Sustainable preparation of metal nanoparticles

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RSC Green Chemistry Series Edited by Rafael Luque and Rajender S Varma Sustainable Preparation of Metal Nanoparticles Methods and Applications Sustainable Preparation of Metal Nanoparticles Methods and Applications RSC Green Chemistry Series Editors: James H Clark, Department of Chemistry, University of York, UK George A Kraus, Department of Chemistry, Iowa State University, Ames, Iowa, USA Andrzej Stankiewicz, Delft University of Technology, The Netherlands Peter Siedl, Federal University of Rio de Janeiro, Brazil Yuan Kou, Peking University, People’s Republic of China Titles in the Series: 1: 2: 3: 4: 5: 6: 7: 8: 9: The Future of Glycerol: New Uses of a Versatile Raw Material Alternative Solvents for Green Chemistry Eco-Friendly Synthesis of Fine Chemicals Sustainable Solutions for Modern Economies Chemical Reactions and Processes under Flow Conditions Radical Reactions in Aqueous Media Aqueous Microwave Chemistry The Future of Glycerol: 2nd Edition Transportation Biofuels: Novel Pathways for the Production of Ethanol, Biogas and Biodiesel 10: Alternatives to Conventional Food Processing 11: Green Trends in Insect Control 12: A Handbook of Applied Biopolymer Technology: Synthesis, Degradation and Applications 13: Challenges in Green Analytical Chemistry 14: Advanced Oil Crop Biorefineries 15: Enantioselective Homogeneous Supported Catalysis 16: Natural Polymers Volume 1: Composites 17: Natural Polymers Volume 2: Nanocomposites 18: Integrated Forest Biorefineries 19: Sustainable Preparation of Metal Nanoparticles: Methods and Applications How to obtain future titles on publication: A standing order plan is available for this series A standing order will bring delivery of each new volume immediately on publication For further information please contact: Book Sales Department, Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge, CB4 0WF, UK Telephone: +44 (0)1223 420066, Fax: +44 (0)1223 420247 Email: booksales@rsc.org Visit our website at http://www.rsc.org/books Sustainable Preparation of Metal Nanoparticles Methods and Applications Edited by Rafael Luque Departamento de Quı´mica Orga´nica, Universidad de Co´rdoba, Spain Email: q62alsor@uco.es Rajender S Varma National Risk Management Research Laboratory, U.S Environmental Protection Agency, Cincinnati, USA Email: varma.rajender@epa.gov RSC Green Chemistry No 19 ISBN: 978-1-84973-428-8 ISSN: 1757-7039 A catalogue record for this book is available from the British Library r The Royal Society of Chemistry 2013 All rights reserved Apart from fair dealing for the purposes of research for non-commercial purposes or for private study, criticism or review, as permitted under the Copyright, Designs and Patents Act 1988 and the Copyright and Related Rights Regulations 2003, this publication may not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry or the copyright owner, or in the case of reproduction in accordance with the terms of licences issued by the Copyright Licensing Agency in the UK, or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the UK Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of Chemistry at the address printed on this page The RSC is not responsible for individual opinions expressed in this work Published by The Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge CB4 0WF, UK Registered Charity Number 207890 For further information see our web site at www.rsc.org Printed in the United Kingdom by CPI Group (UK) Ltd, Croydon, CR0 4YY, UK Preface Nanoscience and Nanotechnology have brought about excitement in fundamental research as well as technological advances The word ‘‘Nano’’ has now become a household name Nanomaterials can be synthesized from simple bench top methodologies all the way to advanced molecular beam epitaxy techniques Advances made in designing new products are seen as important milestones in improving the lifestyle of developed and developing countries Many of these products have found a niche place in the market from catalysts to consumable goods, diagnostics to drug delivery systems, and electronics to energy conversion devices Such developments also mean that a huge production of nanoscale materials become vital to sustain the demand An effort of this large magnitude requires changes not only in production but also in handling and transport, as well as in safety and toxicology control The design of semiconductor and metal nanostructures of different shapes and sizes, in particular, offers new opportunities to tailor the application of nanodevices For example, size quantization effects in 0-D, 1-D and 3-D of semiconductors introduce unique optical and electronic properties The use of semiconductor quantum dots in photovoltaic devices has opened up new ways to boost the efficiency of solar cells The unique aspects such as multiple electron generation and hot electron extraction offer new opportunities to boost the efficiency of next generation of solar cells using semiconductor nanostructures Exciton-plasmon coupling in semiconductor-metal nanostructure composites is another area of research that can aid in developing new strategies to harvest photons Among the large variety of nanoscale materials, metal nanoparticles are considered to be important because of the remarkable changes in their properties as compared to their bulk counterparts Their wide range of applications is seen in diverse areas such as catalysis, biomedicine, energy conversion, RSC Green Chemistry No 19 Sustainable Preparation of Metal Nanoparticles: Methods and Applications Edited by Rafael Luque and Rajender S Varma r The Royal Society of Chemistry 2013 Published by the Royal Society of Chemistry, www.rsc.org