Dr. Maria-Magdalena Titirici, Max-Planck Institute of Colloids and Interfaces, GermanyMaria-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.

• List of Contributors xi Preface xiii1 Green Carbon 1Maria-Magdalena Titirici1.1 Introduction 11.2 Green Carbon Materials 31.2.1 CNTs and Graphitic Nanostructures 41.2.2 Graphene, Graphene Oxide, and Highly Reduced Graphene Oxide 111.2.3 Activated Carbons 141.2.4 Starbons 141.2.5 Use of Ionic Liquids in the Synthesis of Carbon Materials 191.2.6 HTC 271.3 Brief History of HTC 27References 302 Porous Hydrothermal Carbons 37Robin J. White, Tim-Patrick Fellinger, Shiori Kubo, Nicolas Brun, and Maria-Magdalena Titirici2.1 Introduction 372.2 Templating – An Opportunity for Pore Morphology Control 392.2.1 Hard Templating in HTC 402.2.2 Soft Templating in HTC 422.2.3 Naturally Inspired Systems: Use of Natural Templates 492.3 Carbon Aerogels 502.3.1 Ovalbumin/Glucose-Derived HTC-Derived Carbogels 522.3.2 Borax-Mediated Formation of HTC-Derived Carbogels from Glucose 562.3.3 Carbogels from the Hydrothermal Treatment of Sugar and Phenolic Compounds 632.3.4 Emulsion-Templated “Carbo-HIPEs” from the HydrothermalTreatment of Sugar Derivatives and Phenolic Compounds 652.4 Summary and Outlook 69References 703 Porous Biomass-Derived Carbons: Activated Carbons 75Dolores Lozano-Castello, Juan Pablo Marco-Lozar, Camillo Falco, Maria-Magdalena Titirici, and Diego Cazorla-Amoros3.1 Introduction to Activated Carbons 753.2 Chemical Activation of Lignocellulosic Materials 773.2.1 H3PO4 Activation of Lignocellulosic Precursors 783.2.2 ZnCl2 Activation of Lignocellulosic Precursors 823.2.3 KOH and NaOH Activation of Lignocellulosic Precursors 843.3 Activated Carbons from Hydrothermally Carbonized Organic Materials and Biomass 863.3.1 Hydrochar Materials: Synthesis, Structural, and Chemical Properties 883.3.2 KOH Activation of Hydrochar Materials 893.4 Conclusions 95Acknowledgments 95References 964 Hydrothermally Synthesized Carbonaceous Nanocomposites 101Bo Hu, Hai-Zhou Zhu, and Shu-Hong Yu4.1 Introduction 1014.2 HTC Synthesis of Unique Carbonaceous Nanomaterials 1024.2.1 Carbonaceous Nanomaterials 1024.2.2 Carbonaceous Nanocomposites 1104.3 Conclusion and Outlook 121Acknowledgments 121References 1215 Chemical Modification of Hydrothermal Carbonization Materials 125Stephanie Wohlgemuth, Hiromitsu Urakami, Li Zhao, and Maria-Magdalena Titirici5.1 Introduction 1255.2 In Situ Doping of Hydrothermal Carbons 1265.2.1 Nitrogen 1265.2.2 Sulfur 1305.2.3 Boron 1325.2.4 Organic Monomers Sources 1325.2.5 Properties of Heteroatom-Doped Carbon Materials 1335.3 Postmodification of Carbonaceous Materials 1395.3.1 Chemical Handles for Functionalization Present on HTC Materials 1405.3.2 Perspectives on HTC Postmodification Strategies 143References 1456 Characterization of Hydrothermal Carbonization Materials 151Niki Baccile, Jens Weber, Camillo Falco, and Maria-Magdalena Titirici 6.1 Introduction 1516.2 Morphology of HTC Materials 1526.2.1 Morphology of Glucose-Derived Hydrothermal Carbons 1536.2.2 Morphology of Other Carbohydrate-Derived Hydrothermal Carbons 1576.2.3 Morphology of Cellulose- and Biomass-Derived Hydrothermal Carbons 1596.3 Elemental