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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Serie: Wiley Series in Renewable Resources
- Sprache: Englisch
High-Performance Materials from Bio-based Feedstocks 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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Table of Contents
Cover
Series Page
Title Page
Copyright Page
Dedication Page
List of Contributors
Series Preface
1 High‐performance Materials from Bio‐based Feedstocks: Introduction and Structure of the Book
1.1 Introduction
1.2 High‐performance Bio‐based Materials and Their Applications
1.3 Structure of the Book
References
2 Bio‐based Carbon Materials for Catalysis
2.1 Introduction
2.2 Biomass Resources for Carbon Materials
2.3 Thermochemical Conversion Processes
2.4 Fundamentals of Heterogeneous Catalysis
2.5 Catalysis Applications of Selected Bio‐based Carbon Materials
2.6 Summary and Future Aspects
References
3 Starbon
®
: Novel Template‐Free Mesoporous Carbonaceous Materials from Biomass – Synthesis, Functionalisation and Applications in Adsorption, and Catalysis
3.1 Introduction
3.2 Choice of Polysaccharide
References
4 Conversion of Biowastes into Carbon‐based Electrodes
4.1 Introduction
4.2 Conversion Techniques of Biowastes
4.3 Structure and Doping
4.4 Electrochemical Applications
4.5 Conclusion and Outlook
Acknowledgments
References
5 Bio‐based Materials in Electrochemical Applications
5.1 Introduction
5.2 Fundamentals of Bio‐based Materials
5.3 Application of Bio‐based Materials in Batteries
5.4 Application of Bio‐based Polymers in Capacitors
5.5 Alternative Binders for Sustainable Electrochemical Energy Storage
5.6 Application of Bio‐based Polymers in Fuel Cells
5.7 Conclusion and Outlook
References
6 Bio‐based Materials Using Deep Eutectic Solvent Modifiers
6.1 Introduction
6.2 Bio‐based Materials
6.3 Conclusion
References
7 Biopolymer Composites for Recovery of Precious and Rare Earth Metals
7.1 Introduction
7.2 Mechanisms of Metal Adsorption
7.3 Composite Materials and Their Adsorption
7.4 Conclusion and Outlook
References
8 Bio‐Based Materials in Anti‐HIV Drug Delivery
8.1 Introduction
8.2 Biomedical Strategies for HIV Prophylaxis
8.3 Properties of Anti‐HIV Drug Delivery Systems
8.4 Bio‐based Materials for Anti‐HIV Drug Delivery Systems
8.5 Conclusion
References
9 Chitin – A Natural Bio‐feedstock and Its Derivatives: Chemistry and Properties for Biomedical Applications
9.1 Bio‐feedstocks
9.2 Synthetic Route
9.3 Properties of Chitin, ChGC, and Its Derivatives for Therapeutic Applications
9.4 Gene Therapy – A Biomedical Approach
9.5 Cs: Properties and Factors Affecting Gene Delivery
9.6 Organic Modifications of Cs Backbone for Enhancing the Properties of Cs Associated with Gene Delivery
9.7 Multifunctional Modifications of Cs
9.8 Miscellaneous
9.9 Conclusion
Acknowledgments
References
10 Carbohydrate‐Based Materials for Biomedical Applications
10.1 Introduction
10.2 Bio‐based Glycopolymers
10.3 Synthetic Carbohydrate‐based Functionalized Materials
10.4 Conclusion
References
11 Organic Feedstock as Biomaterial for Tissue Engineering
11.1 Introduction
11.2 Protein‐based Natural Biomaterials
11.3 Polysaccharide‐based Natural Biomaterials
11.4 Summary
References
12 Green Synthesis of Bio‐based Metal–Organic Frameworks
12.1 Introduction
12.2 Green Synthesis of MOFs
12.3 Bio‐based Ligands
12.4 Metal Ion Considerations
12.5 Challenges for Further Development Towards Applications
12.6 Conclusion
References
13 Geopolymers Based on Biomass Ash and Bio‐based Additives for Construction Industry
13.1 Introduction
13.2 Pozzolan and Agricultural Waste Ash
13.3 Geopolymer
13.4 Combustion of Biomass
13.5 Properties and Utilization of Biomass Ashes
13.6 Biomass Ash‐based Geopolymer
13.7 Conclusion
References
14 The Role of Bio‐based Excipients in the Formulation of Lipophilic Nutraceuticals
14.1 Introduction
14.2 Emulsions and the Importance of Bio‐based Materials as Emulsifiers
14.3 Novel Formulation Technologies: Colloidal Delivery Vesicles
14.4 Key Drying Technologies Employed During Formulation
14.5 Conclusions and Future Perspectives
References
15 Bio‐derived Polymers for Packaging
15.1 Introduction
15.2 Starch
15.3 Chitin/Chitosan
15.4 Cellulose and Its Derivatives
15.5 Poly(Lactic Acid)
15.6 Bio‐based Active and Intelligent Agents for Packaging
15.7 Conclusion
References
16 Recent Developments in Bio‐Based Materials for Controlled‐Release Fertilizers
16.1 Introduction and Historical Review
16.2 Mechanistic View of Controlled‐Release Fertilizer from Bio‐based Materials
16.3 Controlled Release Technologies from Bio‐based Materials
16.4 Conclusion and Foresight
Acknowledgments
References
Index
End User License Agreement
List of Tables
Chapter 2
Table 2.1
Weight ratio of chemical compositions in lignocellulosic materials
...
Table 2.2
Chemical components in various wood categories [13–18].
Table 2.3
Comparison of typical physical and chemical properties of bio‐base
...
Table 2.4
Comparison of various catalysts for biodiesel production.
Chapter 3
Table 3.1
Summarised IR data of a range of sulphonated and unsulphonated Sta
...
Table 3.2
Textural properties of N‐doped Starbon compared with N‐free analog
...
Table 3.3
Nitrogen content of N‐doped Starbons.
Table 3.4
Collected data for the adsorption of phenols on alginic‐acid‐deriv
...
Table 3.5
Adsorption capacities for various alginic‐acid‐derived Starbons an
...