v vi Preface environmental remediation, optics or telecommunications Such metal nanostructures with unique shapes and sizes can introduce significant enhancement in surface enhanced Raman scattering (SERS) signals, thereby enabling the detection of low level contaminants Localized surface plasmon effects as well as quantized charging effects have been shown to improve charge separation in artificial photosynthetic and photocatalytic systems The production of metal nanoparticles depends on the desired applications For example, wet chemistry methods are frequently used for biomedical applications, while gas phase deposition on solid supports is commonly employed in the preparation of catalysts and electrocatalysts The large volume of production of such nanomaterials poses a high demand on the manufacturers to develop environmentally friendly synthetic methods It is important not only to minimize energy consumption but also use the reactants that have negligible toxic effects In recent years, nanosafety has become a major point of concern in manufacturing nanomaterials The toxicity effects need to be tested for size, shape and chemical structures both during manufacture and usage by the consumers Researchers interested in green production and environmentally safe synthesis of metal nanoparticles will find this book highly useful The selection of topics offers a convenient way to educate important aspects of sustainable production, safe handling, toxicology, environmental remediation and energy conversion aspects of nanomaterials Prof Luis M Liz-Marzan, University of Vigo, Spain Prof Prashant V Kamat, University of Notre Dame, USA Contents Chapter Chapter Introduction Rafael Luque and Rajender S Varma Acknowledgments References 5 Environmentally Friendly Preparation of Metal Nanoparticles Jurate Virkutyte and Rajender S Varma 2.1 2.2 Introduction Biogenic Nanoparticles 2.2.1 Biosynthesis of Nanoparticles Fungi Bacteria Yeasts Algae Actinomycetes Plants Carbohydrates Vitamins 2.3 Other Synthetic Approaches and Further Consideration 2.4 Conclusions References RSC Green Chemistry No 19 Sustainable Preparation of Metal Nanoparticles: Methods and Applications Edited by Rafael Luque and Rajender S Varma r The Royal Society of Chemistry 2013 Published by the Royal Society of Chemistry, www.rsc.org vii 10 11 11 12 13 14 14 15 19 20 21 27 28 viii Chapter Contents Preparation of Metal Nanoparticles Stabilized by the Framework of Porous Materials Mehmet Zahmakiran and Saim Oăzkar 34 3.1 3.2 34 36 Introduction Supported Metal Nanoparticles in Catalysis 3.2.1 Preparation Routes of Supported Metal Nanoparticles Chemical Methods Physical Methods Physicochemical Methods 3.2.2 Types of Supported Metal Nanoparticles Depending on the Nature of Support Material Zeolites, Silica-Based Materials Metal Organic Frameworks (MOFs) Hydroxyapatite (HAp) Hydrotalcite (HT) 3.3 Future Goals Toward Modern Supported Metal Nanoparticles Catalysts References Chapter Energy Conversion and Storage through Nanoparticles Shenqiang Ren and Yan Wang 4.1 Introduction 4.1.1 Quantum Confinement of Nanoparticles 4.1.2 Synthesis of Quantum Dots 4.1.3 The Basic Working Principles of Nanostructured Solar Cells 4.2 Quantum Dot Solar Cells 4.3 Hot Carriers and Multiple Exciton Generation Effects 4.4 Nanoparticle-Based Li Ion Battery 4.4.1 Introduction 4.4.2 Cathode 4.4.3 Anode 4.5 Summary Acknowledgement References 36 36 38 41 41 42 49 54 57 60 60 67 67 69 70 73 76 90 92 92 94 96 99 100 100 ix Contents Chapter The Green Synthesis and Environmental Applications of Nanomaterials Changseok Han, Miguel Pelaez, Mallikarjuna N Nadagouda, Sherine O Obare, Polycarpos Falaras, Patrick S.M Dunlop, J Anthony Byrne, Hyeok Choi and Dionysios D Dionysiou 5.1 Green Chemistry of the Synthesis of Nanomaterials 5.1.1 TiO2 Nanomaterials 5.1.2 Other Semiconductors 5.1.3 Metal and Metal Oxides Nanoparticles 5.1.4 Metallic and Bimetallic Nanoparticles 5.2 Environmental Applications of Nanomaterials 5.2.1 Photocatalytic Degradation of Organic Pollutants in Air, Water, and Soil 5.2.2 Dehalogenation using Metallic and Bimetallic Nanoparticles Metallic Nanoparticles Bimetallic Nanoparticles Iron/Palladium Bimetallic Nanoparticles Iron/Nickel Bimetallic Nanoparticles Iron/Copper Bimetallic Nanoparticles Other Bimetallic Nanoparticles 5.2.3 Photocatalysis for the Disinfection of Drinking Water 5.3 Immobilization of Nanoparticles for Sustainable Environmental Applications 5.3.1 Need for Particle Immobilization 5.3.2 Goals and Strategies of Particle Immobilization 5.3.3 Application Examples of Immobilized Systems using Nanoparticles 5.4 Conclusions Acknowledgements References Chapter Green Nanotechnology – a Sustainable Approach in the Nanorevolution Ajit Zambre, Anandhi Upendran, Ravi Shukla, Nripen Chanda, Kavita K Katti, Cathy Cutler, Raghuraman Kannan and Kattesh V Katti 6.1 Introduction 106 107 107 111 112 117 119 119 122 122 123 123 124 125 125 125 131 131 131 132 134 135 135 144 144 216 Chapter specific surface and the toxic effects, a consensus seems to be emerging in the scientific community that several factors can contribute to the toxicity of these products and that it is currently impossible, with our limited knowledge, to weigh the significance of each of these factors or predict the precise toxicity of a new nanoparticle It is still a matter of debate what is the most relevant parameter for the dose–response analysis in nanotoxicology It has been reported that for the same dose in terms of mass, the toxic response increases as a function of the decreasing nanoparticle size Under these investigations, the surface area has been proposed as the adequate dose metric for analyzing the impact of engineered nanoparticles in a linear