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NANOMATERIALS L u q u e | B Edited by a lu Rafael Luque Producing Fuels and Fine Chemicals Alina Mariana Balu Biomass Using Nanomaterials from Scarcity of resources and increasing population and energy demands are important issues of the twenty-first century. A multidisciplinary approach is needed to produce suitable alternatives—such as renewable resources—for a more sustainable future. One P of the most promising and widely available renewable feedstocks is biomass, which r o has significant potential for conversion to materials, fuels, and chemicals. In addition, d nanomaterials can be designed for a range of applications including energy storage, B u i c fuel production, and nanocatalysis. Designing nanomaterials for the valorization o i m n of biomass and waste feedstocks is a major step in advancing the application of g nanomaterials and helping to move us toward the goal of a sustainable economy. as F s u U e Producing Fuels Producing Fuels and Fine Chemicals from Biomass Using Nanomaterials l s s offers a wide-ranging approach to the development of innovative nanomaterials for in a n biomass conversion and the production of energy and high-added-value chemicals, g d including biochemicals, biomaterials, and biofuels. The book is organized into three N F and parts according to nanomaterial applications: Nanomaterials for Energy Storage and a in n e Conversion, Biofuels from Biomass Valorization Using Nanomaterials, and Production o C m of High-Added-Value Chemicals from Biomass Using Nanomaterials. h Fine Chemicals a e t m Providing a multidisciplinary perspective, this book covers the most important aspects e r i of topics such as solar energy storage, design of carbonaceous nanomaterials i c a a from as heterogeneous catalysts for producing biofuels, catalytic reforming of biogas ls ls into syngas using a range of nanoparticles, and biofuels production from waste f r o oils and fats. It also describes the design and development of biocatalytic, solid m Biomass Using acid, photocatalytic, and nanostructured materials for the conversion of various biomass feedstocks to valuable chemicals as intermediates to end products, such as biopolymers, bioplastics, biofuels, agrochemicals, and pharmaceutical products. Nanomaterials K15273 6000 Broken Sound Parkway, NW Suite 300, Boca Raton, FL 33487 711 Third Avenue New York, NY 10017 an informa business 2 Park Square, Milton Park www.crcpress.com Abingdon, Oxon OX14 4RN, UK www.crcpress.com K15273_cover.indd 1 9/10/13 5:04 PM Producing Fuels and Fine Chemicals from Biomass Using Nanomaterials Edited by Rafael Luque Alina Mariana Balu Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2014 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Version Date: 20130815 International Standard Book Number-13: 978-1-4665-5340-8 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources. 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Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Contents Preface........................................................................................................................v Acknowledgments ....................................................................................................vii Editors .......................................................................................................................ix Contributors ..............................................................................................................xi Chapter 1 Introduction to Production of Valuable Compounds from Biomass and Waste Valorization Using Nanomaterials .......................1 Alina M. Balu and Rafael Luque Section i nanomaterials for energy Storage and conversion Chapter 2 Green Carbon Nanomaterials: From Biomass to Carbon ....................7 Maria-Magdalena Titirici Chapter 3 Carbon Materials and Their Energy Conversion and Storage Applications ........................................................................................59 Ji Liang, Ruifeng Zhou, Denisa Hulicova-Jurcakova, and Shi Zhang Qiao Chapter 4 Solar Energy Storage with Nanomaterials .........................................95 Nurxat Nuraje, Sarkyt Kudaibergenov, and Ramazan Asmatulu Section ii Biofuels from Biomass Valorization Using nanomaterials Chapter 5 Catalytic Reforming of Biogas into Syngas Using Supported Noble-Metal and Transition-Metal Catalysts ...................................121 Albin Pintar, Petar Djinović, Boštjan Erjavec, and Ilja Gasan Osojnik Črnivec iii iv Contents Chapter 6 Sulfated Inorganic Oxides for Methyl Esters Production: Traditional and Ultrasound-Assisted Techniques ............................137 Daria C. Boffito, Carlo Pirola, Claudia L. Bianchi, Giuseppina Cerrato, Sara Morandi, and Muthupandian Ashokkumar Chapter 7 Nanoheterogeneous Design of Biocatalysts for Biomass Valorization ......................................................................................163 Madalina Tudorache, Simona Coman, and Vasile I. Parvulescu Section iii P roduction of High–Added-Value chemicals from Biomass Using nanomaterials Chapter 8 Nanostructured Solid Catalysts in the Conversion of Cellulose and Cellulose-Derived Platform Chemicals .....................................181 Marcus Rose, Peter J. C. Hausoul, and Regina Palkovits Chapter 9 Chemocatalytic Processes for the Production of Bio- Based Chemicals from Carbohydrates ........................................................223 Jan C. van der Waal and Ed de Jong Chapter 10 Synthesis of Fine Chemicals Using Catalytic Nanomaterials: Structure Sensitivity .........................................................................267 Dmitry Yu. Murzin, Yuliya Demidova, Benjamin Hasse, Bastian Etzold, and Irina L. Simakova Chapter 11 Tunable Biomass Transformations by Means of Photocatalytic Nanomaterials ..................................................................................283 