Hybrid nanomaterials synthesis, characterization and applications

Tai ngay!!! Ban co the xoa dong chu nay!!! HYBRID NANOMATERIALS HYBRID NANOMATERIALS SYNTHESIS, CHARACTERIZATION, AND APPLICATIONS Edited by Bhanu P S Chauhan Copyright Ó 2011 by John Wiley & Sons, Inc All rights reserved Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, or online at http://www.wiley.com/go/permission Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose No warranty may be created or extended by sales representatives or written sales materials The advice and strategies contained herein may not be suitable for your situation You should consult with a professional where appropriate Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) 762-2974, outside the United States at (317) 572-3993 or fax (317) 572-4002 Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic formats For more information about Wiley products, visit our web site at www.wiley.com Library of Congress Cataloging-in-Publication Data: Chauhan, Bhanu P S Hybrid nanomaterials : synthesis, characterization, and application / edited by Bhanu P S Chauhan p cm Includes bibliographical references and index ISBN 978-0-470-48760-0 (cloth) Printed in Singapore eBook ISBN: 978-1-118-00347-3 oBook ISBN: 978-1-118-00349-7 ePDF ISBN: 978-1-118-00348-0 10 Om Sat Guru in fond memory of my parents and to my life lines bholu, doujal, and shati CONTENTS Preface ix Contributors xi Hybrids from Polymer Colloids and Metallic Nanoparticles: A Novel Type of “Green” Catalyst Yan Lu and Matthias Ballauff Metal and Metal Oxide Nanostructure on Resin Support 23 Mrinmoyee Basu and Tarasankar Pal Pd-Nanoparticle Catalyzed Poly(hydro)siloxane Grafting: A Selective and Efficient Approach to Organic/Inorganic Hybrid Polymers 65 Bhanu P S Chauhan, Jitendra S Rathore, and Moni Chauhan Design and Synthesis of Nanohybrid Systems Based on Silicon–Oxygen Bond 97 Yusuke Kawakami Nanocrystalline Magnesium Oxide for Asymmetric Organic Reactions 139 Mannepalli Lakshmi Kantam and Venkat Reddy Chintareddy Boron-Based Hybrid Nanostructures: Novel Applications of Modern Materials 181 Zhu Yinghuai, Koh Cheng Yan, John A Maguire, and Narayan S Hosmane The Exploration of Biomedical Multimodality in Small Solid Core Nanoparticles 199 Marc Walters A Survey Study of Interactions of Gold Nanoparticles with Common Human Blood Plasma Proteins 219 Silvia H De Paoli Lacerda, Jack F Douglas, and Alamgir Karim vii viii CONTENTS Genetically Modified Collagen-like Triple Helix Peptide as Biomimetic Template 251 Prerna Kaur, Hanying Bai, and Hiroshi Matsui 10 Polydiacetylene-Containing Liposomes as Sensory Materials 269 Manas K Haldar, Michael D Scott, and Sanku Mallik 11 Block-Copolymer-Templated Synthesis of Ordered Silicas with Closed Mesopores 285 Michal Kruk and Chin Ming Hui 12 Organic–Inorganic Hybrid Nanomaterials: Organization, Functionalization, and Potential Applications in Environmental Domain 299 Ahmad Mehdi Index 331 320 ORGANIC–INORGANIC HYBRID NANOMATERIALS NH2 (EtO)3Si O O + O THF O (EtO)3Si N H COOH NH 1) H 2N + /H 2)H 2O O (HO)3Si N H (HO)3Si N H O COO - +H N NH 3+ -OOC COO - +H N NH O N H Si(OH)3 N H Si(OH)3 O + - OOC Polycondensation COO - + H NCH CH NH + 2 -OOC COO - + H NCH CH NH + 2 - COO - + H NCH CH NH + 2 -OOC COO - + H 3NCH2CH2NH 3+ -OOC - + H NCH CH NH + 2 COO -OOC OOC Scheme 12.18 Preparation of the bis-zwitterionic lamellar hybrid material highlights the great potential offered by the hybrid materials prepared from molecular precursors by the sol-gel process 12.4 POTENTIAL APPLICATIONS As we mentioned earlier, hybrid organic–inorganic materials, combining the properties of organic moieties and inorganic matrix, are a very interesting class of materials that offer a large domain of potential applications Indeed, by changing the nature of the organic moiety, it is possible to obtain materials presenting a wide range of possibilities in terms of chemical or physical properties In order to point out some potential applications, several examples concerning the chemical properties of hybrid materials described above will be given The growing of monodispersed RuO2 nanoparticles was achieved thanks to phosphonate groups contained within ordered mesoporous