Chapter 4
Table 4.1
Conversion techniques and activation procedures for the preparatio
...
Chapter 7
Table 7.1
Adsorption performance of precious and rare earth metals of select
...
Table 7.2
Adsorption performance of precious and rare earth metals of select
...
Table 7.3
Adsorption performance of precious and rare earth metals of select
...
Table 7.4
Adsorption performance of precious metals of selected lignin‐based
...
Chapter 8
Table 8.1
Bio‐based materials used in the development of anti‐HIV drug deliv
...
Chapter 9
Table 9.1
Various bio‐feedstocks for obtaining biopolymers.
Table 9.2
Summary of special characteristics of target ligand‐modified Cs‐ba
...
Table 9.3
Summary of special features/application in multifunctional modific
...
Table 9.4
Summary of special features/biomedical application in Cs‐based nan
...
Chapter 12
Table 12.1
Examples of bio‐based MOFs for which green or near‐green synthesi
...
Table 12.2
Comparison between MOFs and alternative materials.
Chapter 13
Table 13.1
Typical chemical compositions of rice husk ash, palm oil fuel ash
...
Table 13.2
Typical chemical compositions of external‐source materials.
Chapter 15
Table 15.1
Classification of bio‐based polymers.
Table 15.2
Mechanical properties of PLA blends with bio‐based toughening age
...
Chapter 16
Table 16.1
Structures and sources of common biopolymers.
List of Illustrations
Chapter 2
Figure 2.1
Some advantages of bio‐based carbon materials.
Figure 2.2
Classification of biomass.
Figure 2.3
Thermochemical processes for biomass conversion.
Figure 2.4
Examples of chemical reactions catalyzed by biomass‐derived carbo
...
Figure 2.5
Transesterification of triglyceride.
Figure 2.6
Esterification of fatty acid.
Figure 2.7
Esterification of acetic acid.
Figure 2.8
Reduction of nitrobenzene.
Figure 2.9
Conversion of glucose to 5‐hydroxymethylfurfural.
Figure 2.10
Hydrolysis of cellulose.
Figure 2.11
Hydrogenation of levulinic acid.
Chapter 3
Figure 3.1
Role of capillary forces in the collapse of soft porous materials
...
Figure 3.2
Evolution of porosity as a function of water : butanol compositio
...
Figure 3.3
Comparison of porosity of the three major Starbon types.
Figure 3.4
Diesterification of succinic acid in aqueous ethanol as a functio
...
Figure 3.5
Esterification of oleic acid with sulphonated Starbon materials.
...
Figure 3.6
Conversion of xylose to furfural and extraction of furfural.
Figure 3.7
Functionalisation of steroids via Starbon acid‐catalysed Ritter r
...
Figure 3.8
Friedel Crafts reactions catalysed by a range of Starbon acids. (
...
Figure 3.9
Synthesis of an N‐heterocyclic carbine‐based catalyst on the Star
...
Figure 3.10
Preparation of a chiral bis‐oxalolidinone catalyst via surface b
...
Figure 3.11
Selective acylation of a diol by a supported Cu‐bis‐oxalodinone/
...
Figure 3.12
Comparison of pH‐dependent adsorption behaviour (via COD reducti
...
Figure 3.13
Four bioactive molecules studied for adsorption/desorption behav
...
Chapter 4
Figure 4.1
Schematic illustration of the carbon cycle and the production of
...
Figure 4.2
(a) Illustrated procedure of fabricating N, S co‐doped porous car
...
Figure 4.3
(a) Schematic of the synthesis process for the hemp‐derived carbo
...
Figure 4.4
(a) Schematic illustration of the preparation process of N, P‐co‐
...
Figure 4.5
(a) Schematic illustration of the synthetic process of the Co3O4/
...
Figure 4.6
(a) Illustration of fabrication of co‐doped egg‐CMS. SEM images o
...
Chapter 5
Figure 5.1
Schematic diagram showing the different products obtained from se
...
Figure 5.2
Schematic presentation of the charged and discharged structure of
...
Figure 5.3
(a) Schematic illustration of the fabrication procedure for hollo
...
Figure 5.4
Schematic diagram of a supercapacitor.
Figure 5.5
Bio‐based binder structure and features. (a) CMC (sodium carboxym
...
Figure 5.6
Schematic representation of the polymer electrolyte membrane fuel
...
Chapter 6
Figure 6.1
Sample of starch plasticised with glycerol and choline chloride (
...
Figure 6.2
Dry leather samples aqueous post‐tanned in (a) and DES post‐tanne
...
Figure 6.3
Starch‐based thermoplastic wood after forming (a), after grinding
...
Figure 6.4
From the top going clockwise: starch composites made with orange
...
Chapter 7
Figure 7.1
Natural abundance of precious metals and rare earth elements (REE
...
Figure 7.2
(a) SEM images of P‐CNC, P‐CNF, and T‐CNF before (top) and after
...
Figure 7.3
(a) Synthetic route for the preparation of the CMC‐g‐PAA hydrogel
...
Figure 7.4
(a) Preparation of chitosan grafted on persimmon tannin extract (
...
Figure 7.5
Reaction pathway for the synthesis of amidoxime‐modified magnetic
...
Figure 7.6
Removal of Au, Pd, Pt, and Ag by SAPAs, SAPVA, and activated carb
...
Figure 7.7
(a) SEM image of the PNMA‐LS composite spheres, (b) TEM image of
...
Chapter 8
Figure 8.1
Representative images of various drug delivery systems in develop
...
Chapter 9
Figure 9.1
Schematic representation of the cell‐wall fractionation and sea a
...
Figure 9.2
CSMMA NPs for efficient gene transfection and drug delivery.
Chapter 10
Figure 10.1
Carbohydrate–protein interactions between pathogenic agents and
...
Figure 10.2
Exemplified multivalent glycomaterials using different scaffolds
...
Figure 10.3
Chemical structures and applications of cellulose, chitosan, amy
...
Figure 10.4
Chemical structures of the physiological ligand silyl Lewisx and
...