dose-response relationship.15,16 9.1.3 Inhalation of Engineered Nanoparticles The exposure to environmental particles has been a health hazard ever since humans began to use fire and we have been inhaling considerable amounts of particles in the form of smoke or dust since then Since the industrial revolution in the 19th century the amount of potentially noxious nanoparticles that we have been breathing has increased in a significant manner In the latest years novel nanotechnologies have also included the presence of engineered nanoparticles to the total amount of breathable environmental particles with a deeper impact in human health.17 Since engineered nanoparticles (ENPs) are increasingly being applied in many consumer products such as in cosmetics, textiles, and paints, the human and environmental exposure to ENPs is becoming probable.18 Furthermore, the use of nanoparticles as drug-delivery carriers has been known for a long time and a large literature is devoted to the development of ENPs with sizes, surface functionalities and compositions that enhance their medical applicability The respiratory system is usually the main entrance for nanoparticles to the human body The deposition of particles in the lungs varies considerably according to the granulometry of ultrafine dusts and, normally, the deposition of the coarse particles of work environments in the alveolar region increases as particle diameter decreases, reaching a maximum value of around 20% for mm This situation could lead to the misconception of a deeplung deposition of small nanoparticles Nanoparticles with aerodynamic diameters smaller than nm cannot reach the alveoli and 80% of them are deposited in the nose and pharynx The remaining 20% are trapped in the tracheobronchial region At this size, retention of inhaled nanoparticles is nearly 100%.19 By increasing the particle size to nm, 90% of all inhaled particles are retained in the lung and then are deposited in the three regions with relative uniformity Total pulmonary absorption of 20 nm nanoparticles decreases to 80% but more than 50% of 20 nm nanoparticles are deposited in the alveolar region This means that 20% of inhaled particles penetrate the lung but leave it during exhalation Particle granulometry thus has a major impact on the pulmonary deposition site.20 In several nanoparticle production processes, the granulometry can also vary Introduction to Nanosafety 217 considerably according to the stage of production Thus, even though the mass of 20-nm ultrafine particles deposited in the alveolar region represents over 50% of the total mass, the deposited dust concentration, expressed in lung surface units, will still be over 100 times greater in the nasal region and more than 10 times greater in the tracheobronchial region.21 The quantity of particles and the particle deposition site in the pulmonary system are also influenced significantly by the presence of pre-existing lung diseases.22 9.2 Risk-Reduction Strategies The potential exposure to ENPs can be controlled in research centers and industries through an adaptive risk-management program Such programs should provide the framework to anticipate the emergence of nanotechnologies in the design of laboratories, recognize the potential hazards, evaluate the exposure to ENPs, develop controls to prevent or reduce exposure and confirm the efficiency of those controls Exposure assessment is therefore the basic element of an effective risk-management scheme Those tasks contributing more to exposure and workers conducting them should be adequately identified and a register of tasks should be developed This inventory includes information on the duration and frequency of tasks, the amount of the nanomaterial being handled and its physical state and dustiness.23 Occupational exposure limit values (OELs) are a set of recommendations given by competent national authorities or other relevant national institutions as limits for concentrations of hazardous compounds in workplace air OELs for hazardous substances represent an important tool for risk assessment and management and valuable information for occupational safety and health activities concerning hazardous substances These can apply both to marketed products and to waste and byproducts from production processes, setting limits to protect against health effects, but not address safety issues such as flammable concentrations Nevertheless, in the case of nanotechnology there is no clear indication of the adequate metric for determining the impact in health of a specific nanoparticle In fact, the majority of chemical substances that can be found in both research and industry have no established OELs In this case, employers and workers often lack the necessary guidance on the extent to which occupational exposures should be controlled This is especially interesting in an emerging field such as nanotechnology, where materials and applications are rapidly moving forward 9.2.1 Prevention through Design and Good Laboratory Practices Anticipating potential safety and health hazards early in the development of the technology or process is a key point for a risk-reduction scheme Moreover, the incorporation of those safe practices into all design, implementation and operation phases have to be considered Prevention through design (PtD) is a management tool to protect workers from potentially unsafe work conditions 218 Chapter The PtD scheme addresses occupational safety and health needs by eliminating hazards and minimizing risks to workers throughout the life cycle of the process.24 Many nanotechnology research laboratories recognize PtD as a costeffective means to enhance occupational safety and health and have incorporated PtD management practices within their