PROGRESS IN SURFACE AND MEMBRANE SCIENCE
CONTENTS INTRODUCTION CHAPTER 1 THE SEARCH FOR FUNCTIONAL POROUS CARBONS FROM SUSTAINABLE PRECURSORS 11 INTRODUCTION AND SUSTAINABLE PRECURSORS 12 PRINCIPLES OF GREEN CHEMISTRY AND SUSTAINABILITY 13 FUTURE ENERGY/CHEMICAL ECONOMIES AND SUSTAINABLE MATERIALS 131 THE METHANOL ECONOMY 132 THE BIOREFINERY CONCEPT 14 A BRIEF HISTORY OF (POROUS) CARBON MATERIALS FROM SUSTAINABLE PRECURSORS 141 GENERAL ASPECTS OF POROUS MATERIALS 142 ACTIVATED CARBONS 143 MESOPOROUS CARBONS 144 CARBON AEROGELS AND RELATED MATERIALS 145 GRAPHITIC NANOCARBONS – CARBON NANOTUBES AND GRAPHENE 146 IONIC LIQUIDS 147 HIERARCHICALLY POROUS CARBONS SYNTHESISED IN DEEP EUTECTIC SOLVENTS 148 EXPLOITATION OF POLYSACCHARIDE CHIRAL NEMATIC PHASES 15 OVERVIEW AND OUTLOOK OF THE BOOK REFERENCES PART 1: STARBONS® CHAPTER 2 FROM POLYSACCHARIDES TO STARBONS® 21 INTRODUCTION 22 POROUS POLYSACCHARIDE-DERIVED MATERIALS 23 FIRST-GENERATION STARBONS® – FROM STARCH TO CARBON 24 SECOND-GENERATION STARBONS® 241 PECTIN-DERIVED STARBONS® 242 CHITOSAN-DERIVED STARBONS® 243 ALGINIC ACID-DERIVED STARBONS® 25 THE SYNTHESIS OF STARBONS – MECHANISTIC CONSIDERATIONS 26 OUTLOOK AND CONCLUSIONS ACKNOWLEDGMENTS CHAPTER 3 POROUS CARBONACEOUS MATERIALS IN CATALYTIC APPLICATIONS 31 INTRODUCTION 32 BIOMASS-DERIVED POROUS CARBONACEOUS MATERIALS 33 SULFONATED STARBONS® AND CARBONACEOUS MATERIALS AS SOLID ACIDS 34 OTHER ROUTES TO THE INTRODUCTION OF MESOPOROSITY AND ASSOCIATED APPLICATIONS 35 ORDERED POROUS CARBONACEOUS MATERIALS 36 APPLICATION IN HYDROGENATION REACTIONS 37 BIOFUEL SYNTHESIS 38 PHOTOCATALYSIS 39 CONCLUSIONS AND PROSPECTS CHAPTER 4 APPLICATION OF CARBONACEOUS MATERIALS IN SEPARATION SCIENCE 41 INTRODUCTION 42 BACKGROUND TO HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC) AND INTRODUCTION OF POROUS CARBON STATIONARY PHASES 421 OVERVIEW 422 EFFICIENCY OF COLUMN SEPARATION 423 REQUIREMENTS FOR THE “IDEAL” STATIONARY-PHASE MATERIAL 43 INTRODUCTION OF POROUS CARBON STATIONARY PHASES 431 POROUS GRAPHITIC CARBON AND ITS APPLICATION 432 CHROMATOGRAPHIC APPLICATIONS OF POROUS GRAPHITIC CARBON 433 SYNTHESIS AND DRAWBACKS OF POROUS GRAPHITIC CARBON 44 SUSTAINABLE POROUS CARBONS IN SEPARATION SCIENCE 441 STARBONS® 442 ALGINATE-DERIVED MESOPOROUS CARBON SPHERES (AMCS) 45 DOES A SUSTAINABLE POROUS CARBON NEED TO BE GRAPHITIC? 