Sustainable Carbon Materials from Hydrothermal Processes

The production of low cost and environmentally friendly high performing carbon materials is crucial for a sustainable future. Sustainable Carbon Materials from Hydrothermal Processes describes a sustainable and alternative technique to produce carbon from biomass in water at low temperatures, a process known as Hydrothermal Carbonization (HTC).

Sustainable Carbon Materials from Hydrothermal Processes presents an overview of this new and rapidly developing field, discussing various synthetic approaches, characterization of the final products, and modern fields of application for of sustainable carbon materials.

Topics covered include:

• Green carbon materials
• Porous hydrothermal carbons
• HTC for the production of valuable carbon hybrid materials
• Functionalization  of hydrothermal carbon materials
• Characterization of HTC materials
• Applications of HTC in modern nanotechnology: Energy storage, electrocatalysis in fuel cells, photocatalysis, gas storage, water purification, sensors, bioapplications
• Environmental applications of HTC technology: Biochar production, carbon sequestration, and waste conversion
• Scale-up in HTC

Sustainable Carbon Materials from Hydrothermal Processes will serve as a comprehensive guide for students and newcomers in the field, as well as providing a valuable source of information for researchers and investors looking for alternative technologies to convert biomass into useful products.

Dr. Maria-Magdalena Titirici, Max-Planck Institute of Colloids and Interfaces, Germany
Maria-Magdalena has been working in the field of hydrothermal carbonization (HTC) since 2005. Her laboratory at the Max-Planck Institute of Colloids and Interfaces has been driving the renewed interest in HTC for the production of high-tech carbonaceous materials. Since 2005 she has published more than 40 scientific papers on this topic, including 2 reviews, as well as a book chapter.

Preface xiii

1 Green Carbon 1

Maria-Magdalena Titirici

1.1 Introduction 1

1.2 Green Carbon Materials 3

1.2.1 CNTs and Graphitic Nanostructures 4

1.2.2 Graphene, Graphene Oxide, and Highly Reduced Graphene Oxide 11

1.2.3 Activated Carbons 14

1.2.4 Starbons 14

1.2.5 Use of Ionic Liquids in the Synthesis of Carbon Materials 19

1.2.6 HTC 27

1.3 Brief History of HTC 27

References 30

2 Porous Hydrothermal Carbons 37

Robin J. White, Tim-Patrick Fellinger, Shiori Kubo, Nicolas Brun, and Maria-Magdalena Titirici

2.1 Introduction 37

2.2 Templating – An Opportunity for Pore Morphology Control 39

2.2.1 Hard Templating in HTC 40

2.2.2 Soft Templating in HTC 42

2.2.3 Naturally Inspired Systems: Use of Natural Templates 49

2.3 Carbon Aerogels 50

2.3.1 Ovalbumin/Glucose-Derived HTC-Derived Carbogels 52

2.3.2 Borax-Mediated Formation of HTC-Derived Carbogels from Glucose 56

2.3.3 Carbogels from the Hydrothermal Treatment of Sugar and Phenolic Compounds 63

2.3.4 Emulsion-Templated “Carbo-HIPEs” from the Hydrothermal

Treatment of Sugar Derivatives and Phenolic Compounds 65

2.4 Summary and Outlook 69

References 70

3 Porous Biomass-Derived Carbons: Activated Carbons 75

Dolores Lozano-Castello, Juan Pablo Marco-Lozar, Camillo Falco, Maria-Magdalena Titirici, and Diego Cazorla-Amoros

