
High-Performance Materials from Bio-based Feedstocks
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The latest advancements in the production, properties, and performance of bio-based feedstock materials
In High-Performance Materials from Bio-based Feedstocks, an accomplished team of researchers delivers a comprehensive exploration of recent developments in the research, manufacture, and application of advanced materials from bio-based feedstocks. With coverage of bio-based polymers, the inorganic components of biomass, and the conversion of biomass to advanced materials, the book illustrates the research and commercial potential of new technologies in the area.
Real-life applications in areas as diverse as medicine, construction, synthesis, energy storage, agriculture, packaging, and food are discussed in the context of the structural properties of the materials used. The authors offer deep insights into materials production, properties, and performance.
Perfect for chemists, environmental scientists, engineers, and materials scientists, High-Performance Materials from Bio-based Feedstocks will also earn a place in the libraries of academics, industrial researchers, and graduate students with an interest in biomass conversion, green chemistry, and sustainability.
* A thorough introduction to the latest developments in advanced bio-based feedstock materials research
* Comprehensive explorations of a vast range of real-world applications, from tissue scaffolds and drug delivery to batteries, sorbents, and controlled release fertilizers
* Practical discussions of the organic and inorganic components of biomass and the conversion of biomass to advanced materials
* In-depth examinations of the structural properties of commercially and academically significant biomass materials
For more information on the Wiley Series in Renewable Resources, visit www.wiley.com/go/rrs
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Persons
Editors
Andrew J. Hunt, PhD, is a Lecturer in Applied Chemistry at the Materials Chemistry Research Center, Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Thailand.
Nontipa Supanchaiyamat, PhD, is a Lecturer in Applied Chemistry at the Materials Chemistry Research Center, Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Thailand.
Kaewta Jetsrisuparb, PhD, is a Lecturer in Chemical Engineering in the Department of Chemical Engineering, Khon Kaen University, Thailand.
Jesper T.N. Knijnenburg, PhD, is a Lecturer in Biodiversity and Environmental Management at the International College, Khon Kaen University, Thailand.
Content
Series Preface xxi
1 High-performance
Materials from Bio-based
Feedstocks: Introduction and Structure of the Book 1 Kaewta Jetsrisuparb, Jesper T.N. Knijnenburg, Nontipa Supanchaiyamat and Andrew J. Hunt
1.1 Introduction 1
1.2 High-performance Bio-based Materials and Their Applications 4
1.2.1 Biomass Constituents 4
1.2.2 Bioderived Materials 7
1.3 Structure of the Book 10
2 Bio-based Carbon Materials for Catalysis 13 Chaiyan Chaiya and Sasiradee Jantasee
2.1 Introduction 13
2.2 Biomass Resources for Carbon Materials 14
2.2.1 Wood from Natural Forests 14
2.2.2 Agricultural Residues 17
2.3 Thermochemical Conversion Processes 18
2.3.1 Carbonization and Pyrolysis 18
2.3.2 Activation 20
2.3.3 Hydrothermal Carbonization 23
2.3.4 Graphene Preparation from Biomass 24
2.4 Fundamentals of Heterogeneous Catalysis 25
2.5 Catalysis Applications of Selected Bio-based Carbon Materials 26
2.5.1 Biochar 26
2.5.2 Modified Biochar 28
2.5.3 Biomass-Derived Activated Carbon 30
2.5.4 Hydrothermal Bio-based Carbons 34
2.5.5 Sugar-Derived Carbon Catalysts 35
2.5.6 Carbon Nanotubes from Biomass 36
2.5.7 Graphene and Its Derivatives 37
2.6 Summary and Future Aspects 37
3 Starbon®: Novel Template-Free Mesoporous Carbonaceous Materials from Biomass - Synthesis, Functionalisation and Applications in Adsorption, and Catalysis 47 Duncan J. Macquarrie, Tabitha H.M. Petchey and Cinthia J. Meña Duran