46 OTHER SUSTAINABLE CARBONS IN CHROMATOGRAPHY 461 “CHOCOLATE” HYDROPHILIC INTERACTION LIQUID CHROMATOGRAPHY (HILIC) 462 CARBON COATING OF SILICA PARTICLES 47 FUTURE PERSPECTIVES 48 CONCLUSIONS PART 2: HYDROTHERMAL CARBONISATION (HTC) CHAPTER 5 HYDROTHERMAL CARBONISATION (HTC): HISTORY, STATE-OF-THE-ART AND CHEMISTRY 51 INTRODUCTION 52 STATE-OF-THE-ART 53 HUMINS AND ASSOCIATED MATERIALS 54 SOCIETAL AND COMMERCIAL ASPECTS 55 CHEMISTRY BEHIND THE FORMATION OF HTC MATERIALS 56 OUTLOOK AND CONCLUSIONS CHAPTER 6 POROUS HYDROTHERMAL CARBON MATERIALS, NANOPARTICLES, HYBRIDS AND COMPOSITES 61 INTRODUCTION 62 ACTIVATED HYDROTHERMAL CARBONS 63 POROUS HTC VIA HARD TEMPLATING: PREMADE SACRIFICIAL INORGANIC MOULDS 631 SILICA-BASED HARD TEMPLATES 632 NONSILICA-BASED HARD TEMPLATES 64 POROUS HTC VIA SOFT TEMPLATING 641 SUPRAMOLECULAR SELF-ASSEMBLIES: FROM OMCS TO HYBRID HOLLOW SPHERES 65 OIL-IN-WATER MACROEMULSIONS: FROM HYBRID HOLLOW SPHERES TO CARBO-HIPES 651 DILUTED MACROEMULSIONS 652 CONCENTRATED MACROEMULSIONS 66 POLYSTYRENE LATEX DISPERSIONS: FROM HOLLOW SPHERES TO CORAL-LIKE STRUCTURES 67 TEMPLATE-FREE HYDROTHERMAL CARBON HYDROGELS AND RELATED DRIED GELS 671 SALT-MEDIATED HYDROTHERMAL GELATION APPROACHES 672 OVALBUMIN-DERIVED GELATION APPROACH 673 PHENOLIC-DERIVED GELATION APPROACHES 674 CARBON NANOTUBES-ASSISTED STRUCTURE FORMATION 68 POROUS CARBONS FROM DIRECT HYDROTHERMAL TREATMENT OF NATURAL SYSTEMS 681 NATURAL SCAFFOLDS WITH IN SITU HARD TEMPLATES 682 NATURAL SCAFFOLDS WITHOUT IN SITU HARD TEMPLATES 69 BIOMASS-DERIVED HTC NANODOTS AND NANOCOMPOSITES 610 SUMMARY AND OUTLOOK CHAPTER 7 HYDROTHERMAL CARBON MATERIALS FOR HETEROGENEOUS CATALYSIS 71 INTRODUCTION 72 HETEROATOM FUNCTIONALISED HTC MATERIALS IN HETEROGENEOUS CATALYSIS 73 NITROGEN-CONTAINING CARBONS IN CATALYSIS 74 SULFUR-DOPED CARBONS FOR CATALYSIS 75 OTHER HETEROATOM-DOPED CARBONS IN CATALYSIS 76 HTC-SUPPORTED METAL COMPLEXES OR NANOPARTICLE-BASED CATALYSIS 77 HTC IN PHOTOCATALYSIS 78 OTHER CATALYSIS 79 CONCLUSIONS CHAPTER 8 HTC-DERIVED MATERIALS IN ENERGY AND SEQUESTRATION APPLICATIONS 81 INTRODUCTION – ENERGY STORAGE 82 ELECTRODES IN SUPERCAPACITORS 83 ELECTROCATALYSTS IN FUEL CELLS 831 ANODE CATALYST SUPPORTS IN DIRECT METHANOL FUEL CELLS 832 CATALYSTS FOR THE OXYGEN-REDUCTION REACTION (ORR) 84 ELECTRODES IN RECHARGEABLE BATTERIES 841 LI-ION BATTERIES 842 ANODE MATERIALS 843 CATHODE MATERIALS 844 NA-ION BATTERIES 845 LI–S BATTERIES 85 CO2 CAPTURE 86 CONCLUSION PART 3: CHARACTERISATION OF POROUS CARBONACEOUS SOLIDS CHAPTER 9 POROSITY