Composition and Yields 1616.4 FTIR 1646.5 XPS: Surface Groups 1656.6 Zeta Potential: Surface Charge 1666.7 XRD: Degree of Structural Order 1696.8 Thermal Analysis 1706.9 Structure Elucidation of Carbon Materials Using Solid-State NMR Spectroscopy 1726.9.1 Brief Introduction to Solid-State NMR 1726.9.2 Solid-State NMR of Crystalline Nanocarbons: Fullerenes and Nanotubes 1746.9.3 Solid-State NMR Study of Biomass Derivatives and their Pyrolyzed Carbons 1756.9.4 Solid-State NMR Study of Hydrothermal Carbons 1786.10 Porosity Analysis of Hydrothermal Carbons 1906.10.1 Introduction and Definition of Porosity 1906.10.2 Gas Physisorption 1916.10.3 Mercury Intrusion Porosity 2026.10.4 Scattering Methods 204References 2047 Applications of Hydrothermal Carbon in Modern Nanotechnology 213Marta Sevilla, Antonio B. Fuertes, Rezan Demir-Cakan, and Maria-Magdalena Titirici7.1 Introduction 2137.2 Energy Storage 2147.2.1 Electrodes in Rechargeable Batteries 2157.2.2 Electrodes in Supercapacitors 2297.2.3 Heterogeneous Catalysis 2347.2.4 HTC-Derived Materials as Catalyst Supports 2357.2.5 HTC-Derived Materials with Various Functionalities and Intrinsic Catalytic Properties 2397.3 Electrocatalysis in Fuel Cells 2417.3.1 Catalyst Supports in Direct Methanol Fuel Cells 2427.3.2 Heteroatom-Doped Carbons with Intrinsic Catalytic Activity for the ORR 2507.4 Photocatalysis 2557.5 Gas Storage 2607.5.1 CO2 Capture Using HTC-Based Carbons 2607.5.2 Hydrogen Storage Using HTC-Based Activated Carbons 2647.6 Adsorption of Pollutants from Water 2657.6.1 Removal of Heavy Metals 2657.6.2 Removal of Organic Pollutants 2717.7 HTC-Derived Materials in Sensor Applications 2727.7.1 Chemical Sensors 2727.7.2 Gas Sensors 2747.8 Bioapplications 2757.9 Drug Delivery 2767.9.1 Bioimaging 2797.10 Conclusions and Perspectives 282References 2838 Environmental Applications of Hydrothermal Carbonization Technology: Biochar Production, Carbon Sequestration, and Waste Conversion 295Nicole D. Berge, Claudia Kammann, Kyoung Ro, and Judy Libra8.1 Introduction 2958.2 Waste Conversion to Useful Products 2978.2.1 Conversion of MSW 2988.2.2 Conversion of Animal Waste 3028.2.3 Potential Hydrochar Uses 3068.3 Soil Application 3098.3.1 History of the Idea to Sequester Carbon in Soils Using Chars/Coals 3098.3.2 Consideration of Hydrochar Use in Soils 3118.3.3 Stability of Hydrochar in Soils 3118.3.4 Influence of Hydrochar on Soil Fertility and Crop Yields 3188.3.5 Greenhouse Gas Emissions from Char-Amended Soils 3238.3.6 Best-Practice Considerations for Biochar/Hydrochar Soil Application 3258.4 HTC Technology: Commercial Status and Research Needs 325References 3299 Scale-Up in Hydrothermal Carbonization 341Andrea Kruse, Daniela Baris, Nicole Troger, and Peter Wieczorek9.1 Introduction 3419.2 Basic Aspects of Process Development and Upscaling 3439.2.1 Batch/Tubular Reactors 3449.2.2 CSTRs 3459.2.3 Product Handling 3459.3 Risks of Scaling-Up 3469.4 Lab-Scale Experiments 3479.4.1 Experimental 3479.4.2 Results and Discussion 3489.5 Praxis Report 3489.6 Conclusions 352References 353Index

Dr. Maria-Magdalena Titirici, Max-Planck Institute of Colloids and Interfaces, GermanyMaria-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.