facilities.25 PtD strategies follow the standard hierarchy of controlling workplace hazards, which includes (1) eliminating, substituting, or modifying the nanomaterials; (2) engineering the process to minimize or eliminate exposure to the nanomaterials; (3) implementing administrative controls that limit the quantity or duration of exposure to the nanomaterials; and (4) providing use of adequate personal protective equipment A set of adequate regulations should be implemented in all laboratories and installations where chemical reactions are being performed The most common as well as easy to implement are the good laboratory practices (GLP) defined as a worldwide regulatory requirement primarily used in studies that are undertaken to generate data by which the hazards and risks to users, consumers and the environment are assessed.26 In fact, GLPs are a set of principles that provides a framework within which laboratory studies are planned and archived and by definition is referred to the testing of chemicals in an OECD member country in accordance with OECD Test Guidelines GLP helps assure regulatory authorities that the data submitted are a true reflection of the results obtained during the study and can therefore be relied upon when making risk and safety assessments 9.3 Safety and Prevention in the Nanotechnology Laboratory Handling nanomaterials in the workspace is a complex subject that could imply the exposure to potentially hazardous matter In nanotechnology research, it is furthermore complex to eliminate or substitute the nanomaterial However, some aspects of the process could be modified in a way that reduces release of the nanomaterial to the working environment For instance, working with ENPs suspended in a liquid is a significant improvement over working with them in dry powder form, because the potential for airborne release is reduced in most laboratory processes, although physical agitation of the liquid by sonication may aerosolize small droplets containing the ENPs.27 Whenever possible, the use of hazardous substances should be eliminated or those materials should be substituted for less-hazardous forms Research in the synthesis and handling of ENPs often requires the use of solvents and other potentially hazardous chemicals and researchers should select those chemical processes that utilize innocuous or less-toxic alternatives, in order to minimize worker exposures and environmental releases when the process is scaled up While nanotechnology continues to be an engine for economic growth through its use in innovative products, all parties need to find out more about the environmental, health and safety risks arising from nanomaterials during their Introduction to Nanosafety 219 life cycle The industrial interest is to keep pace with technological developments in order to promote risk awareness and management In this section, we will explore the most common approaches for safety and prevention in nanotechnology, namely control banding and nanoparticle emission assessment technique 9.3.1 Control Banding Since there are no relevant exposure limits that could be considered in the workplace, the strategy that is used in this situation is the control banding (CB) This is a qualitative strategy to assess and manage hazards associated with chemical exposures in workplaces As a generic approach, the control measure (e.g dilution ventilation, engineering controls, containment, etc.) is based on a range or ‘‘band’’ of hazards (skin/eye irritant, very toxic, carcinogenic, etc.) and exposures (small, medium, large exposure) This method for controlling workers’ exposure is based on the fact that there is limited number of control approaches and that many problems have been met and solved before This latter aspect, in the case of nanotechnology, requires a deep knowledge of the characteristics and properties of the nanomaterials considered As the CB approaches use the solutions that experts have developed to control an earlier occupational exposure to specific chemicals that are closely related to the synthesized nanoparticles and suggesting them to other tasks with similar exposure situations, this is therefore a procedure that focuses resources on exposure controls and describes how strictly a risk needs to be managed CB tools and strategies are essentially based in the grouping of the exposure to specific nanomaterials according to similar physical and chemical characteristics, planned operations and foreseen situations (amount of ENPs and exposure way) Control strategies for risk management are then determined for each group One of the most common forms of CB, which has been recently proposed for nanotechnology applications, is based in a four-level hierarchy of risk management options:28,29 (1) Good occupational hygiene practices, which is enhanced using the appropriate personal protective equipment; (2) Engineering controls, including local exhaust ventilation; (3) Containment; and (4) Seek specialist advice The correct determination of the control strategy requires information on the characteristics of a specific ENP and parent chemical substances, together with the potential for exposure (quantity in use, dustiness and the relative hazard as described in what is known as a risk phrase, or R-phrase) Determining potential exposures for airborne particulates or vapors involves characterizing the process or activity in which the substance is used CB tools must be used in conjunction with health and safety practices such as substitution Substitution for a less-hazardous material or precursor for the synthesis of the ENPs is highly recommended to prevent exposure It is important to note that CB does not replace the experts in occupational safety and health or eliminate