edited by Thomas E. Rufford Denisa Hulicova-Jurcakova John Zhu GREEN CARBON MATERIALS A A dvances And pplications
GREEN CARBON MATERIALS
GREEN CARBON MATERIALS A A dvances And editors pplications edited by Thomas E. Rufford Preben Maegaard Denisa Hulicova-Jurcakova Anna Krenz John Zhu Wolfgang Palz The Rise of Modern Wind Energy Wind Power for the World
Published by Pan Stanford Publishing Pte. Ltd. Penthouse Level, Suntec Tower 3 8 Temasek Boulevard Singapore 038988 Email: editorial@panstanford.com Web: www.panstanford.com British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Green Carbon Materials: Advances and Applications Copyright 2014 Pan Stanford Publishing Pte. Ltd. All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means, electronic or mechanical, including photocopying, recording or any information storage and retrieval system now known or to be invented, without written permission from the publisher. For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to photocopy is not required from the publisher. ISBN 978-981-4411-13-4 (Hardcover) ISBN 978-981-4411-14-1 (ebook) Printed in the USA
Contents Preface xiii 1. Surface Chemistry of Green Carbons 1 Conchi O. Ania 1.1 Introduction 1 1.2 Surface Functionalities 3 1.2.1 Oxygen-Containing Functionalities 3 1.2.2 Nitrogen Containing Functionalities 7 1.2.3 Sulfur-Containing Functionalities 10 1.2.4 Phosphorus-Containing Functionalities 11 1.2.5 Halogens, Boron and Metallic Doping 12 1.2.5.1 Halogens 12 1.2.5.2 Boron 13 1.2.5.3 Hydrogen 13 1.2.5.4 Metallic doping 13 1.3 Characterization Techniques 14 1.3.1 Thermal Analysis 15 1.3.2 X-Ray Photoelectron Spectroscopy 16 1.3.3 Nuclear Magnetic Resonance 18 1.3.4 Electrochemical Techniques 18 1.3.5 Infrared Spectroscopy 20 1.3.6 Other Techniques 22 1.3.6.1 Elemental analysis 22 1.3.6.2 Boehm titration 22 1.3.6.3 Potentiometric titration 23 1.3.6.4 ph, point of zero charge and isoelectric point 23
vi Contents 2. Preparation of Carbon Materials from Lignocellulosic Biomass 35 Cesar Nieto Delgado and Jose Rene Rangel Mendez 2.1 Introduction 35 2.2 Chemistry of Lignocellulosic Materials 36 2.3 Activation Processes 40 2.3.1 Chemical Activation 40 2.3.1.1 Phosphoric acid activation 41 2.3.1.2 Zinc chloride activation 45 2.3.1.3 Activation with alkali metal hydroxides 47 2.3.1.4 Activating agent recovery 48 2.3.2 Thermal Activation 50 2.3.2.1 Carbonization process 51 2.3.2.2 Activation process 52 2.3.3 Hydrothermal Carbonization 53 2.3.4 Microwave-Assisted Activation 54 2.4 Agave Bagasse as a Precursor of Activated Carbon 55 2.5 Conclusions 57 3. Adsorbed Natural Gas and Hydrogen Storage 65 Juan Alcañiz-Monge, Dolores Lozano-Castelló, Diego Cazorla-Amorós, and Angel Linares-Solano 3.1 Introduction 65 3.2 Adsorption of Methane on Activated Carbon 70 3.2.1 Optimization of Activated Carbons for Methane Storage Applications 70 3.2.2 Correlation of Methane Adsorption with the Micropore Texture 76 3.3 Adsorption of Hydrogen on Activated Carbons 79 3.3.1 Correlation of Hydrogen Adsorption with the Micropore Texture 79 3.3.2 Hydrogen Adsorption in Volumetric Basis and Total Hydrogen Storage Capacity 84 3.4 Conclusions 87
Contents vii 4. Biomass-Derived Carbon Electrodes for Electrochemical Double-Layer Capacitors 93 Thomas E. Rufford, Erika Fiset, Denisa Hulicova-Jurcakova, and Zhonghua Zhu 4.1 Carbons for Electrochemical Double-Layer Capacitors 94 4.2 Effects of Carbon Properties on Capacitance 96 4.2.1 Effect of Pore Structure 96 4.2.2 Effect of Heteroatoms and Surface Functional Groups 97 4.3 Electrodes from Different Waste Biomass Sources 100 4.3.1 Materials and Methods 101 4.3.1.1 Preparation and characterization of activated carbons 101 4.3.1.2 Electrochemical measurements 102 4.3.2 Influence of Carbon Precursor on Activated Carbon Properties 102 4.3.3 Electrochemical Performance 104 4.4 Conclusions 109 5. Cellulose-Based Nanostructured Carbons for Energy Conversion and Storage Devices 115 Joanna Rooke, Romain Sescousse, Tatiana Budtova, Sandrine Berthon-Fabry, Bernard Simon, and Marian Chatenet 5.1 Introduction 116 5.2 Carbon Aerocellulose: Preparation and Morphology 119 5.3 Utilisation of CAC as Pt Support for PEMFC Electrocatalysts 124 5.3.1 Pt Nanoparticle Deposition onto CAC Materials and Their Physicochemical/ Electrochemical Characterisations 126 5.3.2 PEMFC Unit Cell Testing of the Pt/CAC Materials 129 5.4 Utilisation of CAC as Cathode Material in Li/SOCl 2 Primary Batteries 131
