Ionic Liquids - New Aspects for the Future

Cover......Page 1
Ionic Liquids: New Aspects for the Future......Page 2
©......Page 3
Contents......Page 5
Preface......Page 9
Section 1 Fundamental Properties......Page 11
1. Introduction......Page 13
2. Tracking Ionic Motions Through Interionic Interactions: Cross-Correlation, Polarization Effects, and Dynamical Properties......Page 15
3. Theoretical Background......Page 18
3.1. Cross-Correlation Function......Page 19
3.2.1. A Polarizable Model......Page 20
3.2.2. Polarizability Time-Correlation Function (TCF)......Page 21
3.3. Computational Details......Page 23
4. Cross-Correlation, Momentum Correlation, and Polarization Effects......Page 24
5. Relaxation Processes and Dynamical Properties......Page 30
6. Conclusion......Page 34
Author details......Page 35
References......Page 36
1. Introduction......Page 41
2.1. Pure ionic liquids......Page 42
2.2. Binary and ternary mixtures......Page 44
3.1. gE-based models......Page 46
References......Page 52
3.2.1. Peng-Robinson......Page 53
3.2.2. Soave-Redlich-Kwong......Page 54
3.2.3. Statistical associating fluid theory......Page 56
4. Conclusions......Page 58
References......Page 59
1. Introduction......Page 71
3.2. Synthesis of 1-butyl-3-methylimidazolium halide (bmimX, where X- = Br, I) and bmimNTf2......Page 74
3.3.2. Synthesis of N-alkyl-N-methylpiperidinium Iodide (PIP1nI)......Page 75
3.3.3. Synthesis of N-butyl-N-methylpiperidiniumbis(trifluoromethanesulfonyl)imide (PIP14NTf2)......Page 76
4. Thermo-physical properties study......Page 77
4.1. Viscosity......Page 78
4.2. Cyclic voltammetry......Page 79
5.1. Studies of interactions in molecular structure of different ILs using DFT calculations......Page 80
5.2. Experimental and theoretical infrared spectrum of PIP14NTf2......Page 82
5.3. UV-visible spectra of PIP14NTf2 and bmimNTf2......Page 86
6. Conclusion......Page 87
References......Page 88
1. Introduction......Page 95
2. QSAR/Spectral-SAR Modeling of the Structure-EcoToxicity of Ionic Liquids......Page 99
3. Algebraic QSAR: Spectral-SAR [69,70]......Page 100
4. From in Cerebro to in Silico Principles of Ecotoxicity......Page 106
5. Two Cases of Ionic Liquids Ecotoxicity......Page 111
6. Conclusions......Page 124
References......Page 127
1. Introduction......Page 137
2.1. Required characteristics of a lubricant......Page 138
2.2. Hydrodynamic lubrication capacity of ionic liquid......Page 139
2.3. Boundary lubrication capacity of ionic liquid......Page 141
2.4.1. Control of atmospheric air......Page 142
2.4.3. Halogen-free ionic liquid......Page 144
3.2. Occurrence of out-gassing......Page 145
References......Page 147
1. Introduction......Page 153
2. Influencing the specific interfacial area......Page 154
3. Determination of gas holdup......Page 155
4. Bubble Formation and Coalescence......Page 158
5. Gas holdup at low and elevated pressures......Page 161
6.1. Flow patterns......Page 165
6.2. Structure frequencies......Page 167
6.3. Structure velocities......Page 169
References......Page 171
1. Introduction......Page 175
2. Ionic Liquids......Page 177
3. IoNanofluids......Page 179
3.1. Manufacture of IoNanofluids......Page 180
3.2. Experimental properties and their impact on process equipment design......Page 182
3.3.1. Thermal stability......Page 188
3.3.2. Toxicity of ionic liquids, nanomaterials and IoNanofluids......Page 189
4. Theoretical Modelling of Nano and IoNanofluids......Page 191
5. Conclusions and Looking Forward......Page 194
References......Page 195
1. Introduction......Page 205
2. Electrochemical supercapacitors......Page 208
3. Lithium-ion batteries......Page 210
4. IL/electrode interface......Page 211
5. Other electrochemical applications......Page 213
6. Molecular-scale insights into the mechanisms of ionic liquids interactions with carbon nanotubes and graphite surfaces......Page 215
7. Liquid-to-solid phase transition of ionic liquids monolayer confined between graphite walls......Page 222
8. The structure of ionic liquid [C4mim]PF6/rutile (110) interface......Page 223
Author details......Page 226
References......Page 227
Section 2 Energies, Fuels, and Biomass Conversions......Page 241
1. Introduction......Page 243
2.1. Ionic liquids for PEM fuel cells......Page 245
2.2. Ionic liquids for Li-ion batteries......Page 247
2.3. Ionogels......Page 248
3. Structural investigations......Page 249
3.1. Raman spectroscopy: Conformational isomerism......Page 250
3.2. NMR spectroscopy: Heteronuclear coupling......Page 252
3.3. SAXS: Nano-segregation......Page 253
4. Dynamical investigations......Page 255