3.1 Introduction to Activated Carbons 75

3.2 Chemical Activation of Lignocellulosic Materials 77

3.2.1 H3PO4 Activation of Lignocellulosic Precursors 78

3.2.2 ZnCl2 Activation of Lignocellulosic Precursors 82

3.2.3 KOH and NaOH Activation of Lignocellulosic Precursors 84

3.3 Activated Carbons from Hydrothermally Carbonized Organic Materials and Biomass 86

3.3.1 Hydrochar Materials: Synthesis, Structural, and Chemical Properties 88

3.3.2 KOH Activation of Hydrochar Materials 89

3.4 Conclusions 95

Acknowledgments 95

References 96

4 Hydrothermally Synthesized Carbonaceous Nanocomposites 101

Bo Hu, Hai-Zhou Zhu, and Shu-Hong Yu

4.1 Introduction 101

4.2 HTC Synthesis of Unique Carbonaceous Nanomaterials 102

4.2.1 Carbonaceous Nanomaterials 102

4.2.2 Carbonaceous Nanocomposites 110

4.3 Conclusion and Outlook 121

Acknowledgments 121

References 121

5 Chemical Modification of Hydrothermal Carbonization Materials 125

Stephanie Wohlgemuth, Hiromitsu Urakami, Li Zhao, and Maria-Magdalena Titirici

5.1 Introduction 125

5.2 In Situ Doping of Hydrothermal Carbons 126

5.2.1 Nitrogen 126

5.2.2 Sulfur 130

5.2.3 Boron 132

5.2.4 Organic Monomers Sources 132

5.2.5 Properties of Heteroatom-Doped Carbon Materials 133

5.3 Postmodification of Carbonaceous Materials 139

5.3.1 Chemical Handles for Functionalization Present on HTC Materials 140

5.3.2 Perspectives on HTC Postmodification Strategies 143

References 145

6 Characterization of Hydrothermal Carbonization Materials 151

Niki Baccile, Jens Weber, Camillo Falco, and Maria-Magdalena Titirici

6.1 Introduction 151

6.2 Morphology of HTC Materials 152

6.2.1 Morphology of Glucose-Derived Hydrothermal Carbons 153

6.2.2 Morphology of Other Carbohydrate-Derived Hydrothermal Carbons 157

6.2.3 Morphology of Cellulose- and Biomass-Derived Hydrothermal Carbons 159

6.3 Elemental Composition and Yields 161

6.4 FTIR 164

6.5 XPS: Surface Groups 165

6.6 Zeta Potential: Surface Charge 166

6.7 XRD: Degree of Structural Order 169

6.8 Thermal Analysis 170

6.9 Structure Elucidation of Carbon Materials Using Solid-State NMR Spectroscopy 172

6.9.1 Brief Introduction to Solid-State NMR 172

6.9.2 Solid-State NMR of Crystalline Nanocarbons: Fullerenes and Nanotubes 174

6.9.3 Solid-State NMR Study of Biomass Derivatives and their Pyrolyzed Carbons 175

6.9.4 Solid-State NMR Study of Hydrothermal Carbons 178

6.10 Porosity Analysis of Hydrothermal Carbons 190

6.10.1 Introduction and Definition of Porosity 190

6.10.2 Gas Physisorption 191

6.10.3 Mercury Intrusion Porosity 202

6.10.4 Scattering Methods 204

References 204

7 Applications of Hydrothermal Carbon in Modern Nanotechnology 213

Marta Sevilla, Antonio B. Fuertes, Rezan Demir-Cakan, and Maria-Magdalena Titirici

7.1 Introduction 213

7.2 Energy Storage 214

7.2.1 Electrodes in Rechargeable Batteries 215

7.2.2 Electrodes in Supercapacitors 229

7.2.3 Heterogeneous Catalysis 234

7.2.4 HTC-Derived Materials as Catalyst Supports 235

7.2.5 HTC-Derived Materials with Various Functionalities and Intrinsic Catalytic Properties 239

7.3 Electrocatalysis in Fuel Cells 241

7.3.1 Catalyst Supports in Direct Methanol Fuel Cells 242

7.3.2 Heteroatom-Doped Carbons with Intrinsic Catalytic Activity for the ORR 250

7.4 Photocatalysis 255

7.5 Gas Storage 260

7.5.1 CO2 Capture Using HTC-Based Carbons 260

7.5.2 Hydrogen Storage Using HTC-Based Activated Carbons 264

7.6 Adsorption of Pollutants from Water 265

7.6.1 Removal of Heavy Metals 265

7.6.2 Removal of Organic Pollutants 271

7.7 HTC-Derived Materials in Sensor Applications 272

7.7.1 Chemical Sensors 272

7.7.2 Gas Sensors 274

7.8 Bioapplications 275

7.9 Drug Delivery 276

7.9.1 Bioimaging 279

7.10 Conclusions and Perspectives 282

References 283

8 Environmental Applications of Hydrothermal Carbonization Technology: Biochar Production, Carbon Sequestration, and Waste Conversion 295

Nicole D. Berge, Claudia Kammann, Kyoung Ro, and Judy Libra

8.1 Introduction 295

8.2 Waste Conversion to Useful Products 297

8.2.1 Conversion of MSW 298

8.2.2 Conversion of Animal Waste 302

8.2.3 Potential Hydrochar Uses 306

8.3 Soil Application 309

8.3.1 History of the Idea to Sequester Carbon in Soils Using Chars/Coals 309

8.3.2 Consideration of Hydrochar Use in Soils 311

8.3.3 Stability of Hydrochar in Soils 311

8.3.4 Influence of Hydrochar on Soil Fertility and Crop Yields 318

8.3.5 Greenhouse Gas Emissions from Char-Amended Soils 323

8.3.6 Best-Practice Considerations for Biochar/Hydrochar Soil Application 325

8.4 HTC Technology: Commercial Status and Research Needs 325

References 329

9 Scale-Up in Hydrothermal Carbonization 341

Andrea Kruse, Daniela Baris, Nicole Troger, and Peter Wieczorek

9.1 Introduction 341

9.2 Basic Aspects of Process Development and Upscaling 343

9.2.1 Batch/Tubular Reactors 344

9.2.2 CSTRs 345

9.2.3 Product Handling 345

9.3 Risks of Scaling-Up 346

9.4 Lab-Scale Experiments 347

9.4.1 Experimental 347

9.4.2 Results and Discussion 348

9.5 Praxis Report 348

9.6 Conclusions 352

References 353

Index

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