the need for exposure monitoring In fact, the application of a CB approach recommends the use of professionals to provide recommendations 220 Chapter 9.3.2 Nanoparticle Emission Assessment Technique The lack of exposure limits specific to ENPs significantly reduces the applicability of CB tools in nanotechnology In addition, there is also an incomplete international consensus on standards and measurement techniques that should be considered for nanomaterials in both occupational environments and consumer products However, the interest of research centers and industrial facilities devoted to the production and use of nanomaterials in determining the potential for exposure is currently growing The National Institute for Occupational Health and Safety (NIOSH) has developed the nanoparticle emission assessment technique (NEAT) to evaluate the concentration of airborne ENPs in the workplace.30 The NEAT approach is based on the direct reading of the release ENPs using aerosol spectrometers, coupled with air filtering to perform chemical and microscopic analysis for particle identification and chemical speciation The purpose of NEAT is listing target areas, processes or tasks that involve a higher concentration of airborne ENPs, identifying the source of nanomaterial emission depending on the processing method and occupational procedures As was mentioned for CB tools, an adequate understanding of ENPs is needed through material safety data sheets, amount of nanomaterial synthesized or handled and the available literature on both precursors and final product Once potential sources of emissions have been identified and the nature of the ENPs and reagents are known, the procedure for a NEAT analysis involves the following steps:31 (1) Observational survey of the processing area to identify tasks that require air sampling; (2) analysis of the frequency and duration of each operation and the type of equipment used for handling and containment of the ENPs; (3) determination of the presence or absence of exhaust ventilation, both general and local; (4) determination of the points where containment is deliberately breached such as for product retrieval or for cleaning In the latter steps the existence of potential system failure points that could result in emission from the containment/control system, for instance holes in ducts or damaged joints are also considered NEAT is a useful tool for health and safety professionals to define whether a release and potential exposure to ENPs occur in the workplace Several directreading instruments are used in a parallel and differential manner to evaluate the total particle number concentrations relative to background and the relative size distributions of the particles If this initial evaluation indicates an elevated number of small particles, which could potentially be the ENPs of interest, then instruments are used to identify the source of the emissions Based on this identification step, filter-based air samples are collected for qualitative analysis of particle size, shape, and morphology using TEM or SEM analysis and for the determination of mass concentration by chemical analysis.32 9.4 Conclusions Nanotechnology is paving the way of a new industrial revolution Materials synthesized with controlled sizes and tailored properties are solving a myriad of Introduction to Nanosafety 221 concerns in both science and technology that just ten years ago seemed impenetrable Also, the development of nanomaterials for daily-life products, together with novel procedures and techniques that give nanoparticles their properties, are producing an impact in a society every day more aware about science and technology However, those features of engineered nanoparticles that bestow remarkable capacities in several research fields also induce an enhanced toxicological response upon exposure by inhalation or several other routes The design of risk-reduction strategies for engineered nanoparticles is therefore an urgent need for a safer nanotechnology Although exposure reduction by elimination is the best way to reduce risks, most of the time such a procedure it is not possible or even desirable Currently, the most common approaches for risk reduction in the nano realm come from the adaptation of the control measures used for the chemical industry However, the lack of specific regulations and normative regarding nanomaterials reduces their applicability The design of novel assessment methods and procedures for engineered nanomaterials depends on the measurement of the appropriate parameters of nanoparticles using specific techniques References Lux Research, Global Trends in Nanotech and Cleantech, 2010 (www.luxresearchinc.com) T Satterfield, M Kandlikar, C E Beaudrie, J Conti and B Herr Harthorn, Nature Nanotech., 2009, 4, 752 K Schmid and M Riediker, Env Sci Technol., 2008, 42, 2253 K Savolainen, H Alenius, H Norppa, L Pylkkaănen, T Tuomi and G Kasper, Toxicology, 2010, 269, 92 A E Nel, T Xia, L Maădler and N Li, Science, 2006, 311, 622 T Cedervall, I Lynch, M Foy, T Bergga˚rd, S C Donnelly, G Cagney, S Linse and K A Dawson, Angew Chem Int Ed., 2007, 46, 5754 F Balas, M Arruebo, J Urrutia and J Santamarı´ a, Nature Nanotech., 2010, 5, 93 T M Peters, S Elzey, R Johnson, H Park, V H Grassian, T Maher and P O’Shaughnessy, J Occup Env Hyg., 2009, 6, 73 M Seipenbusch, A Binder and G Kasper, Ann Occup Hyg., 2008, 52, 707 10 A Elder, I Lynch, K Grieger, S Chan-Remillard, A Gatti, H Gnewuch, E Kenawy, R Korenstein, T Kuhlbusch, F Linker, S Matias, N Monteiro-Riviere, V R S Pinto, R Rudnitsky, K Savolainen and A Shvedova In Nanomaterials: Risks and Benefits ed I Linkov and J Steevens, Springer, Dordrecht, 2009, p 11 A E Nel, L Maădler, D Velegol, T Xia, E M Hoek, P