3.1 Introduction 47
3.2 Choice of Polysaccharide 48
3.2.1 Synthetic Procedure 49
3.2.2 Derivatisation 51
3.2.3 Applications 56
3.2.4 Adsorption Processes 63
3.2.5 Conclusion 69
4 Conversion of Biowastes into Carbon-based Electrodes 73 Xiaotong Feng and Qiaosheng Pu
4.1 Introduction 73
4.2 Conversion Techniques of Biowastes 74
4.2.1 Carbonization 75
4.2.2 Activation 77
4.3 Structure and Doping 79
4.3.1 Biowaste Selection 79
4.3.2 Structure Control 81
4.3.3 Heteroatom Doping 83
4.4 Electrochemical Applications 84
4.4.1 Supercapacitors 84
4.4.2 Capacitive Deionization Cells 86
4.4.3 Hydrogen and Oxygen Evolution 88
4.4.4 Fuel Cells 90
4.4.5 Lithium-Ion Batteries and Others 94
4.5 Conclusion and Outlook 95
5 Bio-based Materials in Electrochemical Applications 105 Itziar Iraola-Arregui, Mohammed Aqil, Vera Trabadelo, Ismael Saadoune and Hicham Ben Youcef
5.1 Introduction 105
5.2 Fundamentals of Bio-based Materials 106
5.2.1 Bio-based Polymers 106
5.2.2 Carbonaceous Materials from Biological Feedstocks 108
5.3 Application of Bio-based Materials in Batteries 109
5.3.1 General Concept of Metal-Ion Batteries 109
5.4 Application of Bio-based Polymers in Capacitors 115
5.4.1 General Concept of Electrochemical Capacitors 115
5.4.2 Electrode Materials 116
5.5 Alternative Binders for Sustainable Electrochemical Energy Storage 119
5.5.1 Polysaccharides and Cellulose-based Binders 120
5.5.2 Lignin 123
5.6 Application of Bio-based
Polymers in Fuel Cells 123
5.6.1 Chitosan 124
5.6.2 Other Biopolymers 125
5.7 Conclusion and Outlook 126
6 Bio-based Materials Using Deep Eutectic Solvent Modifiers 133 Wanwan Qu, Sarah Key and Andrew P. Abbott
6.1 Introduction 133
6.2 Bio-based Materials 134
6.2.1 Ionic Liquids 136
6.2.2 Deep Eutectic Solvents 136
6.2.3 Morphological/Mechanical Modification 137
6.2.4 Chemical Modification 139
6.2.5 Composite Formation 141
6.2.6 Gelation 143
6.3 Conclusion 145
7 Biopolymer Composites for Recovery of Precious and Rare Earth Metals 151 Jesper T.N. Knijnenburg and Kaewta Jetsrisuparb
7.1 Introduction 151
7.2 Mechanisms of Metal Adsorption 153
7.2.1 Silver 153
7.2.2 Gold and Platinum Group Metals 153
7.2.3 Rare Earth Metals 154
7.3 Composite Materials and Their Adsorption 154
7.3.1 Cellulose-based Composite Adsorbents 154
7.3.2 Chitosan-based Composite Adsorbents 163
7.3.3 Alginate-based Adsorbents 170
7.3.4 Lignin-based Composite Adsorbents 173
7.4 Conclusion and Outlook 175
8 Bio-Based Materials in Anti-HIV Drug Delivery 181 Oranat Chuchuen and David F. Katz
8.1 Introduction 181
8.2 Biomedical Strategies for HIV Prophylaxis 182
8.3 Properties of Anti-HIV Drug Delivery Systems 184
8.4 Bio-based Materials for Anti-HIV Drug Delivery Systems 185
8.4.1 Cellulose 186
8.4.2 Chitosan 190
8.4.3 Polylactic Acid 191
8.4.4 Carrageenan 193
8.4.5 Alginate 194
8.4.6 Hyaluronic Acid 195
8.4.7 Pectin 196
8.5 Conclusion 196
9 Chitin - A Natural Bio-feedstock and Its Derivatives: Chemistry and Properties for Biomedical Applications 207 Anu Singh, Shefali Jaiswal, Santosh Kumar and Pradip K. Dutta
9.1 Bio-feedstocks 207
9.1.1 Chitin 208
9.1.2 Chitosan 208
9.1.3 Glucan 209
9.1.4 Chitin-Glucan Complex 209
9.1.5 Polyphenols 209
9.2 Synthetic Route 210
9.2.1 Isolation of ChGC 210
9.2.2 Derivatives of ChGC and Its Modified Polymers 210
9.2.3 Preparation of d-Glucosamine from Chitin/Chitosan-Glucan 212
9.3 Properties of Chitin, ChGC, and Its Derivatives for Therapeutic Applications 212
9.3.1 Antibacterial Activity 212
9.3.2 Anticancer Activity 212
9.3.3 Antioxidant Activity 212
9.3.4 Therapeutic Applications 213
9.4 Gene Therapy - A Biomedical Approach 213
9.5 Cs: Properties and Factors Affecting Gene Delivery 214
9.6 Organic Modifications of Cs Backbone for Enhancing the Properties of Cs Associated with Gene Delivery 215
9.6.1 Modification of Cs with Hydrophilic Groups 215
9.6.2 Modification in Cs by Hydrophobic Groups 216