Figure 10.5
The natural ligand Man9 for DC‐SIGN and selected mono‐ and multi
...
Figure 10.6
Selected synthetic glyco‐gold nanoparticles and glycol‐quantum d
...
Chapter 11
Figure 11.1
Tissue engineering triad showing the factors influenced in tissu
...
Figure 11.2
Protein‐ or polysaccharide‐based scaffold architecture mimics th
...
Chapter 12
Figure 12.1
Suggested application of the principles of green chemistry to th
...
Figure 12.2
(a) Synthesis of the Zr(IV) MOF UiO‐66‐NH2 by twin‐screw extrusi
...
Figure 12.3
Examples of MOFs with bio‐based aliphatic diacids: (a) Synthesis
...
Figure 12.4
(a) Molecular structure of g‐CD. (b) Single crystal X‐ray struct
...
Figure 12.5
(a) Scanning electron micrograph of MIL‐88A crystallites and (b)
...
Chapter 13
Figure 13.1
Ternary diagram of CaO–SiO2–Al2O3 of selected pozzolans.
...
Figure 13.2
Morphology of fly ash, cement, and various agricultural pozzolan
...
Figure 13.3
XRD patterns of (a) rice husk ash, (b) bagasse ash, and (c) palm
...
Figure 13.4
Compressive strength of rice husk‐ash/fly‐ash geopolymer with Si
...
Chapter 14
Figure 14.1
Mean droplet diameter (d3,2) (a) and zeta potential at pH 7 (b)
...
Figure 14.2
Schematic representation and visual appearance of starch hydroge
...
Figure 14.3
Permeation of peroxyl radicals (a) and oxygen (b) from the aqueo
...
Figure 14.4
Schematic of phospholipids, a phospholipid bilayer, and formatio
...
Figure 14.5
Overview of the complex coacervation process.
Figure 14.6
Weight‐average molecular weight and differential refractive inde
...
Figure 14.7
Scanning electron microscope images of vitamin E microcapsules p
...
Chapter 15
Figure 15.1
Effect of different amylose/amylopectin ratios on properties of
...
Chapter 16
Figure 16.1
Overfertilization incident causes (a) eutrophication and (b) dro
...
Figure 16.2
Examples of nitrogen release profiles controllable by the coatin
...
Figure 16.3
Development of controlled‐release fertilizers (CRFs), which emer
...
Figure 16.4
Release mechanism of polymer‐coated fertilizer granule.
Figure 16.5
Release mechanism of nutrients from matrix‐type slow‐release f
...
Figure 16.6
Schematic diagram of double‐layer slow‐release nitrogen fertiliz
...
Scheme 16.1
Plausible reaction scheme for the synthesis of the basic alkyd r
...
Scheme 16.2
Schematic diagram of the pure PU synthesis mechanism using the p
...
Scheme 16.3
Schematic comparison of conventional PU and the NIPU.
Figure 16.7
Schematic illustration of organic carbon converted to biochar: s
...
Figure 16.8
FESEM image of the swollen surface of SAP‐biochar incorporation
...
Guide
Cover Page
Series Page
Title Page
Copyright Page
Dedication
List of Contributors
Series Preface
Table of Contents
Begin Reading
Index
WILEY END USER LICENSE AGREEMENT
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Wiley Series in Renewable Resources
Series Editor:
Christian V. Stevens,Faculty of Bioscience Engineering, Ghent University, Belgium
Titles in the Series:
Wood Modification: Chemical, Thermal and Other ProcessesCallum A. S. Hill
Renewables‐Based Technology: Sustainability AssessmentJo Dewulf, Herman Van Langenhove
BiofuelsWim Soetaert, Erik Vandamme
Handbook of Natural ColorantsThomas Bechtold, Rita Mussak
Surfactants from Renewable ResourcesMikael Kjellin, Ingegärd Johansson
Industrial Applications of Natural Fibres: Structure, Properties and Technical ApplicationsJörg Müssig
Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and PowerRobert C. Brown
Biorefinery Co‐Products: Phytochemicals, Primary Metabolites and Value‐Added Biomass ProcessingChantal Bergeron, Danielle Julie Carrier, Shri Ramaswamy
Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and ChemicalsCharles E. Wyman
Bio‐Based Plastics: Materials and ApplicationsStephan Kabasci
Introduction toWood and Natural Fiber CompositesDouglas D. Stokke, Qinglin Wu, Guangping Han
Cellulosic Energy Cropping SystemsDouglas L. Karlen
Introduction to Chemicals from Biomass, 2nd EditionJames H. Clark, Fabien Deswarte
Lignin and Lignans as Renewable Raw Materials: Chemistry, Technology and ApplicationsFrancisco G. Calvo‐Flores, Jose A. Dobado, Joaquín Isac‐García, Francisco J. Martín‐Martínez
Sustainability Assessment of Renewables‐Based Products: Methods and Case StudiesJo Dewulf, Steven De Meester, Rodrigo A. F. Alvarenga
Cellulose Nanocrystals: Properties, Production and ApplicationsWadood Hamad
Fuels, Chemicals and Materials from the Oceans and Aquatic SourcesFrancesca M. Kerton, Ning Yan
Bio‐Based SolventsFrançois Jérôme and Rafael Luque
Nanoporous Catalysts for Biomass ConversionFeng‐Shou Xiao and Liang Wang
Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and Power 2nd EditionRobert Brown
Chitin and Chitosan: Properties and ApplicationsLambertus A.M. van den Broek and Carmen G. Boeriu
The Chemical Biology of Plant BiostimulantsDanny Geelen, Lin Xu
Biorefinery of Inorganics: Recovering Mineral Nutrients from Biomass and Organic WasteErik Meers, Evi Michels, René Rietra, Gerard Velthof
Process Systems Engineering for Biofuels DevelopmentAdrián Bonilla‐Petriciolet, Gade P. Rangaiah
Waste Valorisation: Waste Streams in a Circular EconomyCarol Sze Ki Lin, Chong Li, Guneet Kaur, Xiaofeng Yang
Forthcoming Titles:
High‐Performance Materials from Bio‐based FeedstocksAndrew J. Hunt, Nontipa Supanchaiyamat, Kaewta Jetsrisuparb, Jesper T. Knijnenburg
Handbook of Natural Colorants 2nd EditionThomas Bechtold, Avinash P. Manian and Tung Pham
Biogas Plants: Waste Management, Energy Production and Carbon Footprint ReductionWojciech Czekała
High‐Performance Materials from Bio‐based Feedstocks
ANDREW J. HUNT
Materials Chemistry Research Center
Department of Chemistry and Center of Excellence for Innovation in Chemistry
Khon Kaen University
Khon Kaen, Thailand
NONTIPA SUPANCHAIYAMAT
Materials Chemistry Research Center
Department of Chemistry and Center of Excellence for Innovation in Chemistry
Khon Kaen University
Khon Kaen, Thailand
KAEWTA JETSRISUPARB
Department of Chemical Engineering