viii Contents 5.4.1 Interest of using CAC as Cathode Material in Li/SOCl 2 Primary Batteries 133 5.4.2 Electrochemical Characteristics of CAC in Li/SOCl 2 Primary Batteries 134 5.5 Conclusions 136 6. Environmental and Green Chemistry Applications of Nanoporous Carbons 147 Juan Matos 6.1 Introduction 148 6.2 Experimental 148 6.2.1 Materials and Characterization 148 6.2.2 Photocatalytic Tests 149 6.3 Results and Discussion 150 6.3.1 Kinetics of 4CP Disappearance 150 6.3.2 Kinetics of Appearance and Disappearance of Intermediate Products 152 6.4 Conclusions 158 7. Removal of Toxic Gases on Activated Carbons 161 Teresa J. Bandosz 7.1 Introduction 161 7.2 Removal of Ammonia 162 7.3 Removal of Hydrogen Sulfide 166 7.4 Removal of Sulfur Dioxide 172 7.5 Removal of Nitric Oxides 174 7.6 Removal of Other Toxic Gases (HCN, AsH 3, CH 3 SH) 178 7.7 Concluding Remarks 181 8. Conventional and Tailored Activated Carbons for Removing Natural Organic Matter and Targeted Compounds from Drinking Water 199 Fred S. Cannon and Cesar Nieto-Delgado 8.1 Introduction 199 8.1.1 Activated Carbon 199
Contents ix 8.1.1.1 Influence of carbon source on physical-chemical properties 200 8.1.1.2 Thermal activation and reactivation 202 8.1.2 Characteristics of Contaminants That Are Targeted for Adsorption 203 8.1.2.1 Natural organic matter 203 8.1.2.2 Geosmin and methyl isoborneol: algal bloom odorants 206 8.1.2.3 Endocrine-disrupting compounds, pharmaceutical, and personal care products 207 8.1.2.4 Groundwater contaminants 209 8.1.3 Mechanisms for Diffusion and Adsorption, and the Mass Transfer Zone and Bed Life 211 8.1.4 Parameters for Characterizing Activated Carbons, Relative to Their Performance for Adsorbing Targeted Compounds 213 8.1.4.1 Rapid small-scale column tests 214 8.2 GAC in Water Treatment Systems in Combination with Coagulation, Advanced Oxidation and Biological GAC 215 8.2.1 Cincinnati Water Treatment Plant 215 8.2.2 Delaware River Regional Water Treatment Plant, New Jersey 217 8.2.3 Metal Coagulants, Complexation with Natural Organic Matter 218 8.2.4 Retrofitting Conventional Gravity Filters with GAC 219 8.3 Tailoring Activated Carbons for Enhanced Removal of Natural Organic Matter and Odorants 220 8.4 Modeling Sorption of Endocrine-Disrupting Compounds and Pharmaceutical/Personal Care Products 222 8.5 GAC Tailored for Removing Oxyanions 225 8.6 Overview 227
x Contents 9. Adsorption of Volatile Organic Vapours 235 Peter Lodewyckx 9.1 Introduction 235 9.2 Physisorption 236 9.2.1 Polanyi Theory or TVFM Model 236 9.2.2 Isotherm Models and Micropore Volume 238 9.2.2.1 Dubinin plots 238 9.2.2.2 Other isotherm models 240 9.2.3 Physisorption Capacity 241 9.2.4 Selectivity 241 9.3 Specific Interactions 242 9.3.1 Deviations from the TVFM Model 242 9.3.2 Isotherm Models 242 9.4 Adsorption Kinetics 243 9.5 Filter Breakthrough Time 243 9.5.1 Modelling Filter Breakthrough 244 9.5.1.1 Different types of models 244 9.5.1.2 Wheeler Jonas model 245 9.6 Environmental Factors Influencing Adsorption 246 9.6.1 Temperature 246 9.6.2 Humidity 246 9.6.3 Other Vapours or Gases 247 9.7 Influence of the Physical Form of the Carbon 248 9.7.1 Granular Carbon 248 9.7.2 Powdered Carbon 249 9.7.3 Carbon Microbeads 250 9.7.4 Carbon Monoliths 250 9.7.5 Carbon Fibres and Carbon Cloth 251 9.7.6 Carbon Nanotubes 251 9.7.7 Combining Different Physical Forms 251 9.8 Conclusions 252
Contents xi 10. Carbon Foam as a Radionuclide Trap Material for Fast Nuclear Reactors 257 Prasanta Jana and V. Ganesan 10.1 Carbon Foam 257 10.2 Need for Radionuclide Trap 259 10.2.1 Activity Transport 259 10.2.2 Control of Radionuclide Release 260 10.3 Survey of Types of Radionuclide Traps 261 10.4 Experimental Methods 266 10.4.1 Synthesis of Carbon Foam 266 10.4.2 Characterization 266 10.4.3 Cesium Trap Studies 268 10.4.4 Radioactivity Counting 269 10.5 Results and Discussion 270 10.6 Cesium Trap Studies 276 Index 283
Preface Carbon is a versatile material that forms four known allotropes (amorphous, graphite, diamond, and fullerenes) and can be produced in a wide range of forms, including powders, foams, monoliths, cloth fibers, thin films, and granular particles. The physicochemical properties of carbon materials such as surface area, pore size, surface chemistry, and electrical conductivity can be tuned through the choice of precursor materials, preparation methods, and various secondary treatments. The versatility and possibilities to control the properties of carbon have seen carbon materials such as activated carbons used in a wide range of applications, including as adsorbents for wastewater treatment and gas purification, as energy storage materials, and as catalysts. Novel carbon nanomaterials such as carbon nanotubes have shown great potential as electronic materials, catalysts, and adsorbents. However, significant advances in the carbon nanomaterial production techniques are required if the cost of materials such as carbon