• List of Contributors xi Preface xiii1 Green Carbon 1Maria-Magdalena Titirici1.1 Introduction 11.2 Green Carbon Materials 31.2.1 CNTs and Graphitic Nanostructures 41.2.2 Graphene, Graphene Oxide, and Highly Reduced Graphene Oxide 111.2.3 Activated Carbons 141.2.4 Starbons 141.2.5 Use of Ionic Liquids in the Synthesis of Carbon Materials 191.2.6 HTC 271.3 Brief History of HTC 27References 302 Porous Hydrothermal Carbons 37Robin J. White, Tim-Patrick Fellinger, Shiori Kubo, Nicolas Brun, and Maria-Magdalena Titirici2.1 Introduction 372.2 Templating – An Opportunity for Pore Morphology Control 392.2.1 Hard Templating in HTC 402.2.2 Soft Templating in HTC 422.2.3 Naturally Inspired Systems: Use of Natural Templates 492.3 Carbon Aerogels 502.3.1 Ovalbumin/Glucose-Derived HTC-Derived Carbogels 522.3.2 Borax-Mediated Formation of HTC-Derived Carbogels from Glucose 562.3.3 Carbogels from the Hydrothermal Treatment of Sugar and Phenolic Compounds 632.3.4 Emulsion-Templated “Carbo-HIPEs” from the HydrothermalTreatment of Sugar Derivatives and Phenolic Compounds 652.4 Summary and Outlook 69References 703 Porous Biomass-Derived Carbons: Activated Carbons 75Dolores Lozano-Castello, Juan Pablo Marco-Lozar, Camillo Falco, Maria-Magdalena Titirici, and Diego Cazorla-Amoros3.1 Introduction to Activated Carbons 753.2 Chemical Activation of Lignocellulosic Materials 773.2.1 H3PO4 Activation of Lignocellulosic Precursors 783.2.2 ZnCl2 Activation of Lignocellulosic Precursors 823.2.3 KOH and NaOH Activation of Lignocellulosic Precursors 843.3 Activated Carbons from Hydrothermally Carbonized Organic Materials and Biomass 863.3.1 Hydrochar Materials: Synthesis, Structural, and Chemical Properties 883.3.2 KOH Activation of Hydrochar Materials 893.4 Conclusions 95Acknowledgments 95References 964 Hydrothermally Synthesized Carbonaceous Nanocomposites 101Bo Hu, Hai-Zhou Zhu, and Shu-Hong Yu4.1 Introduction 1014.2 HTC Synthesis of Unique Carbonaceous Nanomaterials 1024.2.1 Carbonaceous Nanomaterials 1024.2.2 Carbonaceous Nanocomposites 1104.3 Conclusion and Outlook 121Acknowledgments 121References 1215 Chemical Modification of Hydrothermal Carbonization Materials 125Stephanie Wohlgemuth, Hiromitsu Urakami, Li Zhao, and Maria-Magdalena Titirici5.1 Introduction 1255.2 In Situ Doping of Hydrothermal Carbons 1265.2.1 Nitrogen 1265.2.2 Sulfur 1305.2.3 Boron 1325.2.4 Organic Monomers Sources 1325.2.5 Properties of Heteroatom-Doped Carbon Materials 1335.3 Postmodification of Carbonaceous Materials 1395.3.1 Chemical Handles for Functionalization Present on HTC Materials 1405.3.2 Perspectives on HTC Postmodification Strategies 143References 1456 Characterization of Hydrothermal Carbonization Materials 151Niki Baccile, Jens Weber, Camillo Falco, and Maria-Magdalena Titirici 6.1 Introduction 1516.2 Morphology of HTC Materials 1526.2.1 Morphology of Glucose-Derived Hydrothermal Carbons 1536.2.2 Morphology of Other Carbohydrate-Derived Hydrothermal Carbons 1576.2.3 Morphology of Cellulose- and Biomass-Derived Hydrothermal Carbons 1596.3 Elemental Composition and Yields 1616.4 FTIR 1646.5 XPS: Surface Groups 1656.6 Zeta