
5.1.3;2.3 The Ultraviolet Extinction Curve;41
5.1.4;2.4 Experimental Procedures;41
5.1.5;2.5 Results;42
5.1.5.1;2.5.1 Infrared Spectra;42
5.1.5.2;2.5.2 Ultraviolet Spectra;44
5.1.6;2.6 Conclusions;48
5.2;References;48
6;Chapter 3;50
6.1;The Potential Role Played by the Fullerene-Like Structures of Interstellar Carbon Dust in the Formation of Molecular Hydrogen;50
6.1.1;3.1 General Aspects About Molecular Hydrogen Formation in the Interstellar Medium;50
6.1.2;3.2 Surfaces Involved in the Synthesis of Molecular Hydrogen in the Interstellar Medium;52
6.1.3;3.3 Carbon Surfaces and Molecular Hydrogen Formation;54
6.1.4;3.4 Fullerene-Like Structures on Carbon Dust of the Interstellar Medium: Their Role in Molecular Hydrogen Formation;55
6.1.5;3.5 On the Reversibility of Hydrogen Chemisorption and Release from Fulleranes;60
6.1.6;3.6 Thermal Decomposition of C70H38 and Formation of C70;61
6.1.7;3.7 Conclusions;63
6.2;References;63
7;Chapter 4;65
7.1;Thermodynamic Properties of Fullerene Hydrides C60H2n and Equilibria of Their Reactions;65
7.1.1;4.1 Introduction;65
7.1.2;4.2 Isomerism of C60H2n Fullerene Hydrides;67
7.1.2.1;4.2.1 Isomeric Composition of C60H2;67
7.1.2.2;4.2.2 Isomeric Composition of C60.H4;67
7.1.2.3;4.2.3 Isomeric Composition of C60.H6;68
7.1.2.4;4.2.4 Isomeric Composition of C60.H18;69
7.1.2.5;4.2.5 Isomeric Composition of C60.H36;70
7.1.2.6;4.2.6 Isomeric Composition of C60.H60;71
7.1.3;4.3 Experimental Investigation of Thermodynamic Properties for C60H2n;72
7.1.4;4.4 Thermodynamic Properties of C60H2n in the Ideal-Gas State;73
7.1.4.1;4.4.1 Quantum-Chemical Calculations of Molecular Parameters for C60.H2n;74
7.1.4.2;4.4.2 Thermodynamic Properties of C60H2n in the Ideal-Gas State;77
7.1.4.3;4.4.3 Calculation of .f..Hom for C60H2n in the Ideal-Gas State;77
7.1.4.4;4.4.4 Thermodynamics of Hydrogenation Reactions for Hydrocarbons and Fullerene C60 in the Gas State;80
7.1.5;4.5 Thermodynamic Properties of C60H2n Crystals;81
7.1.5.1;4.5.1 Heat Capacity and Derived Thermodynamic Properties of C60.H2n Crystals;81
7.1.5.2;4.5.2 Formation and Sublimation Enthalpies for C60H2n Crystals;84
7.1.6;4.6 Equilibria of Reactions of C60H2n Hydrides;85
7.1.6.1;4.6.1 Gas-Phase Hydrogenation C60 + nH2 = C60H2n;85
7.1.6.2;4.6.2 Hydrogenation C60(cr)+ nH2(g) = C60H2n(cr);86
7.1.6.3;4.6.3 Hydrogenation with DHA;89
7.1.6.4;4.6.4 Is It Possible to Synthesize C60.H60?;90
7.1.7;4.7 Conclusion;91
7.2;References;92
8;Chapter 5;94
8.1;Fulleranes by Direct Reaction with Hydrogen Gas at Elevated Conditions;94
8.1.1;5.1 Introduction;94
8.1.2;5.2 Hydrogenation of Fullerenes by Hydrogen Gas: Conditions and Characterization of Products;96