4.1. Dielectric spectroscopy: Ionic conductivity......Page 256
4.2. NMR spectroscopy: Self-diffusion......Page 258
4.3. Confocal μ-Raman spectroscopy: In-situ fuel cell diagnostic......Page 260
Acknowledgements......Page 261
References......Page 262
1.1. Dye-sensitized solar cells (DSSCs)......Page 267
1.2. Ionic liquids (ILs)......Page 268
1.3. ILs as the electrolyte for DSSCs......Page 269
2.1. ILs crystals (system A)......Page 271
References......Page 274
2.2. ILs polymers (system B)......Page 275
2.3. ILs conductors (system C)......Page 277
3. Summary and future prospects......Page 278
References......Page 279
1. Introduction......Page 287
2.2. Description of Hydrodesulfurization (HDS) Process......Page 288
2.3. Biodesulfurization (BDS)......Page 289
3.1. Desulfurization of diesel fuels by extraction with N-alkyl-pyridinium-based ionic liquids......Page 290
3.2. Desulfurization of of fuel Using Imidazolium-based ILs......Page 292
3.3. Desulfurization of fuel using quaternary ammonium -based ionic liquids......Page 297
3.4. Extractive Desulfurization Using Fe-Containing Ionic Liquids......Page 298
3.5. Optimization of oxidative desulfurization of dibenzothiophene using acidic ionic liquid......Page 299
Author details......Page 301
References......Page 302
1. Introduction......Page 309
2.1. Changes in chemical components......Page 310
2.2. Morphological changes in wood tissue......Page 314
2.3. Influence of reaction atmosphere......Page 316
3. Liquefaction of cellulose in [C2mim][Cl] with sulfuric acid......Page 319
4. Conclusion......Page 321
References......Page 322
1.1.1. Monolignols......Page 325
1.1.2. Formation of Lignin......Page 327
1.2.1.1. Task-Specific ILs/ (Multi)-Functional ILs......Page 329
1.2.1.4. Switchable Polarity Solvent (SPS)......Page 330
1.2.2. Preparations of ILs......Page 331
1.2.2.2. Halogen Free Synthesis......Page 332
1.2.2.4. Special Cases......Page 333
2. Extracting Lignin with Ionic Liquid......Page 335
2.2. Lignin Extraction without Dissolution of Biomass......Page 336
2.3. Extraction of Lignin through Dissolution of Biomass......Page 339
3.1. Oxidation......Page 341
3.2. Dehydration......Page 343
3.3. Esterification......Page 344
4. Conversion of Lignin to Value-Added Chemicals in Ionic Liquid......Page 345
4.1. Depolymerization of Lignin......Page 346
4.2. Value-added small molecular compounds......Page 347
5. Conclusions and perspectives......Page 350
References......Page 351
Section 3 Organic Reactions and Biological Applications......Page 357
1. Introduction......Page 359
2. Benzene hydroxylation......Page 360
3. Alcohol oxidation......Page 363
4. Olefin oxidation......Page 366
5. Conclusion......Page 369
References......Page 370
1. Introduction......Page 375
2.1. Preparation of ILs and supported ILs......Page 377
2.3. Physical properties equipment......Page 378
3. Results and discussion......Page 379
4. Conclusions......Page 395
References......Page 396
1. Introduction......Page 401
2. Main Objetives......Page 404
3.1. Monocyclic five membered and benzofused five membered nitroheteroaromatic compounds, as dienophiles......Page 405
3.1.1. Nitroindole as dienophiles......Page 412
3.1.2. 2-NitroBenzofuran as dienophile......Page 414
3.2. Azanitronaphathalenes as dienophiles......Page 415
3.3. Nitronaphthalenes as dienophiles......Page 417
4. Diels-Alder reactions employing ionic liquids and microwave irradiation......Page 418
5.1. General......Page 419
5.2. Dienes......Page 421
5.3.1. Five-membered heterocycles......Page 422
5.3.2. Benzofused heterocycles......Page 424
5.4. Ionic Liquids effect......Page 426
5.5.1. Monocyclic five membered nitroheteroaromatic compounds as dienophiles.......Page 427
5.5.2. Nitronaphthalenes as dienophiles......Page 429
5.5.3. Nitroquinolines......Page 430
6. Conclusions......Page 436
References......Page 438
1. Introduction......Page 443
2. Behavior of the Solvents Under Microwave Environment......Page 445
3. Heating Effects of Adding a Small Quantity of Ionic Liquid in Solvents......Page 446
4. Ionic Liquids as Doping Agents (ILDA) in Microwave Assisted Reactions......Page 450
5. Ionic Liquids as Doping Agents in Microwave Assisted N-Alkylation Reactions......Page 455
7. List of Abbreviations......Page 458
References......Page 460
1. Introduction......Page 467
2.1. Synthesis of acyclic products......Page 468
2.2.2. 4CRs yielding heterocycles with ring oxygen and nitrogen atoms......Page 490
2.2.3. 4CRs yielding heterocycles with two ring nitrogens......Page 491
2.2.4. 4CRs yielding heterocycles with >three ring nitrogens......Page 492
References......Page 493
1. Introduction......Page 509
