Nanoparticle synthesis, templated

The acidic conditions of standard SBA-15 synthesis [35] cause the precipitation of metal nanoparticles without silica encapsulation, or the formation of amorphous silica due to the presence of the polymer used for nanoparticle synthesis. Therefore, the SBA-15 framework was synthesized under neutral condition using sodium fluoride as a hydrolysis catalyst and tetramethylorthosilicate (TMOS) as the silica precursor. Pt particles with different sizes were dispersed in the aqueous template polymer solution sodium fluoride and TMOS were added to the reaction mixture. The slurry aged at 313 K for a day, followed by an additional day at 373 K. Pt(X)/SBA-15-NE (X = 1.7, 2.9, 3.6, and 7.1nm) catalysts were obtained by ex-situ calcination (see Section 3.2). TEM images of the ordered... 

By using other templates, the size of metal nanoparticles can be also controlled. Chen et al. reported the sonochemical reduction of Au(III), Ag(I) and Pd(II) and synthesis of Au, Ag and Pd nanoparticles loaded within mesoporous silica [48,49]. Zhu et al. also reported the sonochemical reduction of Mn04 to Mn02 and synthesis of Mn02 nanoparticles inside the pore channels of ordered mesoporous cabon [50]. Taking into account these reports, the rigid pore of inorganic materials can be used as a template for the size controlled metal nanoparticle synthesis even in the presence of ultrasound. 

Scheme 9.4 Schematic of metal nanoparticles synthesis within dendrimer templates. (Reprinted from [54] copyright 2002, Marcel Dekker.)...

Alexandridis P, Sakai T (2005) Amphiphilic block copolymer-templated nanoparticle synthesis and stabilization. Abstracts of Papers, 229th ACS National Meeting, San Diego, CA, USA, March 13-17, 2005, COLL-474... 

Just as DENs particle sizes have some distribution (albeit relatively narrow), there is surely some distribution in particle compositions for bimetallic DENs. This is a fundamentally important aspect of DENs, particularly with regard to their catalytic properties however, there are presently no reliable characterization methods for evaluating particle composition distributions. One method that has been applied to PdAu [21] and PtPd [19] DENs, as well as dendrimer-templated PtAu [24] is to collect single particle EDS spectra from several (15-20) nanoparticles. These experiments indicate that individual particle composition distributions may vary widely, but the difficulty in obtaining data from the smallest particles may skew the results somewhat. EDS spectra collected over large areas, which sample tens or hundreds of particles, generally agree well with the bulk composition measurements [24] and with stoichiometries set in nanoparticle synthesis [19,21,24]. 

Keywords photocatalysis, hydrogen evolution, Ti02, semiconductor nanoparticles, sol-gel synthesis, template synthesis, mesoporous materials, metal-semiconductor nanocomposites... 

As a close relative to the brome mosaic virus the cowpea chlorotic mottle vims (CCMV) possesses an outer diameter of 28 nm, is assembled from 180 subunits that create an icosahedral type structure, and contains an RNA core. " Another similarity is the cationic interior surface of the viral capsid which is formed from subunits with highly basic N-termini (6 positively charged arginine and 3 lysine residues) that project into the cavity and stabilize the RNA core. However as a potential biomineralization template, the electrostatic environment of the virion cavity precludes any cationic metal precursors and thus limits its applicability for nanoparticle synthesis. 

The use of nanoparticles requires the initial synthesis of the nanoparticles, which generally adhere to the template via electrostatic and hydrogen bonding interactions, or on processing of the nanoparticles and template the nanoparticles are physically confined within the template. 

Zeolites are widely used as acid catalysts, especially in the petrochemical industry. Zeolites have several attractive properties such as high surface area, adjustable pore size, hydrophilicity, acidity, and high thermal and chemical stability. In order to fully benefit from the unique sorption and shape-selectivity effects in zeolite micropores in absence of diffusion limitation, the diffusion path length inside the zeolite particle should be very short, such as, e.g., in zeolite nanocrystals. An advantageous pore architecture for catalytic conversion consists of short micropores connected by meso- or macropore network [1]. Reported mesoporous materials obtained from zeolite precursor units as building blocks present a better thermal and hydrothermal stability but also a higher acidity when compared with amorphous mesoporous analogues [2-6]. Alternative approaches to introduce microporosity in walls of mesoporous materials are zeolitization of the walls under hydrothermal conditions and zeolite synthesis in the presence of carbon nanoparticles as templates to create mesopores inside the zeolite bodies [7,8]. 

Making use of constrained polymerisation of divinylbenzene on surfactant-modified colloid silica, Jang and Lim prepared carbon nanocapsules and mesocellular foams. Later, they reported that mesoporous carbons with highly uniform and tunable mesopores were fabricated by one-step vapour deposition polymerisation using colloidal silica nanoparticles as template and polyacrylonitrile as carbon precursor. Hampsey et al. recently reported the synthesis of spherical mesoporous carbons via an aerosol-based, one-step approach using colloidal silica particles and/or silicate clusters as template. ... 

FIGURE 6.8 (a) Schematic illustration of the procedure for the synthesis of polymeric capsules based on surface-initiated RAFT polymerization using silica nanoparticles as templates, (b) TEM image of polymer grafted silica nanoparticles, (c) SEM and (d) TEM images of the synthesized polymeric capsules. Source Huang et al. [15]. Reproduced with permission of American Chemical Society. 

PAMAM dendrimers can also be used as templating agents and nanoparticle stabilizers for the synthesis of bimetallic particles. The unique ability of dendrimers to host various metal precursors enables the simultaneous complexation of multiple metallic species at its various internal functional groups. The three primary methods of bimetallic nanoparticle synthesis through dendrimer stabilization are partial displacement, co-complexation, and sequential complexation. 

Supramolecular gels can also be formed using coordination interactions and gels represent a way to control the positioning of metal ions, for example, in nanoparticle synthesis. The reaction of Fe(N03)3 with 1,3,5-benzenetricarboxylic acid (BTC), for example, forms a coordination polymer gel within minutes. There is extensive cross-linking between the Fe and the tricarboxylic acid which leads to voids within the coordination polymer structure (Scheme 5.10). This gel may be used as a polymerisation template. Methyl methacrylate may be polymerised within the gel matrix by UV irradiation of the monomer, resulting... 

Nash, M. A. Lai, J. J. Hoffman, A. S. Yager, P. Stayton, P. S. Smart diblock copolymers as templates formagnetic-eore gold-shell nanoparticle synthesis. Nano Lett. 2010,10, 85-91. 

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