Somasundaran, F Klaessig, V Castranova and M Thompson, Nature Mater., 2009, 8, 543 222 Chapter 12 USEPA Terms of the Environment U.S Environmental Protection Agency, 2004 http://www.epa.gov/OCEPAterms/ 13 M Simko´ and M O Mattsson, Part Fibre Toxicol., 2010, 7, 42 14 SCENIHR, Risk Assessment of Products of Nanotechnologies, Scientific Committee on Emerging and Newly Identified Health Risks, 2009 http:// ec.europa.eu/health/ph_risk/committees/04_scenihr/docs/scenihr_o_023.pdf 15 G Oberdoărster, E Oberdoărster and J Oberdoărster, Env Health Perspect., 2005, 113, 823 16 T Stoeger, C Reinhard, S Takenaka, A Schroeppel, E Karg, B Ritter, J Heyder and H Schulz, Env Health Perspect., 2006, 114, 328 17 T Xia, N Li and A E Nel, Ann Rev Pub Health, 2009, 30, 137 18 B Nowack and T D Bucheli, Env Pollut., 2007, 150, 19 O Witschger and J F Fabrie`s, Hyg Sec Trav., 2005, 199, 21 20 G Oberdoărster, Int Arch Occup Env Health, 2001, 74, 21 G Oberdorster, A Maynard, K Donaldson, V Castranova, J Fitzpatrick, K Ausman, J Carter, B Karn, W Kreyling, D Lai, S Olin, N MonteiroRiviere, D Warheit and H Yang, Part Fiber Toxicol., 2005, 2, 22 A D Maynard and E D Kuempel, J Nanopart Res., 2005, 7, 587 23 General safe practices for working with engineered nanomaterials in research laboratories, National Institute of Occupational Safety and Health, 2012 http://www.cdc.gov/niosh/docs/2012-147/pdfs/2012-147.pdf 24 P Schulte, R Rinehart, A Okun, C Geraci and D Heidel, J Safety Res., 2008, 39, 115 25 V Murashov and J Howard, Nature Nanotechnol., 2009, 4, 467 26 http://www.nanotox.com/about-us/good-laboratory-practices-glp.html 27 D R Johnson, M N Methner, A J Kennedy and J A Steevens, Env Health Perspect., 2010, 118, 49 28 D M Zalk, S Y Paik and P Swuste, J Nanopart Res., 2009, 11, 1685 29 D M Zalk and S Y Paik, in Assessing Nanoparticle Risks to Human Health, ed G Ramachandran, Elsevier, Waltham MA 2011, p 139 30 http://goodnanoguide.org/NanoparticleỵEmissionỵAssessmentỵTechnique ỵ -ỵNEAT 31 M Methner, J Occup Env Hyg., 2008, 5, D63 32 A L Miller, P L Drake, P J Hintz and M C Habjan, Ann Occup Hyg., 2010, 54, 504 Subject Index absorbed photon-to-current efficiency (APCE) 91 Acanthella elongata 15 Ag nanoparticles algae 14 bacteria 12 carbohydrates 19 framework 47, 49, 55 fungi 12 plants 15–19 production 114 stabilising agents 44 toxicology 196, 201, 203 vitamins 20–1 yeasts 13 Ag nanoparticles-graphene (AgNPs-G) 26 alcohols/sugars oxidation 161–4 alfalfa (Medicago sativa) 15 gamma alumina 24 alumina zirconia solids 24 ‘‘An Inventory of Nanotechnology-based Consumer Products Currently on the Market’’ 195 Anacardium occidentale 16 Andrachnea chordifolia 17 Au nanodogbones 20 Au nanoparticles actinomycetes 15 alcohols and sugars 162, 164 algae 14 anode electrodes 25 bacteria 12 cellulose 169 fuel cells 175–6 medicine 146 plant surfactants 114 plants 15–19 reduction/stabilization 150–1 specificity supported metal nanoparticles 44, 46, 53, 56, 58 synthesis using phytochemicals cinnamon 146–9, 153 cumin 149, 153 green processes 153 introduction 146 tea 149–50, 153 toxicology 194, 201 yeasts 13 Bacillus subtilis 196 battery electric vehicles (BEVs) 100 Bayoxides E33 (arsenic adsorption) 114 bilirubin oxidase (BOD) 177, 179 bimetallic nanoparticles alloys 118 characterization 119 formation 117–18 iron/copper 125 iron/nickel 124 iron/palladium 123–4 other 125 see also biofuels biodiesel production 172–4 224 biofuels/high value added chemicals (sustainable metallic/bimetallic nanoparticles) bimetallic nanoparticles (synthesis) coreduction 160 successive reduction 160–1 thermal decomposition 161 biomass conversion (metallic/bimetallic nanoparticles) alcohols/sugars oxidation 161–4 biodiesel 172–4 cellulose 167–9 decarboxylation of fatty acids 169–72 fuel cells 174–9 hydrocarbons 166–7 sugars 164–6 future 179–80 introduction 157–8 metallic nanoparticles (synthesis) description 158–9 parameters 159 solution synthesis 159 water-in-oil emulsion 160 biogenic nanoparticles cell growth and enzyme activity 10–11 reaction conditions 11 selection of organisms 10 see also biosynthesis of nanoparticles biological factors (toxicology of engineered metallic nanoparticles) in vitro testing 199–200 in vivo testing 200–1 ‘‘biomass refineries’’ (biorefineries) 157 biophysicochemical interactions (toxicology of engineered nanoparticles) aggregation/stability 196–8 cation charge 198 dose metrics 192 form (liquid vs solid) 195–6 redox potential 198–9 Subject Index shapes 192–3 size, surface area, surface reactivity and surface coating 193–5 biosynthesis of nanoparticles actinomycetes 14–15 algae 14 bacteria 12–13 carbohydrates 19–20 fungi 11–12 plants 15–19 reverse micelle route 26 vitamins 20–1 yeasts 13–14 book summary 3–4 Brevibacterium caesi 12 Caenorhabditis elegans 193 Camellia sinensis 16 Candida guilliermondii 13 carbon nanofibers (CNFs) 164–5 carbon nanoparticles (CNPs) 169 carbon nanotubes CNTs) 168–9 CdS nanoparticles 111–12 quantum dots 76, 78, 80, 82 CdSe quantum dots 68, 69–70, 71–5, 78–81 CdTe quantum dots 72, 81 cellobiose dehydrogenase (CDH) 169 cellulose production 167–9 cetyltrimethylammonium bromide (CTAB) 24, 27, 59, 194 chemical bath deposition (CBD) 72 chemical methods for SMNPs preparation chemical vapor deposition 38 coprecipitation 37 deposition-precipitation 37 electrochemical reduction 38 microemulsion 37 photochemical reduction 37–8 wet impregnation 36–7 Chlorella vulgaris 14 chronoamperometry (CA) 174 cinnamon (cin-AuNPs) 146–9, 150, 152 Subject Index circulating tumour cells (CTCs) 152 Citrus sinensis 16 clay supported nanoparticles 22–3 Clostridium perfringens 127 cobalt nanoparticles 42–3, 58 cobalt oxide nanoparticles 132–3 Co-Fe nanoparticles 132–3 CoFe2O4 nanoparticles 22, 132–3 Coleus Amboinicus Lour (Indian Borage) 17 colloidal nanoparticles 67 colloidal quantum dots (CQDs) 71–2 control banding (CB) for hazards in workplace 219, 220 copper nanoparticles 52 Cryptosporidium parvum 127 cumin (cum-AuNPs) phytochemicals 149, 150, 152 cyclic voltammetry (CV) 175–6, 178 Cylindrocladium floridanum 11 Daphnia magna 201 decarboxylation of fatty acids 169–72 Degussa P25 photocatalyst 121, 128, 130 direct electron transfer (DET) 169, 179 direct glucose fuel cell (DGFC) 174–5 ‘‘disruptive science’’ (nanotechnology) 144–6 EGCG-198AuNPs (therapeutic efficacy) 150, 152–3 electric cars 154 electrochemically reduced graphene oxide (ERGO) 25–6 energy conversion and storage through nanoparticles hot carriers and multiple exciton generation effects 90–2 introduction 67–8 lithium ion battery 92–9 quantum confinement 69–70 quantum dot solar cells 76–90 solar cells 73–5 summary 99–100 synthesis of quantum dots 70–3 225 engineered nanoparticles (ENPs) humic acid 203 nanosafety 214–220 see also toxicology environmental applications of nanomaterials conclusions 134–5 dehalogenation (metallic/bimetallic nanoparticles) 122–5 immobilization of nanoparticles examples 132–4 goals and strategies 131–2 introduction 131–4 photocatalysis for disinfection of drinking water 125–31 photocatalytic degradation of organic pollutants in air, water and soil 119–22 environment (toxicology of engineered metallic nanoparticles) biological media/test reagents 203–4 dissolved organic matter 202–3 ionic strength/composition, pH 202 light irradiation 201–2 environmentally friendly preparation of metal nanoparticles biogenic nanoparticles 10–21 conclusions 27–8 introduction 7–10 other approaches 21–7 Escherichia coli Ag nanoparticles 16 biosynthesis of nanoparticles 11 fuel cells 178 PdO/TiON catalysts 129–30 photocatalytic inactivation 127 toxicology of nanoparticles 196, 198, 204 Euphorbia nivulia 16 European Union (EU) and safety of nanomaterials 214 external quantum efficiency (EQE) 74 226 F127 (surfactant) 25 fatty acid methyl esters (FAMEs) 172 Faujasite-type zeolites (FAU) 42 fill factor (FF) in solar cells 73–4, 87 fructose dehydrogenase (FDH) 169 fuel cells 174–9 Fusarium oxysporum 12 gamma-alumina 24 Geobacter sulfurreducens 12 Geotricum sp 12 gold nanoparticles see Au nanoparticles gold-palladium bimetallic (AU-PdNPs) nanoparticles 26 good laboratory practice (GLP) 217–18 granular activated carbon (GAC) 1334 graphene nanosheets (GNS) 26 Graătzel cell 75 ‘‘green’’ chemistry 10 green nanotechnology (sustainable approach) biomedical applications 152–3 gold nanoparticles using phytochemicals 146–50 introduction 144–6 reduction and stabilization 150–1 sustainability 153–4 term 146 green synthesis of nanomaterials (green chemistry) conclusions 134–5 introduction 107 metal/metal oxides nanoparticles 112–17 metallic/bimetallic nanoparticles 117–19 other semiconductors 11–13 TiO2 nanomaterials 107–11 gum kondagogu (Cochlospermum gossypium) 16 Hanensula anomala 13 Hevea brasiliensis 18 hexylphosphonic acid (HPA) 71 Subject Index Hibiscus rosa sinensis 16 high selectivity/reactivity (biomass conversion) 179–80 humic acid (HA) 202–3 hybrid electric vehicles (HEVs) 100 hydrocarbons production 166–7 hydrotalcite (HT) 57–9 hydroxyapatite (HAp) 22, 54–6 hydroxylpropyl cellulose 19 hyperbranched polyglycerol (HPG) 22 Igepal CO-630 surfactant 26 immobilization of nanoparticles (sustainable environmental applications) 131–134 incident photon-to-current efficiency (IPCE) 74, 91 indium tin oxide (ITO) 75, 80, 83–6 intense pulsed light (IPL) 178 ionic liquids 23 iridium nanoparticles 44 iron oxide (hematite) 115, 122 iron-oxide nanoparticles 115, 195 Jatropha oil 172 Klebsomidium flaccidum 14 Korean red ginseng root 17–18 Lactobillus sp 12 Li ion battery (nanoparticles) anode Li4Ti5O12 99 Si 97–9 cathode LiCoO2 94–5 LiFePO4 95–6 LiMn2O4 95 introduction 92–4 lithium (Li) ion batteries 25, 92–3, 93–9, 100 macroporous magnesium oxide 24 Macrotyloma uniflorum 18 magnetic nanoparticles 21–2 Subject Index mahogany leaves (Swietana mahogany JACQ.) 16 Mangifera Indica leaf extract 18 Meldola’s blue (MDB) 175–6 mesocellular foam (MCF) 170 mesoporous alumina layers 23–4 mesoporous nanoparticles 25 metal organic frameworks (MOFs) 49–53 metal-oxides nanoparticles 198, 200–1, 204–5 toxicity 200 metallic nanoparticles dehalogenation 122 green synthesis 117–19 wastes/‘‘sacrificial’’ organisms 26–7 see also biofuels Mg-Al nanoparticles 172 Micrococcus luteus 11 microwave-hydrothermal treatment (MHT) 172–3 mixed oxide nanoparticles 132 multiple exciton generation (MEG) 90–2 (functional) multiwalled carbon nanotubes (fMWCNTs) 38, 178 Mytilus galloprovincialis 196 ‘‘nano’’ revolution 1, 213 nanoceuticals 153 nanocomposites 25–6 nanoferrite dendritic structures 115 nanoparticle definition nanoparticle emission assessment technique (NEAT) 220 nanoparticles (NPs) carbon 169 catalysis 35 clay supported 22–3 colloidal 67 layers magnetic 21–2 mesoporous 25 preparation properties 2, 34–5 stabilization 2–3, 10 227 sustainability 153–4 semi-conductor see quantum dots synthesis 8–9, 35–6 uses 34 nanoparticles (NPs) – metals Ag-graphene (AgNPs–G) 26 Ag–Au 53 Au–Ag 53 AuNi 27 Au–Pd 26, 162 bimetallic 117–19, 123–125, 160–1, 161–79 CdS 111–12 Co 42–3, 58 Co-Fe 132–3 CoFe2O4 22, 132–3 Cu 52 Fe 113 Ir 44 iron-oxide 115, 195 metal oxide 198, 200–1, 204–5 metallic 117–19, 161–79 Mg-Al 172 oxide 173 Pd 12, 21, 52, 54, 57, 59, 122, 170, 174 Pd–Cu 52 Pd/SiO2 26 Pt 13, 19–20, 24, 44, 122, 174–5, 178–9, 201 Pt-Au 176–7 Pt-Cd 179 Pt-Co 179 Pt-graphene 26 Pt-Pd 179 Ru 35, 43–4, 49, 56 RuO2 44–5 SnO2 198 TiO2 19, 121, 197, 198, 201–5 ZnO 111–12, 193, 196, 198–200, 202, 204–5 Zr 25 see also Ag nanoparticles; Au nanoparticles; engineered nanoparticles 228 nanosafety conclusions 