9.6.3 Modification by Cationic Substituents 216
9.6.4 Modification by Target Ligands 217
9.7 Multifunctional Modifications of Cs 218
9.8 Miscellaneous 218
9.9 Conclusion 218
10 Carbohydrate-Based Materials for Biomedical Applications 235 Chadamas Sakonsinsiri
10.1 Introduction 235
10.2 Bio-based Glycopolymers 236
10.2.1 Chitin and Chitosan 236
10.2.2 Cellulose 238
10.2.3 Starch 239
10.2.4 Dextran 239
10.3 Synthetic Carbohydrate-based Functionalized Materials 240
10.3.1 Glycomimetics 240
10.3.2 Presentation of Glycomimetics in Multivalent Scaffolds 241
10.4 Conclusion 243
11 Organic Feedstock as Biomaterial for Tissue Engineering 247 Poramate Klanrit
11.1 Introduction 247
11.2 Protein-based Natural Biomaterials 248
11.2.1 Silk 249
11.2.2 Collagen 249
11.2.3 Decellularized Skins 251
11.2.4 Fibrin/Fibrinogen 252
11.3 Polysaccharide-based Natural Biomaterials 253
11.3.1 Chitosan 253
11.3.2 Alginate 254
11.3.3 Agarose 255
11.4 Summary 255
12 Green Synthesis of Bio-based Metal-Organic Frameworks 261 Emile R. Engel, Bernardo Castro-Dominguez and Janet L. Scott
12.1 Introduction 261
12.2 Green Synthesis of MOFs 262
12.2.1 Solvent-Free and Low Solvent Synthesis 262
12.2.2 Green Solvents 264
12.2.3 Sonochemical Synthesis 266
12.2.4 Electrochemical Synthesis 266
12.3 Bio-based Ligands 266
12.3.1 Amino Acids 266
12.3.2 Aliphatic Diacids 267
12.3.3 Cyclodextrins 269
12.3.4 Other 270
12.3.5 Exemplars: Bio-based MOFs Obtainable via Green Synthesis 271
12.4 Metal Ion Considerations 271
12.4.1 Calcium 272
12.4.2 Magnesium 272
12.4.3 Manganese 273
12.4.4 Iron 273
12.4.5 Titanium 274
12.4.6 Zirconium 274
12.4.7 Aluminium 275
12.4.8 Zinc 275
12.5 Challenges for Further Development Towards Applications 276
12.5.1 Stability Issues 276
12.5.2 Scalability and Cost 278
12.5.3 Competing Alternative Materials 279
12.6 Conclusion 280
13 Geopolymers Based on Biomass Ash and Bio-based Additives for Construction Industry 289 Prinya Chindaprasirt, Ubolluk Rattanasak and Patcharapol Posi
13.1 Introduction 289
13.2 Pozzolan and Agricultural Waste Ash 290
13.3 Geopolymer 292
13.4 Combustion of Biomass 294
13.4.1 Open Field Burning 294
13.4.2 Controlled Burning 294
13.4.3 Boiler Burning 294
13.4.4 Fluidized Bed Burning 295
13.5 Properties and Utilization of Biomass Ashes 295
13.6 Biomass Ash-based Geopolymer 299
13.6.1 Rice Husk Ash-based Geopolymer 300
13.6.2 Bagasse Ash-based Geopolymer 304
13.6.3 Palm Oil Fuel Ash-based Geopolymer 306
13.6.4 Other Biomass-based Geopolymers 308
13.6.5 Use of Biomass in Making Sodium Silicate Solution and Other Products 308
13.6.6 Fire Resistance of Bio-based Geopolymer 309
13.7 Conclusion 309
14 The Role of Bio-based Excipients in the Formulation of Lipophilic Nutraceuticals 315 Alexandra Teleki, Christos Tsekou and Alan Connolly
14.1 Introduction 315
14.2 Emulsions and the Importance of Bio-based Materials as Emulsifiers 316
14.2.1 Conventional Micro-and Nanoemulsions 316
14.2.2 Pickering-Stabilised Emulsions 319
14.3 Novel Formulation Technologies: Colloidal Delivery Vesicles 320
14.3.1 Microgels 320
14.3.2 Nanoprecipitation 321
14.3.3 Liposomes 322
14.3.4 Complex Coacervation 323
14.3.5 Complexation 325
14.4 Key Drying Technologies Employed During Formulation 325
14.4.1 Spray Drying 325
14.4.2 Spray-Freeze Drying 327
14.4.3 Electrohydrodynamic Processing 328
14.4.4 Fluid Bed Drying 329
14.4.5 Extrusion 329
14.5 Conclusions and Future Perspectives 330
15 Bio-derived Polymers for Packaging 337 Pornnapa Kasemsiri, Uraiwan Pongsa, Manunya Okhawilai, Salim Hiziroglu, Nawadon Petchwattana, Wilaiporn Kraisuwan and Benjatham Sukkaneewat
15.1 Introduction 337
15.2 Starch 338
15.3 Chitin/Chitosan 340
15.4 Cellulose and Its Derivatives 342
15.4.1 Cellulose Nanocrystals 343
15.4.2 Cellulose Nanofibers 343
15.4.3 Bacterial Nanocellulose 344
15.4.4 Carboxymethyl Cellulose 344
15.5 Poly(Lactic Acid) 345
15.5.1 Bio-based Toughening Agents Used in PLA Toughness Improvement 346
