Fundamentals of melt infiltration for the preparation of supported metal catalysts. The case of Co/SiO2 for Fischer-Tropsch synthesis

We explored melt infiltration of mesoporous silica supports to prepare supported metal catalysts with high loadings and controllable particle sizes. Melting of Co(NO(3))(2)·6H(2)O in the presence of silica supports was studied in situ with differential scanning calorimetry. The melting point depression of the intraporous phase was used to quantify the degree of pore loading after infiltration. Maximum pore-fillings corresponded to 70-80% of filled pore volume, if the intraporous phase was considered to be crystalline Co(NO(3))(2)·6H(2)O. However, diffraction was absent in XRD both from the ordered mesopores at low scattering angles and from crystalline cobalt nitrate phases at high angles. Hence, an amorphous, lower density, intraporous Co(NO(3))(2)·6H(2)O phase was proposed to fill the pores completely. Equilibration at 60 °C in a closed vessel was essential for successful melt infiltration. In an open crucible, dehydration of the precursor prior to infiltration inhibited homogeneous filling of support particles. The dispersion and distribution of Co(3)O(4) after calcination could be controlled using the same toolbox as for preparation via solution impregnation: confinement and the calcination gas atmosphere. Using ordered mesoporous silica supports as well as an industrial silica gel support, catalysts with Co metal loadings in the range of 10-22 wt % were prepared. The Co(3)O(4) crystallite sizes ranged from 4 to 10 nm and scaled with the support pore diameters. By calcination in N(2), pluglike nanoparticles were obtained that formed aggregates over several pore widths, while calcination in 1% NO/N(2) led to the formation of smaller individual nanoparticles. After reduction, the Co/SiO(2) catalysts showed high activity for the Fischer-Tropsch synthesis, illustrating the applicability of melt infiltration for supported catalyst preparation.     

Syntheses of Conjugated Polymers for Photonics

Summary: By the Suzuki coupling reaction of 9,9-dioctyl-2,7-bis(1,3,2-dioxaborinan-2-yl)fluorene ( I ) and 3,5-di-tert-butylphenyl 2,5-dibromobenzenesulfonate ( II ) the alternating poly{[9,9-dioctylfluoren-2,7-diyl]-alt-[2-(3,5-di-tert-butyl-phenoxysulfonyl)-1,4-phenylene]} ( III ) was synthesized. Alkaline hydrolysis of III gave a conjugated polyelectrolyte carrying sulfonic acid groups ( IV ). Monomers 2,5-dibromo-3-[2-(pyren-1-yl)vinyl]thiophene and 2,5-dibromo-3-[2-(quinolin-4-yl)vinyl)thiophene were prepared and copolymerized with I to afford poly{[9,9-dioctylfluoren-2,7-diyl]-alt-[3-(2-(pyren-1-yl)vinyl)thiophen-2,5-diyl]} ( V ) and poly{[9,9-dioctylfluoren-2,7-diyl]-alt-[3-(2-(quinolin-4-yl)-vinyl)thiophen-2,5-diyl] ( VI ), respectively. Conjugated backbone of V contains the conjugated pyrene unit in the side chain. Similarly the side chain of VI contains the conjugated quinoline structure unit which can be for instance protonated. By the Suzuki polycondensation reaction of I and of the prepared methyl 3-(2,7-dibromocarbazole-9-yl)propionate ( VII ) the new poly{[9,9-dioctylfluorene-2,7-diyl]-alt-[9-(2-methoxycarbonylethyl)carbazole-2,7-diyl]} ( VIII ) was synthesized and characterized.     

Bismuth modified Pd/C as catalysts for hydrogen related reactions

The electrocatalytic activity of bimetallic BiPd catalysts supported on Sibunit carbon towards hydrogen oxidation/evolution reactions (HOR/HER) was studied in a gas diffusion electrode (GDE) setup. Catalysts were synthesized by deposition of Pd on the carbon support, followed by impregnation of Pd/C precursor with Bi(NO₃)₃ solution and reduction in hydrogen. Transmission electron microscopy and local EDX elemental analysis revealed that BiPd/C catalysts contain bimetallic particles with narrow size distribution with maxima at 3.2–4.1 nm. X-ray diffraction evidenced that bimetallic particles are constituted by Pd–Bi solid solution. It was shown that modification of Pd/C by bismuth increases the specific activity of palladium towards HOR/HER by a factor of 3.     

Thermal study of the Ce<Subscript>0.9</Subscript>Tb<Subscript>0.1</Subscript>O<Subscript>2</Subscript> pigment prepared by different synthesis

The inorganic ceramic compounds based on the CeO₂ belong into the group of high-temperature pigments. The pigments have been prepared by the classical dry process (i.e. solid-state reaction) in the temperature range from 1,300 to 1,600 °C and by the coprecipitation at the three different temperatures: 400, 600 and 1,100 °C. The principal of these pigments makes the host lattice of the CeO₂, which is doped by terbium ions. This incorporation of the doped ions leads to obtaining of the interesting dark orange colour after application into ceramic glaze. The aim of our research was to improve and optimize the synthesis conditions of these pigments. The samples were submitted to thermal analysis (TG–DTA) for determination of the temperature interval of the pigment formation and the thermal stability of pigments. The compounds were also measured from the point of view of their colouring, structure and particle size distribution.     