220–1 handling risks 214–15 inhalation of engineered nanoparticles 216–17 introduction 213–14 laboratory control banding 219, 220 description 218–19 nanoparticle emission assessment 220 risk reduction description 217 prevention through design/good laboratory practice 217–18 toxicity 215–16 nanozeolites 47–8, 50 National Institute for Occupational Health and Safety (NIOSH) 220 nitrogen-doped titanium oxide (TiON) 129–30 Nyctanthes arbortristis 18 occupational exposure limit values (OELs) 217 Ocimum Sanctum (tulsi) 16 OECD Test Guidelines (nanosafety) 218 ordered mesoporous alumina (OMA) 24 oxide nanoparticles 173 palladium catalysts 170–1, 173 nanohybrids 173–4 nanoparticles 12, 21, 52, 54, 57, 59, 122, 170, 174 palladized ZVI nanoparticles 133–4 6-palmitoyl ascorbic acid-2-glucoside (PAsAG) 20 PbS quantum dots 78–80, 83–9, 91 PbSe quantum dots 79, 85–7, 89 Pd-Cu nanoparticles 52 Pd/SiO2 nanobeads 26 photocatalysis for disinfection of drinking water 125–31 Subject Index photocatalytic degradation of organic pollutants in air, water and soil 119–22 physical methods for SMNPs preparation laser ablation 40–1 microwave irradiation 39–40 sonochemical 38–39 supercritical fluid 42 physicochemical methods for SMNPs preparation flame-spray pyrolysis 41 sonoelectrochemistry 41 Pichia capsulata 13 Plataforma Solar de Almeria (PSA) 128 platinum nanoparticles 13, 19–20, 24, 44, 122, 174–5, 178–9, 201 platinum nanoparticles-graphene nanosheets 26 plug-in hybrid electric vehicles (PHEVs) 100 polyaniline (PANI) as anode in fuel cells 178 polycyclic aromatic hydrocarbons (PAHs) 121 polyethylene glycol (PEG) 114 polymethyl methacrylate (PMMA) 24–5, 73 porogen surfactant 24 porous materials (preparation of metal nanoparticles) future goals 60 introduction 34–6 supported metal nanoparticles in catalysis 36–59 prevention through design (PtD) 217–18 Pseudokirchneriella subcapitata 201 Pseudomonas aeruginosa 129 Pseudomonas fluorescens 196, 203 Pt nanoparticles-graphene sheets (Pt/GNS) 26 Pt-Au catalysts 174–5 nanoparticles 176–7 229 Subject Index Pt-Bi catalysts 174–5 Pt-Cd nanoparticles 179 Pt-Co nanoparticles 179 Pt-Re catalysts (hydrocarbons) 166 Pt-Ru catalysts 175 quantitative structure-activity relationship (QSAR) 198 quantum dots (QDs) – semiconductor nanoparticles description 67–8 quantum confinement 69–70 synthesis 70–3 quantum dots (QDs) solar cells (structure configuration) 1st: vacuum-deposited 76 2nd: liquid-junction 76–7 3rd: hybrid 78–83 4th: Schottky and depleted 83–90 quantum dot sensitized solar cells (QDSSC) 77 reactive activated carbon (RAC) 134 reactive oxygen species (ROS) 126, 191, 193, 195, 197, 199–204 room-temperature ionic liquids (RTILs) 23 Ru catalysts cellulose 167–9 sugar conversion 164–5 Rubber latex 18 RuO2 nanoparticles 44–5 ruthenium catalysts 168–9 nanoparticles 35, 43–4, 49, 56 Saccharomyces cerevisiae 12, 13 safety see nanosafety Salmonella typhii 11 SBA-15 (mesoporous silicate) 170–1 Scientific Committee on Consumer Risks (SCCS) 214 Scientific Committee on Emerging and Newly Identified Health Risks (SCENIHR) 214 semiconductor nanoparticles (NPs) see quantum dots Shewenella Algae 13 silver nanoparticles see Ag nanoparticles single-walled carbon nanotubes (SWNT) 173 SnO2 nanoparticles 198 SnO2/graphene (SG) composites 26 solar disinfection of water (SODIS) process 126, 128 sorghum (Sorghum sp.) 19 spinal ferrites 22 Spirulena platensis 14 Staphylococcus aureus 11, 13, 16, 19, 129 successive ionic layer adsorption and reaction (SILAR) 72 sugars conversion 164–6 ‘‘supported’’ nanoparticles supported metal nanoparticles (SMNPs) in catalysis preparation chemical methods 36–8 physical methods 38–41 physicochemical methods 38–41 support materials hydrotalcite 57–9 hydroxyapatite 54–6 metal organic frameworks 49–53 zeolites, silica-based materials 42–9 Suzuki coupling reactions 26–7 synthesis of nanomaterials 8–9 tea (T-AuNPs) phytochemicals 149–50, 152 Terminalia chebula 18 Tetraselmis suecica 14 Thermomonospora chromogena 15 Thermomonospora curvata 15 Thermomonospora fucsa 15 Thermomonospora sp 12 230 TiO2 nanomaterials 107–11, 121, 126–30, 132–3 nanoparticles 19, 197, 198, 201–5 toxicology of designer/engineered metallic nanoparticles biophysicochemical interactions biological factors 199–201 engineered nanoparticles 192–9 environmental factors 201–4 introduction 190–2 metal-oxide nanoparticles (doped) 204–5 research gaps and collaboration 205–6 summary and outlook 206 Trichoderma viride 11 N-2, 4, 6-trimethylphenylN-methyldithiocarbamate (TMPMDTC) 72 trioctylphosphine oxide (TOPO) 71, 78 United States Environmental Protection Agency 135, 215 ‘‘unsupported’’ metal nanoparticles (MNPs) Subject Index vanillin (4-hydroxy-3methoxybenzaldehyde) 173 Verticillium (Taxus plant) 12 VeruSOL plant surfactants 114 Vibrio fisheri 196 vitamins B1 112 B2 21 C 20 E 20–1 volatile organic compounds (VOCs) 120 water/dioctyl sulfosuccinate 26 World Gold Council (WGC) 161 Yarrowia lipolytica 13–14 zeolite imidazole framework (ZIF-8) 53 zeolites (support materials) 42–9 zirconia nanoparticles 25 ZnO decolorization of waste water 122 nanoparticles 111–12, 193, 196, 198–200, 202, 204–5 ... 7.2.1 Synthesis of Metallic Nanoparticles 7.2.2 Synthesis of Bimetallic Nanoparticles 7.3 Applications of Metallic and Bimetallic Nanoparticles for Biomass Conversion 7.3.1 Oxidation of Alcohols... Bimetallic Nanoparticles Iron/Palladium Bimetallic Nanoparticles Iron/Nickel Bimetallic Nanoparticles Iron/Copper Bimetallic Nanoparticles Other Bimetallic... Green Chemistry of the Synthesis of Nanomaterials 5.1.1 TiO2 Nanomaterials 5.1.2 Other Semiconductors 5.1.3 Metal and Metal Oxides Nanoparticles 5.1.4 Metallic and Bimetallic Nanoparticles 5.2
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