15.5.2 Toughening of PLA and Its Properties Related to Packaging Applications 346
15.6 Bio-based Active and Intelligent Agents for Packaging 348
15.6.1 Active Agents 348
15.6.2 Intelligent Packaging 351
15.7 Conclusion 351
16 Recent Developments in Bio-Based Materials for Controlled-Release Fertilizers 361 Kritapas Laohhasurayotin, Doungporn Yiamsawas and Wiyong Kangwansupamonkon
16.1 Introduction and Historical Review 361
16.1.1 Early Fertilizer Development and Its Impact on Environment 361
16.1.2 Controlled-Release Fertilizer 362
16.2 Mechanistic View of Controlled-Release Fertilizer from Bio-based Materials 365
16.2.1 Coating Type 366
16.2.2 Matrix Type 367
16.2.3 Other Release Mechanisms 368
16.3 Controlled Release Technologies from Bio-based Materials 368
16.3.1 Natural Polymers and Their Fertilizer Applications 369
16.3.2 Bio-based Modified Polymer Coatings for Controlled-Release Fertilizer 376
16.3.3 Biochar and Other Carbon-based Fertilizers 380
16.4 Conclusion and Foresight 385
Index 399
1
High-performance Materials from Bio-based Feedstocks: Introduction and Structure of the Book
Kaewta Jetsrisuparb1, Jesper T.N. Knijnenburg2, Nontipa Supanchaiyamat3 and Andrew J. Hunt3
1 Department of Chemical Engineering, Khon Kaen University, Khon Kaen, Thailand
2 International College, Khon Kaen University, Khon Kaen, Thailand
3 Materials Chemistry Research Center (MCRC), Department of Chemistry, Centre of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen, Thailand
1.1 Introduction
The overexploitation of the Earth's resources over the last century has led to a decrease in natural resources, a loss of natural habitat, climate change, and degradation of the environment, resulting in the extinction of several species [1]. The recovery of global economics after COVID-19 is also driving lifestyle changes, leading to increased high-performance materials production. As a result, a large number of nonrenewable resources are being utilized, which inevitably contributes to the generation of waste and may lead to detrimental effects to both environment and health. In addition, the scarcity of fossil resources and finite elements with potential global supply chain vulnerabilities are global concerns. Concerns over the supply of natural resources and potential damage to the environment have compelled governments to implement policies that mitigate the risk of further damage. The formation of the World Commission on Environment and Development (WCED) in 1983 and their report called "Our Common Future" in 1987 (also called "Brundtland report") was one of the catalysts for the move toward a sustainable future for humankind [2]. The definition of sustainable development is the development that "meets the needs of the present without compromising the ability of future generations to meet their own needs" [3]. Importantly, sustainability is a complex balance between societal, economic, and environmental needs, where this must be achieved in unison [4]. Implementation of a bio-based circular economy including minimizing the waste by recycling materials and utilization of replenishable resources is key to sustainable development.
Historically, chemistry goes hand in hand with innovation, thus promoting a positive image of this industry. However, the perception of the industry can be tarnished with media reports of life-threatening accidents and environmental pollution [5]. Anastas and Warner pioneered the concept of green chemistry, "the invention, design and application of chemical products and processes to reduce or to eliminate the use and generation of hazardous substances" [6]. Today, green chemistry is recognized and widely accepted to pursue sustainable development. The 12 principles of green chemistry (stated next) are regarded as a blueprint for achieving the aims of green chemistry. Moreover, green chemistry can aid in the development of sustainable bio-based chemicals and importantly also high-performance materials.
