Synthesis of mesoporous bimetallic Pt–Sn catalytic coatings from polynuclear precursors for fine organic synthesis processes
L. B. Okhlopkova1, E. V. Matus1, I. Z. Ismagilov1, M. A. Kerzhentsev1, I. P. Prosvirin1, Z. R. Ismagilov2
1G. K. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk
2Institute of Coal Chemistry and Chemical Materials Science, Siberian Division, Russian Academy of Sciences, Kemerovo
Keywords: capillary microreactors, nanostructured catalysts, mesoporous titanium oxide, sol-gel synthesis, bimetallic clusters, citral hydrogenation
Abstract
A new method is developed to obtain nanosized catalytic Pt–Sn/TiO2 coatings on the inner surface of a capillary microreactor during adsorption of polynuclear carbonyl Pt–Sn complexes on mesoporous TiO2. Titanium oxide sol prepared in the presence of template (Pluronic F127 surfactant) is supported in dynamic mode. Pt–Sn bimetallic catalysts with an average particle size of 1.5-2 nm are synthesized by adsorption of the bimetallic [Pt3(CO)3(SnCl3)2(SnCl2×H2O)]n2n¯ complex followed by thermal treatment. Physicochemical properties of samples (thickness, structure and morphology, chemical composition of the material, electronic state, specific surface area, pore volume and size distribution) are characterized by a set of methods (HR TEM, SEM, powder XRD, XRF, XPS, low-temperature nitrogen adsorption). Conditions to prepare the uniform non-peelable Pt–Sn/TiO2 coating on the inner surface of a silica capillary with good adhesion are determined. To increase the TiO2 thickness, multilayered TiO2 films are synthesized by layer-by layer deposition. The coating thickness is found to increase with an increase in the capillary diameter. The coating of a capillary with a diameter of 0.55 mm after 14-fold deposition is characterized by a thickness of 2 mm and an average pore size of 5.4 nm. The solvent effect on the adsorption of Pt–Sn carbonyl complexes into the TiO2 support is studied. The amount of the adsorbed complex increases in the following order: ethanol < acetone ~ tetrahydrofuran. The physicochemical properties of the active component (surface concentration, dispersion, and composition) can be fine-tuned by varying the deposition method, precursor concentration in the initial solution, and temperature conditions of activation treatment. The catalyst activity in citral hydrogenation was 0.06-0.54 min–1, with the selectivity with respect to unsaturated alcohols reaching 90% at citral conversion above 95%.
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