Mesoporous particle synthesis

A. Tuel, L. G. Hubert-Pfalzgraf, Nanometric monodispersed titanium oxide particles on mesoporous silica synthesis, characterization, and catalytic activity in oxidation reactions in the liquid phase, /. Catal. 217 (2003) 343. 

S. Yang, X. Luo, Mesoporous nano/micro noble metal particles synthesis and applications, Nanoscale 6 (9) (2014) 4438-4457. 

The synthesis of monolithic materials with built-in reactive sites opens up the opportunities for exploiting their reactivity for desired piuqroses with precision. In this context, hydrosilanes containing reactive Si—H bonds in monomeric and polymeric forms have been used for the reduction of organic compounds [60]. Therefore, as a solid material hydrogen silsesquioxane (H—SiOi s, HSQ) represents a reactive solid for which the reactivity can be used for desired purposes. However, the synthesis of monolithic HSQ directly from alkoxide precursor (tri-methoxy/ethoxysilane) is rather difficult, as the Si—H bond is very weak and can easily be cleaved imder basic and nucleophilic conditions, restricting the sol-gel only to the acid-catalyzed route, and only the synthesis of HSQ films and periodic mesoporous particles has been reported so far [61]. 

For L=NH3 (1) and L=Pr2NH (3), the isotherms are of type II as expected for non-porous materials [27]. Sample 2 shows a significant uptake at 0.6

narrow particle-size distribution which results in a more regular packing with interparticle pores of size similar to that of the particles [27]. The latter shows that the ligand-assisted synthesis does not only allow one to affect the total surface area and particle size, but also the size distribution which is an important tool for tailoring the particle properties. 

The mechanical incorporation of active nanoparticles into the silica pore structure is very promising for the general synthesis of supported catalysts, although particles larger than the support s pore diameter cannot be incorporated into the mesopore structure. To overcome this limitation, pre-defined Pt particles were mixed with silica precursors, and the mesoporous silica structures were grown by a hydrothermal method. This process is referred to as nanoparticle encapsulation (NE) (Scheme 2) [16] because the resulting silica encapsulates metal nanoparticles inside the pore structure. 

Similarly, monometallic Rh, Pd, and Au and bimetallic Pt-Rh and Pt-Pd nanowires were prepared in FSM-16 or HMM-1 by the photoreduction method [30,33,34]. The bimetallic wires gave lattice fringes in the HRTEM images, and the EDX analysis indicated the homogeneous composition of the two metals. These results show that the wires are alloys of Pt-Rh and Pt-Pd. Mesoporous silica films were also used as a template for the synthesis of uniform metal particles and wires in the channels [35,36]. Recently, highly ordered Pt nanodot arrays were synthesized in a mesoporous silica thin film with cubic symmetry by the photoreduction method [37]. The... 

Li, Y. and Kim, S.J. (2005) Synthesis and characterization of nano titania particles embedded in mesoporous silica with both high photocatalytic activity and adsorption capability. Journal of Physical Chemistry B, 109, 12309-12315. 

Fuertes A.B. Template synthesis of mesoporous carbons with a controlled particle size, J. Mater. Chem. 2003 13 3085-8. 

The pore size and distribution in the porous particles play essential roles in NPS synthesis. For example, only hollow capsules are obtained when MS spheres with only small mesopores (<3 nm) are used as the templates [69]. This suggests that the PE has difficulty infiltrating mesopores in this size range, and is primarily restricted to the surface of the spheres. The density and homogeneity of the pores in the sacrificial particles is also important to prepare intact NPSs. In a separate study, employing CaC03 microparticles with radial channel-like pore structures (surface area 8.8 m2 g 1) as sacrificial templates resulted in PE microcapsules that collapse when dried, which is in stark contrast to the free-standing NPSs described above [64]. 

Microporous nanoparticles with ordered zeolitic structure such as Ti-Beta are used for incorporation into walls or deposition into pores of mesoporous materials to form the micro/mesoporous composite materials [1-3], Microporous particles need to be small enough to be successfully incorporated in the composite structure. This means that the zeolite synthesis has to be stopped as soon as the particles exhibit ordered zeolitic structure. To study the growth of Ti-Beta particles we used 29Si solid-state and liquid-state NMR spectroscopy combined with x-ray powder diffraction (XRPD) and high-resolution transmission electron microscopy (HRTEM). With these techniques we monitored zeolite formation from the initial precursor gel to the final Ti-Beta product. 

The aluminum is incorporated in a tetrahedral way into the mesoporous structure, given place to Bronsted acidic sites which are corroborated by FTIR using pyridine as probe molecule. The presence of aluminum reduces the quantity of amorphous carbon produced in the synthesis of carbon nanotubes which does not happen for mesoporous silica impregnated only with iron. It was observed a decrease in thermal stability of MWCNTs due to the presence of more metal particles which help to their earlier oxidation process. 

Most examples discussed so far made use of amorphous inorganic supports or sol-gel processed hybrid polymers. Highly disperse materials have recently become accessible via standard processes and, as a result, materials with various controlled particle size, pore diameter are now available. Micelle-templated synthesis of inorganic materials leads to mesoporous materials such as MCM-41, MCM-48, MSU, and these have been extensively used as solid supports for catalysis [52]. Modifications of the polarity of the material can increase the reactivity of the embedded centre, or can decrease its susceptibility to deactivation. In rare cases, enhanced stereo- or even... 

The key effect of oxide supports on the catalytic activities of metal particles is exerted through the interface between oxides and metal particles. The key objective of this study is to develop synthesis methodologies for tailoring this interface. Here, an SSG approach was introduced to modify the surface of mesoporous silica materials with ultrathin films of titanium oxide so that the uniform deposition of gold precursors on ordered mesoporous silica materials by DP could be achieved without the constraint of the low lEP of silica. The surface sol-gel process was originally developed by Kunitake and coworkers.This novel technology enables molecular-scale control of film thickness over a large 2-D substrate area and can be viewed as a solution-based... 

XRD patterns of Pt/FSM-16 [25] (and HMM-1 [32]) show no significant change at 26 = 1-10° before and after the incorporation of metal nanowires and nanoparticles (Figure 15.7). This indicates that the pore structures and mesoporous channels of FSM-16 (and HMM-1) remained unchanged in the synthesis of the Pt wires and Pt particles [18-20, 23, 24] by wet photo-irradiation with methanol -i- water vapor and dry H2 reduction, respectively. Furthermore, in the high 26 region, typical peaks assigned to Pt fee crystalline are observed for both samples of Pt nanowire/FSM-16 and Pt nanoparticles/FSM-16 [25]. 

---