Potential: Surface Charge 1666.7 XRD: Degree of Structural Order 1696.8 Thermal Analysis 1706.9 Structure Elucidation of Carbon Materials Using Solid-State NMR Spectroscopy 1726.9.1 Brief Introduction to Solid-State NMR 1726.9.2 Solid-State NMR of Crystalline Nanocarbons: Fullerenes and Nanotubes 1746.9.3 Solid-State NMR Study of Biomass Derivatives and their Pyrolyzed Carbons 1756.9.4 Solid-State NMR Study of Hydrothermal Carbons 1786.10 Porosity Analysis of Hydrothermal Carbons 1906.10.1 Introduction and Definition of Porosity 1906.10.2 Gas Physisorption 1916.10.3 Mercury Intrusion Porosity 2026.10.4 Scattering Methods 204References 2047 Applications of Hydrothermal Carbon in Modern Nanotechnology 213Marta Sevilla, Antonio B. Fuertes, Rezan Demir-Cakan, and Maria-Magdalena Titirici7.1 Introduction 2137.2 Energy Storage 2147.2.1 Electrodes in Rechargeable Batteries 2157.2.2 Electrodes in Supercapacitors 2297.2.3 Heterogeneous Catalysis 2347.2.4 HTC-Derived Materials as Catalyst Supports 2357.2.5 HTC-Derived Materials with Various Functionalities and Intrinsic Catalytic Properties 2397.3 Electrocatalysis in Fuel Cells 2417.3.1 Catalyst Supports in Direct Methanol Fuel Cells 2427.3.2 Heteroatom-Doped Carbons with Intrinsic Catalytic Activity for the ORR 2507.4 Photocatalysis 2557.5 Gas Storage 2607.5.1 CO2 Capture Using HTC-Based Carbons 2607.5.2 Hydrogen Storage Using HTC-Based Activated Carbons 2647.6 Adsorption of Pollutants from Water 2657.6.1 Removal of Heavy Metals 2657.6.2 Removal of Organic Pollutants 2717.7 HTC-Derived Materials in Sensor Applications 2727.7.1 Chemical Sensors 2727.7.2 Gas Sensors 2747.8 Bioapplications 2757.9 Drug Delivery 2767.9.1 Bioimaging 2797.10 Conclusions and Perspectives 282References 2838 Environmental Applications of Hydrothermal Carbonization Technology: Biochar Production, Carbon Sequestration, and Waste Conversion 295Nicole D. Berge, Claudia Kammann, Kyoung Ro, and Judy Libra8.1 Introduction 2958.2 Waste Conversion to Useful Products 2978.2.1 Conversion of MSW 2988.2.2 Conversion of Animal Waste 3028.2.3 Potential Hydrochar Uses 3068.3 Soil Application 3098.3.1 History of the Idea to Sequester Carbon in Soils Using Chars/Coals 3098.3.2 Consideration of Hydrochar Use in Soils 3118.3.3 Stability of Hydrochar in Soils 3118.3.4 Influence of Hydrochar on Soil Fertility and Crop Yields 3188.3.5 Greenhouse Gas Emissions from Char-Amended Soils 3238.3.6 Best-Practice Considerations for Biochar/Hydrochar Soil Application 3258.4 HTC Technology: Commercial Status and Research Needs 325References 3299 Scale-Up in Hydrothermal Carbonization 341Andrea Kruse, Daniela Baris, Nicole Troger, and Peter Wieczorek9.1 Introduction 3419.2 Basic Aspects of Process Development and Upscaling 3439.2.1 Batch/Tubular Reactors 3449.2.2 CSTRs 3459.2.3 Product Handling 3459.3 Risks of Scaling-Up 3469.4 Lab-Scale Experiments 3479.4.1 Experimental 3479.4.2 Results and Discussion 3489.5 Praxis Report 3489.6 Conclusions 352References 353Index

Dr. Maria-Magdalena Titirici, Max-Planck Institute of Colloids and Interfaces, GermanyMaria-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.