nanotubes are to be reduced and their available volumes are to be increased to a level that would allow their widespread industrial application. In contrast, activated carbons, graphite, and graphitic materials have been used for many years as economically viable adsorbents, catalyst supports, and catalyst materials. In this book, we examine the recent advances in technologies to produce low-cost carbons using less energy-intensive production processes and the application of these so-called green carbons in the development of cleaner and more efficient energy production and utilization processes. Of particular interest in this book is the use of agricultural and food industry waste materials as a feedstock for activated carbon production. The content of this book is organized into 10 chapters written by experts in their fields. The first chapter provides an introduction to the functional groups that can be found on the surface of carbon materials described in the rest of the book, including a brief
xiv Preface description of the most commonly used analytical techniques to characterize these surface functional groups. Chapter 2 provides an overview of the technologies used to produce activated carbon from lignocellulosic biomass materials, including conventional methods such as chemical and thermal activation and novel methods such as hydrothermal carbonization. Chapters 3 to 5 highlight the recent advances in the use of carbon materials in energy storage and conversion. Carbons with high specific surface areas have been studied for the adsorption of hydrogen and methane for use onboard hydrogen- or natural gas powered vehicles (Chapter 3, by Alcañiz-Monge et al.) as well as electrode materials for electric double-layer capacitors (Chapter 4, by Rufford et al.) and lithium-ion batteries (Chapter 5, by Rooke et al.). Chapter 5 also covers the use of cellulose-based carbons as platinum catalyst supports in proton exchange membrane fuel cells (PEMFC). The second half of the book (Chapters 6 to 10) focuses on the use of carbon materials in pollution control, including the capture of toxic pollutants and volatile organic compounds (VOCs) from wastewater and industrial gases. Chapter 6 (Matos) reports the effect of the surface chemistry of activated carbon prepared from saw dust on the degradation of 4-chlorophenol by photooxidation in the presence of TiO 2. Chapter 7 (Bandosz) surveys the recent advances in the use of activated carbons to remove toxic gases such as ammonia, hydrogen sulfide, and sulfur dioxide from the emissions of industrial processes. This chapter studies the role of surface functional groups, the inorganic content of the carbon, and carbon pore structure in adsorption-reactive adsorption mechanisms involving the toxic gases. Chapter 8 (Cannon and Nieto-Delgado) presents the tailoring of the activated carbon properties for removing the natural organic matter, algal odorants, and endocrine disrupting compounds from water, along with case studies from municipal wastewater treatment plants. In Chapter 9, Dr. Peter Lodewyckx reviews the fundamentals of the adsorption of VOCs on carbon and the kinetics of the adsorption of VOCs in fixed beds. The final chapter (Chapter 10, by Jana and Gamesan) investigates the use of carbon foams prepared from sucrose as a radionuclide trap in sodium-cooled fast nuclear reactors.
Preface xv The multiple authors in this book have covered many of the significant industrial applications of carbon materials. However, the content of the book is not exhaustive and some notable omissions from the scope of the book include the use of carbon materials as catalysts and catalyst supports (aside from the discussion of PEMFC catalysts in Chapter 5) and the capture of carbon dioxide from flue gases. Each of these topics is significant industrially and scientifically, and as such have been covered in detail in other books (for example, Carbon Materials for Catalysis, edited by Phillipe Serp and José Luis Figueiredo, Wiley 2008) and review articles (for example, Marta Sevilla and Antonio B. Fuetes in Energy & Environmental Science, 2011, 4, pp. 1765 1771). We thank all the authors for their contributions and efforts to submit materials in a timely manner. We also thank our colleagues at the University of Western Australia and the University of Queensland who reviewed sections of this book and provided helpful suggestions. We also wish to thank Stanford Chong and Sarabjeet Garcha at Pan Stanford for their helpful advice and support (including their reminders of deadlines) during various stages in the preparation of this manuscript. Thomas E. Rufford Denisa Hulicova-Jurcakova Zhonghua (John) Zhu