silicas.82 The use of mesoporous nanomaterials containing RuO2 nanoparticles (RuO2@SiO2 nanomaterials) as catalytic filters for gas sensors, as well as after deposition as “on-chip” POTENTIAL APPLICATIONS C3 H5 CO 321 NO2 CO2 NO2 Catalytic filter CO C3 H5 CO2 NO2 H2 O CO2 Sensitive layer Gas sensor Scheme 12.19 Nanomaterials containing RuO2 NPs as catalytic filters for gas sensors filters or as external filters, revealed their very interesting catalytic behavior for the preferential detection of propane in a gas mixture of propane/carbon monoxide/ nitrogen dioxide in air (Scheme 12.19) The efficiency of the propane discrimination was dependent on the metal content of the nanocomposite materials: a higher Ru/Si weight ratio induced higher SC3H8/SCO ratios The RuO2@SiO2 nanomaterials partially removed CO from the gas mixture by selectively oxidizing it to CO2, leaving the hydrocarbon content unaltered The catalytic behavior of these nanomaterials was greatly enhanced in comparison with another hybrid nanomaterial similarly prepared from unfunctionalized commercial silica for which nanoparticles that were not well dispersed in the silica grains were observed This synthetic method was a simple and reproducible way to produce wellcontrolled composite metal- or metal-oxide-containing silica nanomaterials displaying interesting catalytic properties for gas-sensing applications This study demonstrated that a single approach, deposition of a catalyst suspended in a liquid, may allow the sensitivity of gas sensors to be modulated; it also showed that the nature of the material employed was critical for obtaining reproducible results In the context of sustainable development, efforts have to be made to produce goods, raw materials, and chemicals by taking into account environmental constraints Particularly, catalysis has an important role to play, because it enables one to achieve reactions with higher rates and higher selectivity in the desired products In this context, the metathesis of functionalized olefins, mainly with Ru-based catalysts, has become a key reaction in organic synthesis, because it is atom economical (no or little by-products, reduction of the number of steps) and environmentally friendly (low temperatures of reaction, etc.) In fact, it represents a good example of a “green reaction.” From the industrial point of view, this reaction is already very important in petrochemical processes, for example, propene production by cross-metathesis of ethene and 2-butene, and there is a large research effort in industry to incorporate this reaction to produce bulk and fine chemicals However, until now, there is no key 322 ORGANIC–INORGANIC HYBRID NANOMATERIALS industrial process relying on the metathesis of functionalized olefins, and this originates from the following two major reasons (i) The existing highly active homogeneous catalysts based on ruthenium are very expensive and deactivate rapidly (needs high loading) Moreover, contamination of the reaction products by metals and the difficulty to remove traces of metals in organic products are also key problems for the drug industry (ii) The classical heterogeneous or homogeneous supported catalysts, developed so far, display very poor performances and not present any advantage compared to the best homogeneous catalysts (need high loading, no regeneration, etc.) Thus, we developed successfully a stable well-defined catalytic hybrid nanomaterial that is highly active in the metathesis reaction of functionalized olefins.83 This material was achieved by generating well-defined ruthenium–N-heterocyclic carbene ligands (Ru–NHC) supported systems perfectly dispersed in a mesoporous hybrid material and further stabilized by surface ligands (Scheme 12.20) These catalytic nanomaterials display high activity (TOF) and stability (TON vs time, recycling, and leaching) Furthermore, from the overall catalytic performances and stereochemical studies, we demonstrated that the active “single site” corresponds to a Ru–NHC species Finally, the versatility of such a synthetic methodology and its transfer to various metals and ligands (including sensitive ones) is a very promising approach toward a wide range of tailor-made well-defined heterogeneous