• List of Contributors xi Preface xiii1 Green Carbon 1Maria-Magdalena Titirici1.1 Introduction 11.2 Green Carbon Materials 31.2.1 CNTs and Graphitic Nanostructures 41.2.2 Graphene, Graphene Oxide, and Highly Reduced Graphene Oxide 111.2.3 Activated Carbons 141.2.4 Starbons 141.2.5 Use of Ionic Liquids in the Synthesis of Carbon Materials 191.2.6 HTC 271.3 Brief History of HTC 27References 302 Porous Hydrothermal Carbons 37Robin J. White, Tim-Patrick Fellinger, Shiori Kubo, Nicolas Brun, and Maria-Magdalena Titirici2.1 Introduction 372.2 Templating – An Opportunity for Pore Morphology Control 392.2.1 Hard Templating in HTC 402.2.2 Soft Templating in HTC 422.2.3 Naturally Inspired Systems: Use of Natural Templates 492.3 Carbon Aerogels 502.3.1 Ovalbumin/Glucose-Derived HTC-Derived Carbogels 522.3.2 Borax-Mediated Formation of HTC-Derived Carbogels from Glucose 562.3.3 Carbogels from the Hydrothermal Treatment of Sugar and Phenolic Compounds 632.3.4 Emulsion-Templated “Carbo-HIPEs” from the HydrothermalTreatment of Sugar Derivatives and Phenolic Compounds 652.4 Summary and Outlook 69References 703 Porous Biomass-Derived Carbons: Activated Carbons 75Dolores Lozano-Castello, Juan Pablo Marco-Lozar, Camillo Falco, Maria-Magdalena Titirici, and Diego Cazorla-Amoros3.1 Introduction to Activated Carbons 753.2 Chemical Activation of Lignocellulosic Materials 773.2.1 H3PO4 Activation of Lignocellulosic Precursors 783.2.2 ZnCl2 Activation of Lignocellulosic Precursors 823.2.3 KOH and NaOH Activation of Lignocellulosic Precursors 843.3 Activated Carbons from Hydrothermally Carbonized Organic Materials and Biomass 863.3.1 Hydrochar Materials: Synthesis, Structural, and Chemical Properties 883.3.2 KOH Activation of Hydrochar Materials 893.4 Conclusions 95Acknowledgments 95References 964 Hydrothermally Synthesized Carbonaceous Nanocomposites 101Bo Hu, Hai-Zhou Zhu, and Shu-Hong Yu4.1 Introduction 1014.2 HTC Synthesis of Unique Carbonaceous Nanomaterials 1024.2.1 Carbonaceous Nanomaterials 1024.2.2 Carbonaceous Nanocomposites 1104.3 Conclusion and Outlook 121Acknowledgments 121References 1215 Chemical Modification of Hydrothermal Carbonization Materials 125Stephanie Wohlgemuth, Hiromitsu Urakami, Li Zhao, and Maria-Magdalena Titirici5.1 Introduction 1255.2 In Situ Doping of Hydrothermal Carbons 1265.2.1 Nitrogen 1265.2.2 Sulfur 1305.2.3 Boron 1325.2.4 Organic Monomers Sources 1325.2.5 Properties of Heteroatom-Doped Carbon Materials 1335.3 Postmodification of Carbonaceous Materials 1395.3.1 Chemical Handles for Functionalization Present on HTC Materials 1405.3.2 Perspectives on HTC Postmodification Strategies 143References 1456 Characterization of Hydrothermal Carbonization Materials 151Niki Baccile, Jens Weber, Camillo Falco, and Maria-Magdalena Titirici 6.1 Introduction 1516.2 Morphology of HTC Materials 1526.2.1 Morphology of Glucose-Derived Hydrothermal Carbons 1536.2.2 Morphology of Other Carbohydrate-Derived Hydrothermal Carbons 1576.2.3 Morphology of Cellulose- and Biomass-Derived Hydrothermal Carbons 1596.3 Elemental