Khon Kaen University
Khon Kaen, Thailand
JESPER T.N. KNIJNENBURG
International College
Khon Kaen University
Khon Kaen, Thailand
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List of Contributors
Andrew P. Abbott School of Chemistry, University of Leicester, Leicester, UK
Mohammed Aqil Materials Science, Energy and Nanoengineering Department (MSN), Mohammed VI Polytechnic University (UM6P), Benguerir, Morocco
Hicham Ben Youcef High Throughput Multidisciplinary Research Laboratory (HTMR‐Lab), Mohammed VI Polytechnic University (UM6P), Benguerir, Morocco
Bernardo Castro‐Dominguez Department of Chemical Engineering, University of Bath, Bath, UK
Chaiyan Chaiya Department of Chemical Engineering and Materials, Rajamangala University of Technology Thanyaburi, Pathum Thani, Thailand
Prinya Chindaprasirt Sustainable Infrastructure Research and Development Center, Department of Civil Engineering, Khon Kaen University, Khon Kaen, Thailand
and
Academy of Science, Royal Society of Thailand, Bangkok, Thailand
Oranat Chuchuen Department of Chemical Engineering, Khon Kaen University, Khon Kaen, Thailand
Alan Connolly DSM Nutritional Products Ltd., Nutrition R&D Center Forms and Application, Basel, Switzerland
Doungporn Yiamsawas National Nanotechnology Center, National Science and Technology Development Agency, Pathum Thani, Thailand
Pradip K. Dutta Polymer Research Group, Department of Chemistry, Motilal Nehru National Institute of Technology, Allahabad, Prayagraj, India
Emile R. Engel Department of Chemistry, University of Bath, Bath, UK
Xiaotong Feng College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, Gansu, China
Salim Hiziroglu Department of Natural Resource Ecology and Management, Oklahoma State University, Stillwater, OK, USA
Andrew J. Hunt Materials Chemistry Research Center (MCRC), Department of Chemistry, Centre of Excellence for Innovation in Chemistry, Khon Kaen University, Khon Kaen, Thailand
Itziar Iraola‐Arregui High Throughput Multidisciplinary Research Laboratory (HTMR‐Lab), Mohammed VI Polytechnic University (UM6P), Benguerir, Morocco
Shefali Jaiswal Polymer Research Group, Department of Chemistry, Motilal Nehru National Institute of Technology, Allahabad, Prayagraj, India
Sasiradee Jantasee Department of Chemical Engineering and Materials, Rajamangala University of Technology Thanyaburi, Pathum Thani, Thailand
Kaewta Jetsrisuparb Department of Chemical Engineering, Khon Kaen University, Khon Kaen, Thailand
Wiyong Kangwansupamonkon National Nanotechnology Center, National Science and Technology Development Agency, Pathum Thani, Thailand
Pornnapa Kasemsiri Department of Chemical Engineering, Khon Kaen University, Khon Kaen, Thailand
David F. Katz Departments of Biomedical Engineering & Obstetrics and Gynecology, Duke University, Durham, NC, USA
Sarah Key School of Chemistry, University of Leicester, Leicester, UK
Poramate Klanrit Department of Biochemistry, Faculty of Medicine, Khon Kaen University, Khon Kaen, Thailand
Jesper T.N. Knijnenburg International College, Khon Kaen University, Khon Kaen, Thailand
Wilaiporn Kraisuwan Department of Chemical Engineering, Srinakharinwirot University, Nakhon Nayok, Thailand
Santosh Kumar Department of Organic and Nano System Engineering, Konkuk University, Seoul, South Korea
Kritapas Laohhasurayotin National Nanotechnology Center, National Science and Technology Development Agency, Pathum Thani, Thailand
Duncan J. Macquarrie Green Chemistry Centre of Excellence, Department of Chemistry, University of York, York, UK
Cinthia J. Meña Duran Green Chemistry Centre of Excellence, Department of Chemistry, University of York, York, UK
Manunya Okhawilai Metallurgy and Materials Science Research Institute, Chulalongkorn University, Bangkok, Thailand
Tabitha H.M. Petchey Green Chemistry Centre of Excellence, Department of Chemistry, University of York, York, UK
Nawadon Petchwattana Department of Chemical Engineering, Srinakharinwirot University, Nakhon Nayok, Thailand
Uraiwan Pongsa Division of Industrial Engineering Technology, Rajamangala University of Technology Rattanakosin Wang Klai Kang Won Campus, Prachuap Khiri Khan, Thailand
Patcharapol Posi Department of Civil Engineering, Rajamangala University of Technology Isan Khon Kaen Campus, Khon Kaen, Thailand
Qiaosheng Pu College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, Gansu, China
Wanwan Qu School of Chemistry, University of Leicester, Leicester, UK
Ubolluk Rattanasak Department of Chemistry, Faculty of Science, Burapha University, Chonburi, Thailand
Ismael Saadoune Technology Development Cell (TechCell), Mohammed VI Polytechnic University (UM6P), Benguerir, Morocco
and
IMED‐Lab, Faculty of Science and Technology, Cadi Ayyad University, Marrakesh, Morocco
Chadamas Sakonsinsiri Department of Biochemistry, Khon Kaen University, Khon Kaen, Thailand
Janet L. Scott Department of Chemistry, University of Bath, Bath, UK
Anu Singh Polymer Research Group, Department of Chemistry, Motilal Nehru National Institute of Technology, Allahabad, Prayagraj, India
Benjatham Sukkaneewat Divison of Chemistry, Udon Thani Rajabhat University, Udon Thani, Thailand
Nontipa Supanchaiyamat Materials Chemistry Research Center (MCRC), Department of Chemistry, Centre of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen, Thailand
Alexandra Teleki Science for Life Laboratory, Department of Pharmacy, Uppsala University, Uppsala, Sweden
Vera Trabadelo High Throughput Multidisciplinary Research Laboratory (HTMR‐Lab), Mohammed VI Polytechnic University (UM6P), Benguerir, Morocco
Christos Tsekou DSM Nutritional Products Ltd., Nutrition R&D Center Forms and Application, Basel, Switzerland
Series Preface
Renewable resources, their use and modification, are involved in a multitude of important processes with a major influence on our everyday lives. Applications can be found in the energy sector, paints and coatings, and the chemical, pharmaceutical, and textile industries, to name but a few.