The 12 principles of green chemistry as stated by Anastas and Warner [6] are:
- Prevention
It is better to prevent waste than to treat or clean up waste after it has been created.
- Atom Economy
Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product.
- Less Hazardous Chemical Syntheses
Wherever practicable, synthetic methods should be designed to use and generate substances that possess little or no toxicity to human health and the environment.
- Designing Safer Chemicals
Chemical products should be designed to effect their desired function while minimizing their toxicity.
- Safer Solvents and Auxiliaries
The use of auxiliary substances (e.g. solvents, separation agents, etc.) should be made unnecessary wherever possible and innocuous when used.
- Design for Energy Efficiency
Energy requirements of chemical processes should be recognized for their environmental and economic impacts and should be minimized. If possible, synthetic methods should be conducted at ambient temperature and pressure.
- Use of Renewable Feedstocks
A raw material or feedstock should be renewable rather than depleting whenever technically and economically practicable.
- Reduce Derivatives
Unnecessary derivatization (use of blocking groups, protection/deprotection, temporary modification of physical/chemical processes) should be minimized or avoided if possible because such steps require additional reagents and can generate waste.
- Catalysis
Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.
- Design for Degradation
Chemical products should be designed so that at the end of their function they break down into innocuous degradation products and do not persist in the environment.
- Real-time Analysis for Pollution Prevention
Analytical methodologies need to be further developed to allow for real-time, in-process monitoring and control prior to the formation of hazardous substances.
- Inherently Safer Chemistry for Accident Prevention
Substances and the form of a substance used in a chemical process should be chosen to minimize the potential for chemical accidents, including releases, explosions, and fires. [6]
By examining the 12 principles of green chemistry, the use of waste biomass and bio-based products to produce high-performance materials is in agreement with the seventh principle, which encourages the use of renewable feedstocks. The utilization of renewable resources has an added benefit as they can potentially lead to the development of carbon-neutral products.
According to the Kirk-Othmer Encyclopedia of Chemical Technology, bio-based materials refer to "products that mainly consist of a substance (or substances) derived from living matter (biomass) and either occur naturally or are synthesized, or it may refer to products made by processes that use biomass" [7]. Strictly speaking, this also includes traditional materials such as paper, leather, and wood, but these traditional uses are outside the scope of this book. It is important to note that bio-based materials are different from biomaterials (which involve biocompatibility), and being bio-based does not always mean the material will be biodegradable or safe.
The use of bio-based materials seems to be an appropriate approach to minimize the negative impact on the environment while harnessing the unique properties they offer. The development application of high-performance advanced bio-based materials through green synthetic approaches (i.e. application of the 12 principles of green chemistry) can aid in developing sustainable circular economies, while still minimizing environmental impacts. High-performance bio-based materials can be applied in catalysis, energy materials, polymers, medical devices, and even construction materials to name but a few.
A significant source of biomass which is ripe for exploitation into high-performance materials comes in the form of waste or agricultural residues. These include residues from food (e.g. corncob, sugarcane bagasse, rice husk, rice straw, and wheat straw) and non-food production (e.g. cellulose and lignin), forest residues, industrial by-products (e.g. ashes from biomass power generation), animal wastes (e.g. manure) as well as municipal wastes [7, 8]. These resources offer a complex mixture of polymers, inorganics, and chemicals, which can include but are not limited to polysaccharides, lignin, proteins, and ash, all of which are attractive alternative feedstocks to replace nonrenewable fossil-based resources. Exhaustion of fossil fuels and other finite resources is a driver for bio-based materials for high-performance applications. The structural diversity of biomass constituents and their unique properties are also promising for new applications including high-performance products.
Despite the great potential, some of the biggest challenges in using biomass as feedstock for high-performance applications are its heterogeneity, seasonal variation, and complexity regarding separation. In many cases, biomass needs to undergo some form of processing prior to being used as high-performance materials. Typically, the processing of biomass can be performed using chemical, biochemical, and thermochemical processes. These challenges are being tackled as part of the growth in holistic biorefineries, and such approaches that generate no waste are vital for maximizing the value of biomass.
However, unlike petrochemical feedstocks that require significant functionalization, bio-based feedstocks are blessed with an abundance of functionalities. As such, the development of high-performance materials from biomass requires different chemistries compared to those from fossil resources. The benefits of biomass utilization for industrial-scale production of high-performance materials are that they can potentially reduce waste and production costs, in addition to being carbon neutral, low cost, versatile, and renewable.
1.2 High-performance Bio-based Materials and Their...
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