CHARACTERISATION OF CARBON MATERIALS 91 INTRODUCTION AND DEFINITIONS 92 DEFINITIONS 93 METHODS 931 GAS ADSORPTION TECHNIQUES 932 SCATTERING AND DIFFRACTION METHODS 933 MICROSCOPY 934 OTHER METHODS 94 CONCLUSION CHAPTER 10 BULK AND SURFACE ANALYSIS OF CARBONACEOUS MATERIALS 101 INTRODUCTION 102 THERMAL GRAVIMETRIC ANALYSIS 1021 INTRODUCTION 1022 RESULTS AND DISCUSSION 103 X-RAY PHOTOELECTRON SPECTROSCOPY (XPS) 1031 INTRODUCTION 1032 ELEMENTAL ANALYSIS 1033 HIGH-RESOLUTION C1S SPECTRA 1034 HIGH-RESOLUTION O1S SPECTRA 1035 DISCUSSION 104 INFRARED (IR) SPECTROSCOPY 1041 INTRODUCTION 1042 EXPERIMENTAL 105 BOEHM TITRATION 1051 INTRODUCTION 1052 EXPERIMENTAL 1053 RESULTS AND DISCUSSION 106 BROMINATION 1061 INTRODUCTION 1062 EXPERIMENTAL 1063 RESULTS AND DISCUSSION 107 SOLID-STATE NUCLEAR MAGNETIC RESONANCE (SSNMR) 1071 INTRODUCTION 1072 FULLERENES AND NANOTUBES 1073 LIGNIN, CELLULOSE AND THEIR CHARS FROM PYROLYSIS 1074 CARBONACEOUS MATERIALS PREPARED VIA HYDROTHERMAL PROCESSING 108 LINEAR SOLVATION ENERGY RELATIONSHIP ANALYSIS USING 19F MAS NMR SPECTROSCOPIC PROBES 1081 VALIDATION OF 19F MAS NMR SPECTROSCOPIC PROBING METHOD 1082 THEORETICAL BACKGROUND OF 19F MAS NMR PROBE SPECTROSCOPY 1083 ESTIMATION OF THE ELECTROMAGNETIC TERM (?SHIELDING) 1084 ESTIMATION ADSORPTION OF ALIPHATIC AND AROMATIC REPORTER MOLECULES 109 CONCLUSION CHAPTER 11 MICROSCOPY AND RELATED TECHNIQUES IN THE ANALYSIS OF POROUS CARBONACEOUS MATERIALS 111 INTRODUCTION 112 TUTORIAL OVERVIEW OF A TEM TECHNIQUE 1121 TEM AS A VISUALISATION TOOL 1122 TEM AS A TOOL FOR ANALYSING NANOSTRUCTURE OF POROUS CARBONACEOUS MATERIALS 1123 ELECTRON TOMOGRAPHY – “3D-TEM” 113 EXAMPLES OF MICROSCOPY ANALYSES OF POROUS CARBONACEOUS MATERIALS 1131 ULTRAMICROTOME AND TEM IN THE ANALYSIS OF NANOSTRUCTURED POROUS CARBONACEOUS MATERIALS 1132 TEM TOMOGRAPHY IN THE ANALYSIS OF NANOSTRUCTURED CARBONACEOUS MATERIALS 114 CONCLUSION PART 4: COMMERCIALISATION CHAPTER 12 OTHER APPROACHES AND THE COMMERCIALISATION OF SUSTAINABLE CARBONACEOUS MATERIAL TECHNOLOGY 121 INTRODUCTION 122 OTHER INNOVATIVE APPROACHES TO POROUS CARBONS FROM SUSTAINABLE PRECURSORS 1221 BACTERIAL CELLULOSE 1222 FILAMENTOUS FUNGI 1223 GELATIN 1224 SILK COCOON 1225 FLAVONOIDS AND TANNIN 1226 LIGNIN 1227 IONIC LIQUIDS AS A SOLVENT IN HYDROTHERMAL CARBONISATION 123 COMMERCIALISATION OF SUSTAINABLE CARBON MATERIALS 1231 STARBON® TECHNOLOGIES LTD 1232 HYDROTHERMAL CARBONISATION 124 SUMMARY AND OUTLOOK