Composition and Yields 1616.4 FTIR 1646.5 XPS: Surface Groups 1656.6 Zeta Potential: Surface Charge 1666.7 XRD: Degree of Structural Order 1696.8 Thermal Analysis 1706.9 Structure Elucidation of Carbon Materials Using Solid-State NMR Spectroscopy 1726.9.1 Brief Introduction to Solid-State NMR 1726.9.2 Solid-State NMR of Crystalline Nanocarbons: Fullerenes and Nanotubes 1746.9.3 Solid-State NMR Study of Biomass Derivatives and their Pyrolyzed Carbons 1756.9.4 Solid-State NMR Study of Hydrothermal Carbons 1786.10 Porosity Analysis of Hydrothermal Carbons 1906.10.1 Introduction and Definition of Porosity 1906.10.2 Gas Physisorption 1916.10.3 Mercury Intrusion Porosity 2026.10.4 Scattering Methods 204References 2047 Applications of Hydrothermal Carbon in Modern Nanotechnology 213Marta Sevilla, Antonio B. Fuertes, Rezan Demir-Cakan, and Maria-Magdalena Titirici7.1 Introduction 2137.2 Energy Storage 2147.2.1 Electrodes in Rechargeable Batteries 2157.2.2 Electrodes in Supercapacitors 2297.2.3 Heterogeneous Catalysis 2347.2.4 HTC-Derived Materials as Catalyst Supports 2357.2.5 HTC-Derived Materials with Various Functionalities and Intrinsic Catalytic Properties 2397.3 Electrocatalysis in Fuel Cells 2417.3.1 Catalyst Supports in Direct Methanol Fuel Cells 2427.3.2 Heteroatom-Doped Carbons with Intrinsic Catalytic Activity for the ORR 2507.4 Photocatalysis 2557.5 Gas Storage 2607.5.1 CO2 Capture Using HTC-Based Carbons 2607.5.2 Hydrogen Storage Using HTC-Based Activated Carbons 2647.6 Adsorption of Pollutants from Water 2657.6.1 Removal of Heavy Metals 2657.6.2 Removal of Organic Pollutants 2717.7 HTC-Derived Materials in Sensor Applications 2727.7.1 Chemical Sensors 2727.7.2 Gas Sensors 2747.8 Bioapplications 2757.9 Drug Delivery 2767.9.1 Bioimaging 2797.10 Conclusions and Perspectives 282References 2838 Environmental Applications of Hydrothermal Carbonization Technology: Biochar Production, Carbon Sequestration, and Waste Conversion 295Nicole D. Berge, Claudia Kammann, Kyoung Ro, and Judy Libra8.1 Introduction 2958.2 Waste Conversion to Useful Products 2978.2.1 Conversion of MSW 2988.2.2 Conversion of Animal Waste 3028.2.3 Potential Hydrochar Uses 3068.3 Soil Application 3098.3.1 History of the Idea to Sequester Carbon in Soils Using Chars/Coals 3098.3.2 Consideration of Hydrochar Use in Soils 3118.3.3 Stability of Hydrochar in Soils 3118.3.4 Influence of Hydrochar on Soil Fertility and Crop Yields 3188.3.5 Greenhouse Gas Emissions from Char-Amended Soils 3238.3.6 Best-Practice Considerations for Biochar/Hydrochar Soil Application 3258.4 HTC Technology: Commercial Status and Research Needs 325References 3299 Scale-Up in Hydrothermal Carbonization 341Andrea Kruse, Daniela Baris, Nicole Troger, and Peter Wieczorek9.1 Introduction 3419.2 Basic Aspects of Process Development and Upscaling 3439.2.1 Batch/Tubular Reactors 3449.2.2 CSTRs 3459.2.3 Product Handling 3459.3 Risks of Scaling-Up 3469.4 Lab-Scale Experiments 3479.4.1 Experimental 3479.4.2 Results and Discussion 3489.5 Praxis Report 3489.6 Conclusions 352References 353Index