Granulation of activated sludge in a laboratory upflow sludge blanket reactor

The creation of anoxic granulated biomass has been monitored in a laboratory USB (Upflow Sludge Blanket) reactor with the volume of 3.6 L. The objective of this research was to verify the possibilities of post-denitrification of residual NO₃-N concentrations in treated wastewater (denitrification of 10-20 mg L⁻¹ NO₃-N) and to determine the maximum hydraulic and mass loading of the granulated biomass reactor. G-phase from biodiesel production and methanol were both tested as external organic denitrification substrates. The ratio of the organic substrate COD to NO₃-N was 6. Only methanol was proven as a suitable organic substrate for this kind of reactor. However, the biomass adaptation to the substrate took over a week. The cultivation of anoxic granulated biomass was reached at hydraulic loading of over 0.35 m h⁻¹. The size of granules was smaller when compared with results found and described in literary reports (granules up to 1 mm); however, settling properties were excellent and denitrification was deemed suitable for the USB reactor. Sludge volume indexes of granules ranged from 35-50 mL g⁻¹ and settling rates reached 11 m h⁻¹. Maximum hydraulic and mass loadings in the USB reactor were 0.95 m3 m⁻² h⁻¹ and 6.6 kg m⁻³ d⁻¹. At higher loading levels, a wash-out of the biomass occurred. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

Control of EOF in CE by different ways of application of radial electric field

Various ways of application of radial electric field for the control of electrokinetic potential and EOF in a home-made device for CE are presented. The device comprises three high-voltage power supplies, which are used to form a radial electric field across the fused-silica capillary wall. One power supply provides the internal electric field - a driving force for electrophoretic migration of charged analytes and for the EOF. Two power supplies are connected to the ends of the outer low-conductivity polymeric coating, which is formed by the dispersion of insoluble conductive copolymer of aniline and p-phenylendiamine in polystyrene matrix (dissolved in N-methylpyrrolidone) attached to the original outer polyimide coating of the capillary. They are able to constitute the external longitudinal electric field with variable values of electric potential at both ends of the outer coating. The potential gradient between the external and internal electric field is perpendicular to the capillary wall and forms a radial electric field across the capillary wall, which affects the electrokinetic potential at the solid-liquid interface and EOF inside the capillary. The developed device and methodology has been applied for the analysis of both chiral and achiral molecules such as terbutaline enantiomers and oligopeptides (diglycine and triglycine). The effect of magnitude, orientation, and different ways of application of the radial electric field on the flow rate of the EOF and on the speed, efficiency, and resolution of CZE separations of the above analytes in the internally noncoated fused-silica capillaries have been evaluated.     

Secretory phospholipase A2 hydrolysis of phospholipid analogues is dependent on water accessibility to the active site

A new and unnatural type of phospholipids with the head group attached to the 2-position of the glycerol backbone has been synthesized and shown to be a good substrate for secretory phospholipase A2 (sPLA2). To investigate the unexpected sPLA2 activity, we have compared three different phospholipids by using fluorescence techniques and HPLC, namely: (R)-1,2-dipalmitoyl-glycero-3-phosphocholine (hereafter referred to as 1R), (R)-1-O-hexadecyl-2-palmitoyl-glycero-3-phoshocholine (2R), and (S)-1-O-hexadecyl-3-palmitoyl-glycero-2-phosphocholine (3S). Furthermore, to understand the underlying mechanisms for the observed differences, we have performed molecular dynamics simulations to clarify on a structural level the substrate specificity of sPLA2 toward phospholipid analogues with their head groups in the 2-position of the glycerol backbone. We have studied the lipids above 1R, 2R, and 3S as well as their enantiomers 1S, 2S, and 3R. In the simulations of sPLA2-1S and sPLA2-3R, structural distortion in the binding cleft induced by the phospholipids showed that these are not substrates for sPLA2. In the case of the phospholipids 1R, 2R, and 3S, our simulations revealed that the difference observed experimentally in sPLA2 activity might be caused by reduced access of water molecules to the active site. We have monitored the number of water molecules that enter the active site region for the different sPLA2-phospholipid complexes and found that the probability of a water molecule reaching the correct position such that hydrolysis can occur is reduced for the unnatural lipids. The relative water count follows 1R > 2R > 3S. This is in good agreement with experimental data that indicate the same trend for sPLA2 activity: 1R > 2R > 3S.     

Metadynamics in essential coordinates: free energy simulation of conformational changes

We propose an approach that combines an extraction of collective motions of a molecular system with a sampling of its free energy surface. A recently introduced method of metadynamics allows exploration of the free energy surface of a molecular system by means of coarse-grained dynamics with flooding of free energy minima. This free energy surface is defined as a function of a set of collective variables (e.g., interatomic distances, angles, torsions, and others). In this study, essential coordinates determined by essential dynamics (principle component analysis) were used as collective variables in metadynamics. First, dynamics of the model system (explicitly solvated alanine dipeptide, Ace-Ala-Nme) was simulated by a classical molecular dynamics simulation. The trajectory (1 ns) was then analyzed by essential dynamics to obtain essential coordinates. The free energy surface as a function of the first and second essential coordinates was then explored by metadynamics. The resulting free energy surface is in agreement with other studies of this system. We propose that a combination of these two methods (metadynamics and essential dynamics) has great potential in studies of conformational changes in peptides and proteins.