The area interconnects several scientific disciplines (agriculture, biochemistry, chemistry, technology, environmental sciences, forestry, etc.), which makes it very difficult to have an expert view on the complicated interactions. Therefore, the idea to create a series of scientific books, focusing on specific topics concerning renewable resources, has been very opportune and can help to clarify some of the underlying connections in this area.
In a very fast‐changing world, trends are not only characteristic of fashion and political standpoints; science too is not free from hypes and buzzwords. The use of renewable resources is again more important nowadays; however, it is not part of a hype or a fashion. As the lively discussions among scientists continue about how many years we will still be able to use fossil fuels – opinions ranging from 50 to 500 years – they do agree that the reserve is limited and that it is essential not only to search for new energy carriers but also for new material sources.
In this respect, the field of renewable resources is a crucial area in the search for alternatives for fossil‐based raw materials and energy. In the field of energy supply, biomass‐ and renewables‐based resources will be part of the solution alongside other alternatives such as solar energy, wind energy, hydraulic power, hydrogen technology, and nuclear energy. In the field of material sciences, the impact of renewable resources will probably be even bigger. Integral utilization of crops and the use of waste streams in certain industries will grow in importance, leading to a more sustainable way of producing materials. Although our society was much more (almost exclusively) based on renewable resources centuries ago, this disappeared in the Western world in the nineteenth century. Now it is time to focus again on this field of research. However, it should not mean a “retour à la nature,” but should be a multidisciplinary effort on a highly technological level to perform research towards new opportunities, and to develop new crops and products from renewable resources. This will be essential to guarantee an acceptable level of comfort for the growing number of people living on our planet. It is “the” challenge for the coming generations of scientists to develop more sustainable ways to create prosperity and to fight poverty and hunger in the world. A global approach is certainly favored.
This challenge can only be dealt with if scientists are attracted to this area and are recognized for their efforts in this interdisciplinary field. It is, therefore, also essential that consumers recognize the fate of renewable resources in a number of products. Furthermore, scientists do need to communicate and discuss the relevance of their work. The use and modification of renewable resources may not follow the path of the genetic engineering concept in view of consumer acceptance in Europe. Related to this aspect, the series will certainly help to increase the visibility of the importance of renewable resources. Being convinced of the value of the renewables approach for the industrial world, as well as for developing countries, I was myself delighted to collaborate on this series of books focusing on the different aspects of renewable resources. I hope that readers become aware of the complexity, the interaction, and interconnections, and the challenges of this field, and that they will help to communicate on the importance of renewable resources.
I certainly want to thank the people of Wiley's Chichester office, especially David Hughes, Jenny Cossham, and Lyn Roberts, in seeing the need for such a series of books on renewable resources, for initiating and supporting it, and for helping to carry the project to the end.
Last, but not least, I want to thank my family, especially my wife Hilde and children Paulien and Pieter‐Jan, for their patience, and for giving me the time to work on the series when other activities seemed to be more inviting.
Christian V. StevensFaculty of Bioscience Engineering, Ghent University, BelgiumSeries Editor, “Renewable Resources”June 2005
1High‐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 Applications
Bio‐based materials can be synthesized directly from biomass constituents (such as polysaccharides and other polymers, proteins and amino acids, and active biological compounds) that are directly extracted from biomass, but also from biomass‐derived materials (e.g. bio‐derived polymers, porous carbons, or ashes) that require additional processing steps such as polymerization, carbonization, or combustion.
1.2.1 Biomass Constituents
1.2.1.1 Polysaccharides
Polysaccharides are biopolymers that are made up of monosaccharide units connected by glycosidic linkages. Polysaccharides can be obtained from plants (e.g. cellulose, starch, and pectin), algae (alginate), animals (chitin/chitosan), bacteria (bacterial cellulose), and fungi (pullulan). In contrast to synthetic polymers, polysaccharides are abundant in nature, renewable and biodegradable, and are therefore considered as promising replacements of nonrenewable fossil fuel‐based materials in a wide range of applications [9]. Yet, polysaccharides alone frequently present insufficient physicochemical properties, necessitating physical and/or chemical modifications to meet the required product specifications.
The hydrophilic nature of many polysaccharides presents a poor mechanical strength, which is a major hurdle for their widespread use. For this reason, polysaccharides are often blended with other polymers and/or chemically modified to improve their properties. In addition, inorganic additives can also play a key role to enhance materials properties from boosting strength to improving oxygen barrier and antibacterial properties. For example, esterification, etherification, acetylation, hydroxylation, and oxidation of starch, as well as the blending of starch with other biodegradable polymers can improve its physical and mechanical properties for food‐packaging applications (Chapter 15). Similarly, the substitution of hydrogen by alkyl groups to form cellulose ethers including ethyl cellulose (EC) and carboxymethyl cellulose (CMC) increases the hydrophobicity of cellulose. The addition of CMC into food packaging can improve mechanical, thermal, and barrier properties (Chapter 15). Although biopolymers account for less than 1% of the total plastic production [9], there is a strong growth potential toward their wider application driven by the circular economy trend. Novel biopolymers with improved properties and new functionalities for various applications such as packaging films and coatings as well as textile applications have been developed for commercialization and are reviewed in Chapter 15 with the emphasis on the packaging.