Juan Carlos Colmenares Quintero Preface The design of novel and innovative methodologies to maximize current available resources without compromising the future of coming generations is one of the most important challenges of the 21st century. The scarcity of resources and the expected increase in population and energy demands are two of the most important issues to be addressed. In this regard, green chemical and low environmental-impact technologies combined with renewable resources through innovation will be able to offer alternatives to potentially useful processes for a more sustainable bio-based society in which we will move away from the petrol-based economy we have relied upon the past 50-plus years. Biomass is one of the most promising and widely available renewable feedstocks that has a significant potential to offer a number of alternatives to be converted to materials, fuels, and chemicals. Waste residues can also par- tially help in contributing to this aim, leading to advanced valorization technologies for energy and fuels production. On the other hand, nanotechnology and nanomaterials development have experienced a staggering evolution in recent decades to the point that scientists are currently able to design and optimize a surprisingly significant number of nanomaterials for an extensive range of applications including energy storage, fuels production, biomedicine, and nanocatalysis, which are also taken to industrial and commercial practices. Combining the design of nanomaterials for the valorization of biomass and waste feedstocks to energy and chemicals as well as to (solar) energy storage can constitute a major step forward to further advancing current society in a scientific understanding of properties and alternative applications of nanomaterials in our goal toward a sustainable biorefinery-based economy. In light of these premises, this book aims to provide a comprehensive and most varied approach to the development of innovative nanomaterials for the production of energy and high added-value chemicals through the use of nanomaterials via energy storage, solar conversion, and biomass and waste valorization practices. The book contains a range of topics bringing together disciplines such as photocatalysis, energy storage, biofuels, cellulose conversion, carbonaceous nanomaterials, supported nanoparticles, among others, aiming to provide a multidisciplinary approach to the fascinating area of nanomaterials properties and applications. We hope this timely book will be able to inspire scientists to devise ever innovative and low environmental-impact alternatives to contribute to the advancement of mankind and we look forward to enjoying further advances in the field in the next few years. With best wishes for an enjoyable reading. v Acknowledgments Rafael Luque gratefully acknowledges support from the Spanish MICINN via the concession of a RyC contract (ref. RYC-2009-04199) and funding under projects P10- FQM-6711 (Consejeria de Ciencia e Innovacion, Junta de Andalucia) and CTQ2011 28954-C02-02 (MICINN). He is also indebted to his co-editor, Alina Mariana Balu, for her hard work, dedication, support, and patience in the process of developing the book. Both editors would like to dedicate this book to the memory of their former men- tor, colleague, and friend Professor Juan Manuel Campelo, who unexpectedly passed away in October 2012. vii Editors Rafael Luque earned his PhD in 2005 from Universidad de Cordoba, Spain. He has amassed significant experience on biomass and waste valorization practices to materials, fuels, and chemicals over the past 10 years. He has also published over 150 research articles, filed 3 patent applications, and edited 5 books as well as made numerous con- tributions to book chapters. He has been an invited guest, and keynote lecturer worldwide in the areas of (nano)materials science, heterogeneous (nano)catalysis, microwave and flow chemistry, biofuels, and green chemical methods in synthetic organic chemistry. Dr. Luque is also a mem- ber of the editorial advisory boards of several journals including Chemical Society Reviews, Catalysis Communications, Current Organic Synthesis, Current Green Chemistry, Journal of Technology Innovations in Renewable Energy, Sustainable Chemical Processes, and has recently been appointed as editor-in-chief of the section “Porous Materials” of the journal Materials. Among recent awards and recognition to his scientific career, Dr. Luque was awarded the Marie Curie Prize from Instituto Andaluz de Quimica Fina in Spain (2011), the Green Talents award from the Federal Ministry of Education and Research in Germany (2011), and the TR35 Spain 2012 from MIT (USA) as one of the top 10 innovative young entrepreneurs of Spain last year. He has also been recently hon- ored as Distinguished Engineering Fellow 2013 from the Hong Kong University of Science and Technology (HKUST). Dr. Luque also combines his academic duties with his activities as a young entrepreneur after co-founding the spinoff companies Starbon® Technologies at York, UK (2011), and Green Applied Solutions S.L. in Cordoba, Spain (2012). Alina Mariana Balu earned her PhD in 2012 from Universidad de Cordoba, Spain. Her work focuses on alternative and greener methodologies in chemistry, including novel technologies for materials preparation, the production of biofuels, and photocatalysis—a greener alternative for the production of chemicals and energy. As part of her PhD thesis, Balu brought together three important disciplines— nanomaterials, energy, and environment— and led a multidisciplinary team to develop more sustainable processes for the preparation of supported nano particles for various energy and environmental applications. This included the production of advanced second- generation biofuels and high added-value chemicals as well as biomass valorization and environmental remediation. Dr. Balu has ix