catalysts The chelating capability of the lamellar nanomaterials containing different organic groups (SH, NH2, COOH, etc.) has been tested for transition metal and lanthanide ions Materials with SH groups were treated with an aqueous solution of HgCl2 at room temperature It was observed that the ratio of metal ions per thiol moieties was found to be around 1/3, confirming the high mercury adsorption capacity (2.3 mmol of Hg2 ỵ per gram) These values are high in comparison with most of those obtained for thiol-modified mesoporous silica described in the literature.84 This high adsorption affinity toward mercury ions renders these materials promising for removal of other heavy metal ions from aqueous solutions (i.e., environmental remediation) Amino-functionalized materials are probably the most widely studied organic– inorganic materials due to their numerous potential applications such as catalysis and metal sorbents.85 Amine-containing materials were also often prepared as sorbents for gas removal, in particular, CO2.86 The accessibility of the amine groups in the lamellar nanomaterials as well as their chelating ability toward transition metal or lanthanide anhydrous salts was N Cl COOMe + Cl N Mes Ru Si + COOMe Scheme 12.20 Catalytic hybrid nanomaterials for alkenes metathesis L Ph POTENTIAL APPLICATIONS 323 investigated For that purpose, the materials were treated with an ethanolic solution of CuCl2, Eu(NO3)3, or Gd(NO3)3 The N/Cu molar ratio was found to be around That means that two amino groups are necessary on average for chelating one Cu2 ỵ , which is very low Indeed, in solution, the complexation of Cu2 ỵ requires generally four nitrogen atoms Thus, it appears that all the amino groups are operative as ligands and that, in this case, long-range order does not improve considerably the chelating properties of the materials In the case of complexation of europium salts, the N/Eu molar ratio was found to be 6.5 and 4.8 for materials obtained from 3-aminopropyltrimethoxysilane and N-(6-aminohexyl)-3-aminopropyltrimethoxysilane, respectively.77 It is worth noting that complexation of CuCl2 and EuCl3 was also investigated within amine-free materials containing only long alkylene chains In all cases, a salt uptake less than 1% was obtained, showing that the salt uptake was due to a complexation reaction and not adsorption This result renders these materials as good candidates for ion separation, including actinides Similar study was done on materials containig carboxylic acid groups For that purpose, the carboxylic acid groups were transformed into potassium carboxylate salts by treating M1(n ¼ 3), M2 (n ¼ 5), and M3 (n ¼ 11), with either a t-BuOK solution in t-BuOH at 25 C or potassium acetylacetonate (K(acac)) in ethanol, giving rise to materials named M1K–M3K (Scheme 12.21) The exchange reactions were confirmed by elemental analyses The K/Si molar ratio was found to be 0.90, 0.99, and 0.93 for M1K, M2K, and M3K respectively These values are very close to the theoretical values (1), indicating that the overall COOH HOOC COOH HOOC COOH HOOC COOH HOOC COOH HOOC COOH HOOC M1-M3 Siloxanes t BuOK or K(acac) COOK KOOC COOK KOOC COOK KOOC COOK KOOC COOK KOOC COOK KOOC M1K-M3K = Eu3 + COO- - COO- - - - COO EuX3 OOC COO- - OOC COO- - - - OOC COO OOC OOC OOC M1Eu-M3Eu Scheme 12.21 Chelating ability of M1K–M3K toward europium salts 324 ORGANIC–INORGANIC HYBRID NANOMATERIALS –COOH groups were accessible Finally, the chelating ability of M1K–M3K toward europium salts was tested.79 The solids were treated with an ethanolic solution of EuCl3 at room temperature The resulting solids were copiously washed with ethanol to eliminate any noncomplexed salts and named M1Eu, M2Eu, and M3Eu, respectively (Scheme 12.21) The titration by EDTA of the whole filtrate containing the noncomplexed salt was done and revealed the incorporation of one EuIII per three carboxylate units for M1K and M2K on average Interestingly, the EuIII uptake within M3K was found to be one EuIII per two carboxylate units Elemental analyses of Si and Eu in M1Eu–M3Eu confirmed the content in europium obtained by titration Furthermore, it is worth noting that the content in potassium in M1Eu–M3Eu was found to be very low (