Similar modifications to the hydrophobicity of biopolymers have been used in coating materials in controlled release fertilizers. In coated fertilizers, the hydrophilicity of native biopolymers results in the buildup of osmotic pressure inside the fertilizer beads. This causes the coatings to break prematurely, resulting in burst release of the nutrients. Naturally obtained biopolymers are thus not ideal fertilizer‐coating materials owing to the lack of hydrophobicity and modifications are necessary to help control the nutrient release. By replacing hydroxy groups with ester groups, cellulose acetate (CA), which is a common cellulose derivative, can be prepared. The presence of ester introduces its pH sensitivity property to the materials and can be beneficial for applications not only in slow‐release fertilizers (Chapter 16) but also in drug delivery (Chapter 8).
In other applications, the hydrophilicity and swelling behavior of biopolymers are used as an advantage. A different class of fertilizers is that of hydrogel‐based fertilizers, which absorb and retain high amounts of water. Hydrogel composites with plant nutrients embedded in their network structure using alginate or chitosan have been developed to reduce the frequency of irrigation as well as controlling the rate of nutrient release (Chapter 16). Hydrogels also find applications in targeted drug delivery. The biocompatibility, biodegradability, and non‐toxicity as well as high affinity for water make biopolymers like alginate, hyaluronic acid, pectin, and carrageenan attractive in controlled release and targeted drug delivery systems for HIV prophylaxis (Chapter 8). Alginate microparticles and films have also been used for anti‐HIV drug delivery due to their excellent biocompatibility and biodegradability (Chapter 8), and alginate has been blended with other polymers to adjust the hydrophobicity of polyelectrolyte films for food‐packaging applications (Chapter 15).
An interesting group of oligosaccharides with both hydrophilic and hydrophobic properties is that of cyclodextrins. The truncated cone structure of these circular oligosaccharides exhibits a hydrophobic inner cavity, while the upper and lower rims are hydrophilic. These unique properties enable cyclodextrins to contain hydrophobic molecules, but the high costs limit the applicability in foods (Chapter 14). Cyclodextrins can also be used to form metal–organic frameworks (MOFs) that have been investigated for a variety of potential applications including molecular separations, drug delivery, and biomedicine. Organic ligands are the main factors that determine if an MOF is bio‐based, but the sustainability and safety of the metal ions should also be considered (Chapter 12).
Biodegradability is preferred in some applications such as packaging and fertilizers. The biodegradability needs to be tuned, however, to meet the desired product specifications. For example, in fertilizers, polysaccharide‐based coatings based on, e.g. starch or cellulose, are too biodegradable, leading to premature nutrient release into the soil. To reduce the rate of degradation in soil and extend its service time, the biopolymer can be grafted with rubber or a different polymer with a lower biodegradability and higher hydrophobicity (Chapter 16). In food packaging, many packaging materials are based on blends of biodegradable polysaccharides such as starch, cellulose, and chitosan. In addition, cellulose nanocrystals, nanofibers, and bacterial cellulose have been used as biodegradable reinforcing fillers in various packaging films (Chapter 15).
Due to their biological nature, the biocompatibility of polysaccharides can be taken advantage of in applications where the polymer requires intimate contact with cells. For example, mucoadhesive films based on derivatives of cellulose, alginate, or chitosan can provide sustained release of several antiretroviral agents (Chapter 8). Moreover, biomaterials are critical to success in tissue engineering, act as a scaffold for tissue and cells to grow on. Such scaffolds can be derived from protein or carbohydrate biopolymers, including silk, collagen, fibrin, chitosan, alginate, and agarose. Biocompatibility and the ability to contribute to biological functions with the cells are necessary properties. Chapter 11 highlights bio‐based feedstock that can be used in scaffold manufacturing for tissue engineering.
Carbohydrate‐based materials play an essential role in cellular recognition processes. Carbohydrate‐protein interactions can be probed by synthetic glycomaterials to diagnose viral and bacterial infections. In Chapter 10, bio‐based glycomaterials and carbohydrate‐functionalized materials are discussed including their application in drug/gene delivery, wound healing, biorecognition, and sensing.
Chitosan and chitin/glucan complexes have been used in a wide range of applications such as anticancer, antibacterial, antioxidant as well as gene delivery due to their unique biochemical properties (Chapter 9). The major limitation of these biopolymers is their insolubility in water and, as such, steps have been taken to improve their solubility by various modification methods. Other applications of chitosan include fertilizers (Chapter 16) and antibacterial food packaging (Chapter 15). For food‐packaging applications, chitosan is limited by its low mechanical strength, rigid structure, and low thermal stability, which can be overcome by blending chitosan with other (bio)polymers (Chapter 15).
Due to their safety and biocompatibility, polysaccharide‐based materials find applications in the food industry as emulsion stabilizers. Starch modified with octenyl succinic anhydride (OSA) generates an amphiphilic character of the starch, making it an effective stabilizer of oil‐in‐water emulsions. Gums such as gum acacia, gum tragacanth, xanthan gum, and guar gum are used as surfactants to stabilize emulsions and liposomes in the food industry, as well as the formation of coacervates. Additionally, cellulose nanocrystals find applications in food applications in the stabilization of Pickering emulsions (Chapter 14).
Polysaccharides have a high abundance of functional groups, e.g. hydroxyl groups of cellulose, amine of chitosan, and carboxylic acid of alginate. These functional groups have a good affinity for complexation of metal ions through mechanisms such as reduction, chelation, and complexation. The polysaccharides alone are poor sorbents due to their low stability and need to be improved by chemical (e.g. introduction of other functional groups) as well as physical modification (e.g. forming composites with other polymers as well as inorganic materials). The use of bio‐based composites for the recovery of precious and heavy metals is discussed in detail in Chapter 7.