8.1.3;5.3 Mass Spectrometric Characterization of Complex Fullerane Mixtures;102
8.1.4;5.4 High Pressure (GPa) Methods of Fullerane Synthesis;105
8.1.5;5.5 Future Outlook;108
8.1.5.1;5.5.1 Fulleranes with Composition C60Hx and Number of Hydrogen atoms X Below 60;108
8.1.5.2;5.5.2 Fragmented Fullerenes, e.g. C59Hx, C58Hx etc.;109
8.1.5.3;5.5.3 Fullerene Fragments;109
8.1.5.4;5.5.4 Hydrogenation of Peapods;109
8.2;References;110
9;Chapter 6;113
9.1;Chemical Methods to Prepare [60]Fulleranes;113
9.1.1;6.1 Introduction;114
9.1.2;6.2 C60H2;114
9.1.3;6.3 [60]Fulleranes with More Than 2 But Less Than 18 Hydrogens: C60H236;129
9.1.7;6.7 Conclusion;130
9.1.8;6.8 Author Biographies;131
9.2;References;131
10;Chapter 7;134
10.1;Synthesis, Stability and Spectroscopy of Perdeuterofulleranes: C60D36 and C70D38;134
10.1.1;7.1 Introduction;134
10.1.2;7.2 Experimental;135
10.1.2.1;7.2.1 Materials and Equipment;135
10.1.2.2;7.2.2 Synthesis of C60H38 in n-Hexane;136
10.1.2.3;7.2.3 Synthesis of C70H38 in n-Hexane;136
10.1.2.4;7.2.4 Synthesis of Perdeuterofullerane;136
10.1.2.5;7.2.5 Synthesis of C70H38 in Toluene;137
10.1.2.6;7.2.6 Synthesis of C70H38 in Benzene;137
10.1.2.7;7.2.7 Synthesis of C70.D38 in Toluene;137
10.1.3;7.3 Results and Discussion;138
10.1.3.1;7.3.1 Electronic Absorption Spectra of C60.H36 and C60.D36;138
10.1.3.2;7.3.2 The Electronic Absorption Spectra of Fulleranes C70.H38 and C70D38;139
10.1.3.3;7.3.3 Aspects on Deuteration: the Isotope Effect;141
10.1.3.4;7.3.4 FT-IR Spectroscopy of C60.D36 and C60.H36;142
10.1.3.5;7.3.5 FT-IR Spectroscopy of C70.D38 and C70.H38;144
10.1.3.6;7.3.6 Thermal Analysis (TGA, DTG and DTA) of C60.D36 and C60.H36;146
10.1.3.7;7.3.7 Thermal Stability of C70D38 in Comparison to C70H38;148
10.1.3.8;7.3.8 Stability of C60D36 Exposed to Air at Room Temperature;150
10.1.3.9;7.3.9 Oxidation Stability of C70D38 and C70H38;152
10.2;References;154
11;Chapter 8;156
11.1;Isotope Effect in the UV Photolysis of Hydrogenated and Perdeuterated Fulleranes;156
11.1.1;8.1 Introduction;157
11.1.2;8.2 Experimental;158
11.1.2.1;8.2.1 Reagents and Equipment;158
11.1.2.2;8.2.2 Photolysis of C60H36;159
11.1.2.3;8.2.3 Photolysis of C60D36;160
11.1.2.4;8.2.4 Photolysis of C70H38;160
11.1.2.5;8.2.5 Photolysis of C70D38;160
11.1.2.6;8.2.6 Preparation of C60H18 in n-Hexane and Subsequent Photolysis Under He;161
11.1.2.7;8.2.7 Preparation of C60D18 in n-Hexane and Subsequent Photolysis Under He;161
11.1.2.8;8.2.8 Photolysis of C3n Isomer of C60H18 in Tetradecane Under Ar;162
11.1.3;8.3 Results and Discussion;162
11.1.3.1;8.3.1 Kinetics of the Fulleranes C60H36 and C60D36 Photolysis;162
