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41 SURFACE MODIFICATION OF INORGANIC NANOPARTICLES BY ORGANIC FUNCTIONAL GROUPS  APPLICATIONS
                            APPLICATION 41

                   41       SURFACE MODIFICATION OF INORGANIC NANOPARTICLES BY ORGANIC
                            FUNCTIONAL GROUPS



                  Nanoparticles are considered as key materials in  nanoparticles are synthesized by reducing noble
                  informational, environmental and medical technolo-  metal ions in the presence of thiols [1]. While the
                  gies. Various methods are proposed to synthesize the  reduced noble metal atoms aggregate to form
                  nanoparticles of metal, metal oxide and organic mate-  nanoparticles, thiol molecules attach on the surface
                  rials. The merits to use nanoparticles in these fields  of the nanoparticle to passivate the growing surface
                  are summarized as below:                       and minimize the chance to aggregate. The surface
                                                                 modification by alkanethiol (C H 2n 1 SH) produces
                                                                                           n
                    (a) We can design new materials with hybridized  hydrophobic nanoparticles because SH groups bind
                       functions by dispersing nanoparticles in a liq-  with noble metal atoms and the nanoparticles are
                       uid or solid.                             covered with alkyl groups. The modification can be
                                                                 performed with other molecules that have sulfur
                    (b) We can reduce resources and costs required to
                                                                 atoms [2]. The binding energy between noble metals
                       enable various functions that emerge at surfaces.
                                                                 and sulfur atoms is not so strong as covalent bonds.
                    (c) We can bind nanoparticles with biomolecules  Based on this nature, we can realize surface modifi-
                       to enable diagnosis and cure with the minimal  cation with two kinds of thiols by dispersing thiol-
                       invasion.                                 modified noble metal nanoaparticles in a solution
                                                                 with a different kind of thiol. The exchange reaction
                    (d) We can fabricate nanostructures with less effort
                                                                 between the thiol on the nanoparticles and the thiol in
                       by organizing different kinds of nanoparticles.
                                                                 solution occurs to produce binary modified noble
                    (e) We can explore new properties that arise based  metal nanoparticles. Most noble metal nanoparticles
                       on quantum size effects.                  including gold, silver, copper, palladium, platinum
                                                                 and nickel can be modified with thiols. Due to its
                  These merits emerge from the two characters of  easy experimental procedure, many researches have
                  nanoparticles: (1) the new phase of materials that can  studied the surface modification of noble metal
                  mix with solids or liquids to form virtually continuous  nanoparticles by thiols.
                  phases, and (2) the minimum unit of materials that
                  have defined structure and functions, which arise  2. Organic modification of metal oxide
                  from the decreased size of nanoparticles itself.
                  However the decreased size also results in the difficult  nanoparticles
                  handling.  We cannot manipulate each nanoparticle
                  and the nanoparticles tend to aggregate. This nature of  Metal oxides have various properties including
                  nanoparticles prohibits the handling similar to that of  electron transport, semiconducting property, ferro-
                  micrometer-sized particles.                    magnetism, giant magnetoresistance, luminescence,
                    These tendencies come from the effects of surface  ferroelectric property and catalysis (Table 41.1). In
                  atoms, which plays dominant role in the dispersion,  addition, most oxides are stable even in air and
                  aggregation and hybridization in the nanometer-sized  water. Due to these practical merits, various metal
                  materials. However, we can exploit this tendency to  oxides are used in functional devices. However,
                  control the behavior of nanoparticles.  The surface  incorporation of these properties of metal oxides
                  properties of nanoparticles are possibly changed by  into nanoscale devices requires two techniques, that
                  functional groups on the surface nanoparticles. Based  is, synthesis of metal oxide nanoparticles and their
                  on this idea, we propose the chemical modification of  surface modification. So far, few studies have been
                  the surface of nanoparticles to realize better handling  performed to synthesize surface-modified metal
                  of nanoparticles. In this chapter, we discuss the  oxide nanoparticles.  We are studying the metal
                  attachment of organic functional groups on the sur-  oxide nanoparticles whose surface is covered by
                  face of inorganic nanoparticles.               organic functional groups.  We have developed
                                                                 simultaneous synthesis and modification of metal
                  1. Surface-modified noble metal nanoparticles  oxide nanoparticles because nanoparticles easily
                                                                 aggregate together irreversibly. Fig. 41.1 shows our
                  Sulfur atom has large affinity with noble metals. This  method to synthesize surface-modified metal oxide
                  affinity is used to produce surface-modified noble  nanoparticles. During hydrothermal synthesis, the
                  metal nanoparticles.  Thiol-capped noble metal  growth of metal oxide nanoparticles proceeds by


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