In electrochemical storage devices, synthetic binders such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF) are traditionally used, which suffer from environmental and safety issues. As a green and renewable replacement, various biopolymer‐based binders have been used in either pristine or modified forms. For example, cellulose and its modified forms such as CMC, EC, and CA, but also chitosan, alginate, and gums have shown great potential as environmentally friendly binders (Chapter 5). Biopolymers such as chitosan, cellulose, and carrageenan can also be used as components of proton exchange membranes in fuel cells. Especially, chitosan is a highly promising biopolymer for fuel cell applications due to its low cost, environmental friendliness, hydrophilicity, ease of modification, and low methanol permeability (Chapter 5).
As mentioned in Section 1.1, a major challenge in the use of biomass feedstocks is the complex processing to obtain sufficient purity and quantity for the use in high‐performance products. Deep eutectic solvents (DES) comprise a class of solvents formed by eutectic mixtures of Lewis or Brønsted acids and bases, with physical properties similar to ionic liquids but different chemical properties [10]. These green solvents have the advantage over traditional ionic liquids since they are derived from biological resources and can be designed to have low toxicity and good biocompatibility. Chapter 6 of this book highlights a versatile approach of how biocompatible DES can be used as synthetic modifiers to achieve materials with a wide range of properties.
1.2.1.2 Other Biopolymers
Lignin is a three‐dimensional biopolymer composed of coniferyl alcohol, sinapyl alcohol, and p‐coumaryl alcohol monomers, but its specific structure and composition depend on the biomass [11]. A large number of hydroxyl groups in lignin provide a template for modification with specific functional groups. The ease and variability of lignin modification enable tailoring of the lignin structure to recover precious metals and rare earth metals (Chapter 7). Lignin has been used in fertilizer formulations, with the addition of plasticizers to improve the film‐forming properties (Chapter 16). Other applications of lignin are as binders in Li‐ion batteries (Chapter 5).
1.2.1.3 Proteins and Amino Acids
Proteins are biomolecules that are composed of amino acids and can be divided into plant‐based (e.g. soy protein, zein, and gliadin) and animal‐based proteins (e.g. gelatin, casein, and whey proteins). Plant proteins such as zein (extracted from maize) and gliadin (a component of gluten, extracted from wheat) are applied in the food industry as stabilizers of Pickering emulsions. However, pure protein emulsions are sensitive to changes in pH, which can be overcome by the formation of polymer‐biopolymer complexes. Zein nanoparticles can also be used to protect a hydrophobic core (such as vitamins) against oxidation and hydrolysis. Soy protein isolate, whey protein isolate, and casein are used in the formation of coacervates to encapsulate lipophilic‐active ingredients (Chapter 14). Gelatin, a natural water‐soluble protein obtained from collagen, is used in food‐packaging applications (Chapter 15).
Amino acids, the building blocks of proteins, and aliphatic diacids, like fumaric, glutaric, azelaic, and itaconic acids, have been used for the synthesis of MOFs with good water sorption and heat transfer applications (Chapter 12).
1.2.1.4 Active Biological Compounds
Apart from biopolymers and proteins, bio‐based resources may contain various active compounds that possess unique properties. Such high‐value chemicals may include fragrances, flavoring agents, and nutraceuticals like vitamins and antioxidants, and are generally extracted first before further processing of the biomass [12]. Naturally occurring fat‐soluble (A, D, E, and K) and water‐soluble vitamins (B and C) find applications in food. Here the key challenge is to retain the stability of the vitamins during storage and processing, which can be done by encapsulating the vitamin into delivery vesicles such as liposomes or coacervates (Chapter 14). Lecithins (such as phosphatidylcholine) and saponins (such as Quillaja saponins) are molecules with amphiphilic properties, which are used as natural surfactants to stabilize various vitamin‐containing emulsions (Chapter 14). Other active compounds include antioxidants, essential oils (e.g. oregano, thyme, clove, and cinnamon), and various extracts (e.g. from spent coffee grounds). Their incorporation into food packaging can prolong the shelf life of foods (Chapter 15).
1.2.2 Bioderived Materials
1.2.2.1 Polymers Derived from Biological Monomers
Polylactic acid (PLA) is a bio‐based thermoplastic composed of lactic acid monomers that are derived from renewable resources such as corn, sugarcane, or cassava. Due to its outstanding properties (biocompatible, biodegradable, and good mechanical strength), PLA and poly(lactic‐co‐glycolic) acid (PLGA) in biomedical applications such as anti‐HIV drug delivery, in the form of drug‐loaded nanoparticle formulations, topical products, and long‐acting inserts (Chapter 8). The good mechanical strength, optical transparency, biodegradability, and processability make PLA attractive for food‐packaging applications. A limitation of PLA is its poor impact force, which can be improved by addition of toughening agents [13]. Further modification of PLA can also improve properties such as antibacterial, antifogging, and gas barrier properties (Chapter 15).
Another interesting group of biomolecules is vegetable oils (VOs), which are composed of triglycerides from fatty acids. The VOs can be modified and used as monomers for the synthesis of alkyd resins and polyurethanes that find applications as coating materials in fertilizers (Chapter 16).
1.2.2.2 Carbon‐based Materials Derived from Biomass
After the extraction of valuable compounds, a significant proportion of the biomass remains with inferior composition and value. Or, in some cases, it may not be possible to extract valuables from the biomass due to, e.g. technical, financial, compositional, or hygienic reasons. Instead of leaving them to decay, these biomass feedstocks can be used as a carbon source to produce various carbon‐based materials. Carbon materials are inert, possess high mechanical stability, high surface area, and are chemically stable in the absence of oxygen under high or low pH. These properties make carbon materials appealing and suitable for various applications ranging from chemical sorbents, electrode materials, catalysts, and catalyst supports to slow‐release fertilizers [14–16].