11.1.3.2;8.3.2 Photolysis of C70H38 and C70D38;165
11.1.3.3;8.3.3 Photolysis of C60H18 and C60D18 in n-Hexane Under Helium: Determination of the Kinetic Isotope Effect;167
11.1.3.4;8.3.4 Photolysis of C3n-C60H18 in Tetradecane Under Ar;170
11.1.3.5;8.3.5 Discussion of the Photolysis Data in an Astrochemical Context;172
11.1.3.6;8.3.6 Photolysis Stability of C60H36: A Comparison with Other Fulleranes and with Polyynes;175
11.1.4;8.4 Conclusions;175
11.2;References;176
12;Chapter 9;178
12.1;Characterization of Hydrogenated Fullerenes by NMR Spectroscopy;178
12.1.1;9.1 Introduction;178
12.1.2;9.2 Synthesis and Sample Preparation;180
12.1.3;9.3 1H NMR Spectroscopy;181
12.1.4;9.4 13C NMR Spectroscopy;184
12.1.5;9.5 Two-Dimensional NMR Techniques;188
12.1.6;9.6 3He-NMR Spectroscopy;190
12.1.7;9.7 Specific Isomers of Hydrogenated Fullerenes Studied with NMR Spectroscopy;194
12.1.7.1;9.7.1 C60H2;194
12.1.7.2;9.7.2 C60H4;196
12.1.7.3;9.7.3 C60H6;198
12.1.7.4;9.7.4 C60H18;199
12.1.7.5;9.7.5 C60H36;200
12.1.7.6;9.7.6 C70H2;202
12.1.7.7;9.7.7 C70H4;203
12.1.7.8;9.7.8 C70H8;204
12.1.7.9;9.7.9 C70H10;205
12.1.7.10;9.7.10 C70H38;205
12.1.8;9.8 Conclusions;206
12.2;References;207
13;Chapter 10;210
13.1;Low Temperature Infrared Spectroscopy of C60 and C70 Fullerenes and Fullerane C60H18;210
13.1.1;10.1 Introduction;211
13.1.2;10.2 Experimental;211
13.1.2.1;10.2.1 Materials and Equipment;211
13.1.2.2;10.2.2 Experimental Procedure;212
13.1.3;10.3 Results and Discussion;213
13.1.3.1;10.3.1 The Low Temperature and High Temperature Gas Phase FT-IR Spectra of C60 Fullerene;213
13.1.3.2;10.3.2 The Low Temperature and High Temperature Gas Phase FT-IR Spectra of C70 Fullerene;219
13.1.3.3;10.3.3 The Low Temperature FT-IR Spectra of C60.H18 Fullerane;223
13.1.3.4;10.3.4 The Low Temperature FT-IR Spectra of Mixture of Fulleranes C60Hx (77%) and C70Hy (22%);227
13.1.4;10.4 Conclusions;229
13.2;References;230
14;Chapter 11;231
14.1;High-Pressure Hydrogenated Carbon Nanostructures;231
14.1.1;11.1 Experimental Methods for Testing of Samples;233
14.1.2;11.2 High-Pressure Hydrogenated Single-Walled Carbon Nanotubes and Nanofibers;234
14.1.3;11.3 High-Pressure Hydrogenated C60;247
14.2;References;255
15;Chapter 12;257
15.1;Topological Modeling of C60H36 Hydrides;257
15.1.1;12.1 Introduction;257
15.1.2;12.2 Topological Model;262
15.1.3;12.3 Topological Modeling of C60H18;264
15.1.4;12.4 Topological Modeling of C60H36;268
15.1.5;12.5 C60H36 Isomers with Extremal W or r Values;274
15.1.5.1;12.5.1 C60H36(C1*);274
15.1.5.2;12.5.2 C60H36(C1*)(2);274
15.1.6;12.6 C60H36(C3*);276
15.1.7;12.7 Conclusions;277
15.2;References;277