2. Applications of ionic liquids in organic synthesis......Page 510
2.1. Heck reaction......Page 511
2.2. Sonogashira reaction......Page 514
2.3. Suzuki coupling......Page 516
2.4. Stille coupling......Page 518
2.5. Diels-Alder reaction......Page 519
2.6. Acetalisation reactions......Page 521
3. Environmental fate of ionic liquids......Page 522
3.1. Toxicity and eco(toxicity) of ionic liquids......Page 523
3.2. Biodegradation of ionic liquids......Page 526
3.3. Guidelines for designing ‘Green’ ionic liquid catalysts/solvents......Page 529
4. Green chemistry metrics......Page 530
5. Case study......Page 531
6. Conclusion......Page 535
Author details......Page 536
References......Page 537
1. Introduction......Page 547
2.1. Lipases......Page 548
2.3. Oxidoreductases......Page 549
3. Factors affecting enzymes in ionic liquids......Page 550
5. First generation of ionic liquids......Page 552
7. Third generation of ionic liquids......Page 553
9. Modification of solvent media......Page 554
11. Applications of ionic liquids in biocatalysis......Page 555
Nomenclature......Page 556
References......Page 558
1. Introduction......Page 567
2.1. Salification of APIs......Page 571
2.2. Synthesis of ILs from APIs......Page 573
2.3. ILs characterization......Page 574
3. Pharmaceutical activity assessment......Page 578
List of Abbreviations......Page 583
References......Page 584
1. Introduction......Page 591
2. Dependence of the remaining activity of lysozyme on the concentration of ionic liquids after the incubation at 25 oC......Page 593
3.1. Thermal inactivation of lysozyme......Page 594
3.2. Refolding of lysozyme by ionic liquids......Page 596
3.3. Dependence of the remaining activity of lysozyme on the concentration of ionic liquids via heat treatment......Page 597
3.4. Dependence of the remaining activity of lysozyme on the temperature of heat treatment......Page 598
3.5. Time course of remaining activity of lysozyme via heat treatment with or without ionic liquids......Page 599
Author details......Page 600
References......Page 601
Section 4 Materials and Processing......Page 605
1. Introduction......Page 607
2. XPS analysis......Page 608
3. MALDI Mass Spectroscopy......Page 609
4. Use of ILs for SEM observations......Page 610
5. Observation of electrochemical reactions......Page 613
6. EDX analysis......Page 614
7. Preparation of metal nanoparticles by plasma deposition method......Page 616
8. Nanoparticle synthesis by sputtering......Page 617
9. Nanoparticle preparation by quantum Beam......Page 620
Author details......Page 621
References......Page 622
1. Introduction......Page 627
2. Gas-liquid interfacial plasma process using ionic liquid substrate......Page 628
3.1. Periodic nanoparticle structure formed by periodic plasma......Page 630
3.2. Ring-shaped nanoparticle structure formed by structure-controlled plasma......Page 633
3.3. Size control of ring-shaped nanoparticle structure under inhomogeneous conversing magnetic fields......Page 637
4. Conclusion......Page 638
References......Page 639
1. Introduction......Page 643
1.1. Development of Innovative Synthesis Methods of Ceramic Nano-materials Using Ionic Liquid......Page 644
2.1. The fabrication of BaCO3 nanostructures as nanofillers for electromagnetic-absorbing coatings......Page 648
2.2. Fern-like, fish skeleton-like, bunched cubic, and butterfly-like BaO nanostructures as nanofillers for Radar-absorbing coatings......Page 651
2.3. Morphology evolution of the ZnO/Zn(OH)2 nanofillers using ionic liquids......Page 655
References......Page 657
1. Introduction......Page 663
2.1. FRET......Page 664
2.2. FRET in Systems of Rhodamine 6G with BMIMCl......Page 665
3.1. Polymeric Ionic Liquids......Page 666
3.2. Preparation of Transparent Polymeric Ionic Liquid Films......Page 668
3.3. Preparation and Multicolor Emissions of Fluorescent Polymeric Ionic Liquid Films......Page 670
4.1. Ion Gels of Polysaccharides with Ionic Liquids......Page 673
4.2. FRET Function of Ion Gel of Guar Gum with an Ionic Liquid......Page 674
4.3. Fluorescent Behaviors of Ion Gel of Xanthan Gum with an Ionic Liquid......Page 676
5. Conclusion......Page 678
References......Page 679
1. Introduction......Page 683
2. Preparation and physicochemical properties of DEMM-TFSI......Page 684
3.1. Radical polymerization of ionic liquid monomer; DEMM-TFSI......Page 686
3.2. Molecular weight control of poly(DEMM-TFSI)......Page 688
4. Physicochemical properties of poly(DEMM-TFSI)......Page 690
5. High rate performance of a lithium polymer battery using an ionic liquid polymer composite......Page 694
6. Conclusion......Page 700
References......Page 702