Mesoporous catalyst films

The titanosilicate version of UTD-1 has been shown to be an effective catalyst for the oxidation of alkanes, alkenes, and alcohols (77-79) by using peroxides as the oxidant. The large pores of Ti-UTD-1 readily accommodate large molecules such as 2,6-di-ferf-butylphenol (2,6-DTBP). The bulky 2,6-DTBP substrate can be converted to the corresponding quinone with activity and selectivity comparable to the mesoporous catalysts Ti-MCM-41 and Ti-HMS (80), where HMS = hexagonal mesoporous silica. Both Ti-UTD-1 and UTD-1 have also been prepared as oriented thin films via a laser ablation technique (81-85). Continuous UTD-1 membranes with the channels oriented normal to the substrate surface have been employed in a catalytic oxidation-separation process (82). At room temperature, a cyclohexene-ferf-butylhydroperoxide was passed through the membrane and epoxidation products were trapped on the down stream side. The UTD-1 membranes supported on metal frits have also been evaluated for the separation of linear paraffins and aromatics (83). In a model separation of n-hexane and toluene, enhanced permeation of the linear alkane was observed. Oriented UTD-1 films have also been evenly coated on small 3D objects such as glass and metal beads (84, 85). 

Well ordered mesoporous silicate films were prepared in supercritical carbon dioxide.[218] In the synthesis in aqueous or alcoholic solution, film morphology of preorganized surfactants on substrate cannot be fully prescribed before silica-framework formation, because structure evolution is coincident with precursor condensation. The rapid and efficient preparation of mesostructured metal oxides by the in situ condensation of metal oxides within preformed nonionic surfactants can be done in supercritical CCU- The synthesis procedure is as follows. A copolymer template is prepared by spin-coating from a solution containing a suitable acid catalyst. Upon drying and annealing to induce microphase separation and enhance order, the acid partitions into the hydrophilic domain of the template. The template is then exposed to a solution of metal alkoxide in humidified supercritical C02. The precursor diffuses into the template and condenses selectively within the acidic hydrophilic domain of the copolymer to form the incipient metal oxide network. The templates did not go into the C02 phase because their solubility is very low. The alcohol by-product of alkoxide condensation is extracted rapidly from the film into the C02 phase, which promotes rapid and extensive network condensation. Because the template and the metal oxide network form in discrete steps, it is possible to pattern the template via lithography or to orient the copolymer domains before the formation of the metal oxide network. 

The synthesis of mesoporous silica films typically begins with the preparation of precursor solutions. These solutions contain a silica source (typically an alkoxide, although chloride and colloidal precursors can be used), a surfactant molecule used to template the mesostructure, an acid or base catalyst, and solvents. The nanoscale structure is then formed by a cooperative self-assembly of monomeric or partially... 

Another use of nonpermselective membranes is in multiphase organic reactions involving trickle-bed type reactors (Harold et al., 1989, 1994 Cini and Harold, 1991). The reactor consists essentially of a hollow macroporous membrane tube coated on the inside with a hollow mesoporous catalyst layer, as shown in Figure 24.Id. Liquid and gas are allowed to flow on opposite sides of the membrane. Because the gas comes into direct contact with the liquid-fllled catalyst, it resembles a trickle-bed reactor. However, because there is no separate liquid film to hamper the supply of gas to the catalyst sites, it performs better than the traditional trickle-bed reactor. 

Figure 4.49. Electrocatalytic activity of mesoporous PtRu as a function of CH3OH concentration. Catalyst film prepared by liquid crystal (surfactant Ci EOg) templated reduction using Zn. Electrode potential 0.38 Vvs. RHE, 333 K. Data taken after 900 s of polarization [247]. (Reprodueed from Journal of Electroanalytical Chemistry, 543(2), Jiang J, Kucemak A, Electrooxidation of small organic molecules on mesoporous precious metal catalysts II CO and methanol on platinum-ruthenium alloy, 187-99, 2003, with permission from Elsevier.)...

Kerzhentsev, M.A., Rebrov, E.V., and Schouten, J.C. (2009) Design of Pt-Sn catalysts on mesoporous titania films for microreactor application. Catal. Today, 147 (1), S81-S86. 

The classic sensitizer dye employed in DSC is a Ru(II) bipyridyl dye, cis-bis(isothiocyanato)-bis(2,2/-bipyridyl-4,4/-dicarboxylato)-Ru(II), often referred to as N3 , or in its partially deprotonated form (a di-tetrabutyl-ammonium salt) as N719. The structure of these dyes are shown in 2 and 26. The incorporation of carboxylate groups allows immobilization of sensitizer to the film surface via the formation of bidendate coordination and ester linkages, whilst the (- NCS) groups enhance the visible light absorption. Adsorption of the dye to the mesoporous film is achieved by simple immersion of the film in a solution of dye, which results in the adsorption of a dye monolayer to the film surface. The counter electrode is fabricated from FTO-coated glass, with the addition of a Pt catalyst to catalyze the reduc-... 

Finally, Vroon et al. [82,97] reported the synthesis of continuous porous films of ZSM5 on top of y-alumina supported membranes (pore diameter 4 nm) by slip-casting with a zeolite crystal suspension. The porous zeolite layers (thickness 1-2.5 pm) consist of densely packed zeolite crystals with a diameter of 70-80 nm and with micropores in the zeolite and mesopores (diameter 8-24 nm) between the zeolite particles. This zeolite layer can be used as a support for further processing, e.g., pore filling of the mesopores or deposition of catalysts. First experiments by Vroon et al. to fill the mesopores by in situ crystallisation of MFI in the pores did not result in gas-tight membranes... 

Self-assembly plays a key role in many areas (Fig. 9). Using self-aggregates as templates has proven to be an extremely powerful approach for developing novel materials, especially mesoporous particles and films for use as catalysts, catalyst supports, sorbents, and molecular sieves. Biological systems offer many examples of highly complex process in which intricate structures formed by self-assembly play a key role. Understanding these systems will help drive the development of next-generation materials. 

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