edited by Thomas E. Rufford Denisa Hulicova-Jurcakova John Zhu GREEN CARBON MATERIALS pplications dvances And

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1 edited by Thomas E. Rufford Denisa Hulicova-Jurcakova John Zhu GREEN CARBON MATERIALS A A dvances And pplications

3 GREEN CARBON MATERIALS

5 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

6 Published by Pan Stanford Publishing Pte. Ltd. Penthouse Level, Suntec Tower 3 8 Temasek Boulevard Singapore editorial@panstanford.com Web: 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 (Hardcover) ISBN (ebook) Printed in the USA

7 Contents Preface xiii 1. Surface Chemistry of Green Carbons 1 Conchi O. Ania 1.1 Introduction Surface Functionalities Oxygen-Containing Functionalities Nitrogen Containing Functionalities Sulfur-Containing Functionalities Phosphorus-Containing Functionalities Halogens, Boron and Metallic Doping Halogens Boron Hydrogen Metallic doping Characterization Techniques Thermal Analysis X-Ray Photoelectron Spectroscopy Nuclear Magnetic Resonance Electrochemical Techniques Infrared Spectroscopy Other Techniques Elemental analysis Boehm titration Potentiometric titration ph, point of zero charge and isoelectric point 23

8 vi Contents 2. Preparation of Carbon Materials from Lignocellulosic Biomass 35 Cesar Nieto Delgado and Jose Rene Rangel Mendez 2.1 Introduction Chemistry of Lignocellulosic Materials Activation Processes Chemical Activation Phosphoric acid activation Zinc chloride activation Activation with alkali metal hydroxides Activating agent recovery Thermal Activation Carbonization process Activation process Hydrothermal Carbonization Microwave-Assisted Activation Agave Bagasse as a Precursor of Activated Carbon Conclusions Adsorbed Natural Gas and Hydrogen Storage 65 Juan Alcañiz-Monge, Dolores Lozano-Castelló, Diego Cazorla-Amorós, and Angel Linares-Solano 3.1 Introduction Adsorption of Methane on Activated Carbon Optimization of Activated Carbons for Methane Storage Applications Correlation of Methane Adsorption with the Micropore Texture Adsorption of Hydrogen on Activated Carbons Correlation of Hydrogen Adsorption with the Micropore Texture Hydrogen Adsorption in Volumetric Basis and Total Hydrogen Storage Capacity Conclusions 87

9 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 Effects of Carbon Properties on Capacitance Effect of Pore Structure Effect of Heteroatoms and Surface Functional Groups Electrodes from Different Waste Biomass Sources Materials and Methods Preparation and characterization of activated carbons Electrochemical measurements Influence of Carbon Precursor on Activated Carbon Properties Electrochemical Performance Conclusions 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 Carbon Aerocellulose: Preparation and Morphology Utilisation of CAC as Pt Support for PEMFC Electrocatalysts Pt Nanoparticle Deposition onto CAC Materials and Their Physicochemical/ Electrochemical Characterisations PEMFC Unit Cell Testing of the Pt/CAC Materials Utilisation of CAC as Cathode Material in Li/SOCl 2 Primary Batteries 131

10 viii Contents Interest of using CAC as Cathode Material in Li/SOCl 2 Primary Batteries Electrochemical Characteristics of CAC in Li/SOCl 2 Primary Batteries Conclusions Environmental and Green Chemistry Applications of Nanoporous Carbons 147 Juan Matos 6.1 Introduction Experimental Materials and Characterization Photocatalytic Tests Results and Discussion Kinetics of 4CP Disappearance Kinetics of Appearance and Disappearance of Intermediate Products Conclusions Removal of Toxic Gases on Activated Carbons 161 Teresa J. Bandosz 7.1 Introduction Removal of Ammonia Removal of Hydrogen Sulfide Removal of Sulfur Dioxide Removal of Nitric Oxides Removal of Other Toxic Gases (HCN, AsH 3, CH 3 SH) Concluding Remarks 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 Activated Carbon 199

11 Contents ix Influence of carbon source on physical-chemical properties Thermal activation and reactivation Characteristics of Contaminants That Are Targeted for Adsorption Natural organic matter Geosmin and methyl isoborneol: algal bloom odorants Endocrine-disrupting compounds, pharmaceutical, and personal care products Groundwater contaminants Mechanisms for Diffusion and Adsorption, and the Mass Transfer Zone and Bed Life Parameters for Characterizing Activated Carbons, Relative to Their Performance for Adsorbing Targeted Compounds Rapid small-scale column tests GAC in Water Treatment Systems in Combination with Coagulation, Advanced Oxidation and Biological GAC Cincinnati Water Treatment Plant Delaware River Regional Water Treatment Plant, New Jersey Metal Coagulants, Complexation with Natural Organic Matter Retrofitting Conventional Gravity Filters with GAC Tailoring Activated Carbons for Enhanced Removal of Natural Organic Matter and Odorants Modeling Sorption of Endocrine-Disrupting Compounds and Pharmaceutical/Personal Care Products GAC Tailored for Removing Oxyanions Overview 227

12 x Contents 9. Adsorption of Volatile Organic Vapours 235 Peter Lodewyckx 9.1 Introduction Physisorption Polanyi Theory or TVFM Model Isotherm Models and Micropore Volume Dubinin plots Other isotherm models Physisorption Capacity Selectivity Specific Interactions Deviations from the TVFM Model Isotherm Models Adsorption Kinetics Filter Breakthrough Time Modelling Filter Breakthrough Different types of models Wheeler Jonas model Environmental Factors Influencing Adsorption Temperature Humidity Other Vapours or Gases Influence of the Physical Form of the Carbon Granular Carbon Powdered Carbon Carbon Microbeads Carbon Monoliths Carbon Fibres and Carbon Cloth Carbon Nanotubes Combining Different Physical Forms Conclusions 252

13 Contents xi 10. Carbon Foam as a Radionuclide Trap Material for Fast Nuclear Reactors 257 Prasanta Jana and V. Ganesan 10.1 Carbon Foam Need for Radionuclide Trap Activity Transport Control of Radionuclide Release Survey of Types of Radionuclide Traps Experimental Methods Synthesis of Carbon Foam Characterization Cesium Trap Studies Radioactivity Counting Results and Discussion Cesium Trap Studies 276 Index 283

15 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

16 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.

17 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 ). 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

Hydrophobic and Superhydrophobic Organic-Inorganic Nanohybrids. Chang-Sik Ha Saravanan Nagappan

Hydrophobic and Superhydrophobic Organic-Inorganic Nanohybrids Chang-Sik Ha Saravanan Nagappan Hydrophobic and Superhydrophobic Organic-Inorganic Nanohybrids Hydrophobic and Superhydrophobic Organic-Inorganic