Conversion of carbon‐rich biomasses can be carried out through thermochemical processes such as carbonization, pyrolysis, or similar techniques to produce porous carbons with tunable porosity. The porous structure can vary greatly depending on the cellulose content and source of the biomass as well as the pyrolysis conditions (e.g. temperature, atmosphere, duration, and presence of additives). The simplest form of porous carbon is biochar, which can directly be used as heterogeneous catalyst or catalyst support (Chapter 2). In soil, the porous biochar structure serves as a nutrient host to improve nutrient use efficiency. The water retention capacity, porosity, and high porous area of biochars can help slow down the nutrient release and thereby increase fertilizer use efficiency (Chapter 16).
Porous carbons can be categorized according to their pore size: microporous (<2 nm), mesoporous (2–50 nm), and microporous (>50 nm) [17]. High surface area and proper surface chemistry play a key role in catalysis and adsorption, and especially mesoporous carbons offer a wide range of applications. Most porous carbons, however, are microporous, allowing only small molecules or atoms to diffuse into the pore structure. Various activation techniques involving gases such as steam or CO2 (physical activation) or compounds such as KOH, H3PO4, or ZnCl2 (chemical activation) can be used to open the structure. The synthesis of porous carbons from various biomasses and the relations between synthesis conditions and material properties are discussed in detail in Chapter 2 for applications as catalyst or catalyst support, and in Chapter 4 for electrochemical applications.
Surface modification of porous carbons can be carried out to incorporate heteroatoms and functional groups through different methods including surface oxidation, halogenation, sulfonation, grafting, and impregnation [18]. Oxygen‐containing moieties such as carboxylic acids and phenolic hydroxyl groups have been successfully introduced onto the carbon surface via oxidative modification [18]. Apart from oxygen, also the incorporation of N‐, S‐, and P‐containing groups has been widely investigated. Sulfonation has been carried out to introduce –SO3H group to the porous structure, offering enhanced catalytic activity (Chapters 2 and 3). The incorporation of nitrogen‐containing pyridine‐N and pyrrole‐N into carbon electrodes improves the pseudocapacitance as well as catalytic activity for the oxygen reduction reaction in fuel cells (Chapter 4). The presence of phosphorus groups in biowastes can improve the pseudocapacitance of the carbon electrodes (Chapter 4).
Examples of other carbon materials that have been applied in energy storage applications include hard carbon, carbon nanofibers (CNFs), carbon nanotubes (CNTs), graphene, and carbon aerogels. Hard carbon can be produced from pyrolysis of biowastes such as fruit waste, sucrose, or glucose, and possesses a highly irregular and disordered carbon structure that make it a promising anode material for Na‐ion batteries [19]. The preparation of these carbons from biomass feedstocks and electrochemical applications are presented in Chapters 4 and 5. Production of biomass‐derived CNT and graphene and their catalytic performance are discussed in Chapter 2.
Starbon® is a special type of porous carbon with high mesoporosity, produced from polysaccharide hydrogels as structural templates. The relatively large pores (compared to the more traditional activated carbons) can effectively adsorb and desorb bulky molecules, showing promising applications as catalysts, catalyst supports, adsorbents, and recently as battery materials. Surface modification through sulfonation of Starbon® is very promising for catalysis applications. Chapter 3 highlights the synthesis and properties of (modified) Starbon® and its applications in adsorption and catalysis.
The versatility, environmental compatibility, and high availability are the driving forces for using bio‐ and agricultural wastes as starting materials of bio‐based carbon materials. For high‐performance applications, (modified) porous carbons have shown tremendous benefits and will continue developing to meet new application demands. Surface modification is necessary to fully exploit the potential of carbon materials. The challenges include the large‐scale yet well‐controlled and cost‐effective synthesis approaches. In addition, the inconsistency of the feedstocks and contamination may adversely affect the performance. Another concern is that biomass feedstock should not compete with food supply. Lignocellulosic biomass is particularly interesting for material development and plays an important role, both now and in the future.
1.2.2.3 Inorganic Materials Derived from Biomass
The elements C, O, H, and N generally present the major organic constituents of biomass in the form of polysaccharides, proteins, lipids, or other molecules. In addition to these, biomasses may also contain a significant fraction of inorganic material. The inorganic fraction can be separated from the organic matrix by combustion in the form of ash, of which the amount and elemental composition vary greatly between biomass sources and combustion conditions [20, 21]. Most commonly, inorganic elements consist of Si, Ca, K, P, Al, Mg, Fe, S, Na, and Ti with different proportions depending on the biomass source [20].
Biomasses such as rice husk contain relatively high amounts of Si, which can be extracted and used in various applications from energy storage to construction materials [22]. The successful use of Si derived from biomass is shown as anode material for Li‐ion batteries. A major challenge for Si‐based anodes is the low capacity retention, large volume change during lithium insertion/deinsertion process, and poor electrical conductivity, which can be partly overcome by using nanostructured materials [23]. Chapter 4 provides some critical perspectives on the application of biomass‐derived Si in Li‐ion batteries.
Another potential use of biomass ashes is demonstrated in the production of construction materials. Removal of the organic matrix by controlled combustion produces Si‐rich ash that can be used to produce geopolymer materials as an alternative to traditional Portland cement [24]. These biomass ashes can substitute aluminosilicate sources instead of traditional fly ash from coal burning and leads to lower greenhouse gas production. Although large‐scale application of bio‐based inorganic materials is not available at the present time, the utilization of inorganic materials from biomasses is expected to increase with increasing environmental awareness. Challenges include the reduction of transportation cost of bulky biomass, and the inhomogeneity of ashes needs to be overcome to promote their usage. Various treatment options and applications of biomass ashes for geopolymer applications are discussed and assessed in Chapter 13.
1.3 Structure of the Book
This book covers a wide range of bio‐based materials for high‐performance applications, including their processing and comparison to state‐of‐the‐art materials. First, Chapters 2–5 focus on the synthesis and applications of biomass‐derived carbons. Chapter 2 starts with presenting the characteristics of biomasses and their thermochemical conversion into carbon‐based catalysts and catalyst supports, with examples of their application in various reactions. Chapter 3 focuses on Starbon®, a mesoporous carbonaceous material derived from waste polysaccharides. The unique properties of pristine and modified Starbon® are highlighted with selected applications in adsorption and catalysis. Chapter 4
