Catalysts highly dispersed, preparation

Nappom WT, Laborde H, Leger J-M, Lamy C. 1995. Flectro-oxidation of Ci molecules at Pt-based catalysts highly dispersed into a polymer matrix Effect of the method of preparation. J Electroanal Chem 404 153-159. 

The reverse of reaction (2.1) is methanation. Used to remove residual CO traces from ammonia synthesis feedstocks, it was also developed as an important source of substitute natural gas (SNG) in the synthetic fuels industry. Since this reaction is exothermic, equilibrium yields are better at low temperatures (300-500 C). Thus, high activity is critical. Nickel must be highly dispersed. Preparational methods are required to produce small nickel crystallites. This high metal area must be maintained in the presence of extreme exothermicity, so that sintering must be avoided. This is partially accomplished through proper catalyst design, but process reactor type must also be considered. Recycle, fluidized, and slurry reactors are appropriate. 

Supported catalysts are prepared for a large variety of applications such as obtaining bifunctional catalysts, high dispersion of the active phase, better diffusion of gases through the bed, better mechanical resistance to attrition (moving or fluidized-bed reactors), better thermal conductivity, and improved catalytic properties induced by active phase-support interaction, to name but a few of the many potential applications/requirements of oxides as heterogeneous catalysts. 

Successful and reproducible preparation of highly dispersed catalysts crucially depends on the state of the carrier surface and on the concentration and pH of the impregnating solution. It is an art and a science for which several goodbooks and reviews exist.1 5... 

MgO-supported model Mo—Pd catalysts have been prepared from the bimetallic cluster [Mo2Pd2 /z3-CO)2(/r-CO)4(PPh3)2() -C2H )2 (Fig. 70) and monometallic precursors. Each supported sample was treated in H2 at various temperatures to form metallic palladium, and characterized by chemisorption of H2, CO, and O2, transmission electron microscopy, TPD of adsorbed CO, and EXAFS. The data showed that the presence of molybdenum in the bimetallic precursor helped to maintain the palladium in a highly dispersed form. In contrast, the sample prepared from the monometallie precursors was characterized by larger palladium particles and by weaker Mo—Pd interactions. ... 

Usually noble metal NPs highly dispersed on metal oxide supports are prepared by impregnation method. Metal oxide supports are suspended in the aqueous solution of nitrates or chlorides of the corresponding noble metals. After immersion for several hours to one day, water solvent is evaporated and dried overnight to obtain precursor (nitrates or chlorides) crystals fixed on the metal oxide support surfaces. Subsequently, the dried precursors are calcined in air to transform into noble metal oxides on the support surfaces. Finally, noble metal oxides are reduced in a stream containing hydrogen. This method is simple and reproducible in preparing supported noble metal catalysts. 

Hi ly dispersed supported bimetallic catalysts with bimetallic contributions have been prepared from molecular cluster precursors containing preformed bimetallic bond [1-2]. For examples, extremely high dispersion Pt-Ru/y-AUOa could be prepared successfully by adsorption of Pt2Ru4(CO)ison alumina [2]. By similar method, Pt-Ru cluster with carbonyl and hydride ligands, Pt3Ru6(CO)2i(p3-H)(p-H)3 (A) was used in this work to adsorb on MgO support. The ligands were expectedly removable from the metal framework at mild conditions without breaking the cluster metal core. 

XRD analysis of the solid product showed three main peaks at 28.5 , 47.4 and 56.3 , which indicated that pure crystalline CuCl was formed [3]. Several well-known dispersants polyvinyl pyrrolidone (PVP), sodium hexameta phosphate (SHP), the sodium salt of EDTA (EDTA-Na), sodium dodecyl sulfonate (SDS), and sodium dodecyl benzene sulfonate (SDBS), were introduced to obtain a highly dispersed catalyst. The X-ray patterns obtained with these were basically the same as the patterns obtained with the solids prepared in the other experiments described here. 

Mesoporous carbon materials were prepared using ordered silica templates. The Pt catalysts supported on mesoporous carbons were prepared by an impregnation method for use in the methanol electro-oxidation. The Pt/MC catalysts retained highly dispersed Pt particles on the supports. In the methanol electro-oxidation, the Pt/MC catalysts exhibited better catalytic performance than the Pt/Vulcan catalyst. The enhanced catalytic performance of Pt/MC catalysts resulted from large active metal surface areas. The catalytic performance was in the following order Pt/CMK-1 > Pt/CMK-3 > Pt/Vulcan. It was also revealed that CMK-1 with 3-dimensional pore structure was more favorable for metal dispersion than CMK-3 with 2-dimensional pore arrangement. It is eoncluded that the metal dispersion was a critical factor determining the catalytic performance in the methanol electro-oxidation. 

In summary, large (>lpm) single crystal platelets of aurichalcite produced highly dispersed Cu and ZnO particles with dimensions on the order of 5 nm, as a result of standard catalyst preparation procedures used in the treatment of the precipitate precursors. The overall platelet dimensions were maintained throughout the preparation treatments, but the platelets became porous and polycrystalline to accommodate the changing chemical structure and density of the Cu and Zn components. The morphology of ZnO and Cu in the reduced catalysts appear to be completely determined by the crystallography of aurichalcite. 

The same behaviour has been found with Cu/ZrOa. A highly dispersed Cu phase was obtained at the surface of zirconla by reacting the support with Cu acetylacetonate [19]. This procedure yields an active catalyst. This catalyst was selective for Na formation at low temperature (< 550 K), but produced only NO2 when the temperature becomes higher than 650 K. However, the same type of catalyst prepared from sulfated zirconia did not produce NO2 but selectively reduces NO to N2 whatever the temperature, with a yield of about 40% at 670 K, and a GHSV of 70000 h l, using only 300 ppm of decane. 

Figure 3. Two major categories for preparing highly dispersed gold catalysts.

The activity of gold catalyst is normally strongly size dependent and the control as well as the narrowest possible distribution of particle size represent the main goal for the production of an active gold catalyst. From a catalytic point of view, several preparation methods have been proposed for obtaining highly dispersed gold catalyst, most of them derived from deposition-precipitation method proposed by Haruta et al. [3]. 

The solid base catalysts were prepared by dissolving Cs(N03)2 (Aldrich, 99%) in the minimum amount of distilled water before addition to the silica support by spray impregnation a method used to give a high dispersion of the metal salt on the support. The amount of each precursor added was calculated in order to give a 10% loading of metal on each catalyst. The catalyst was then dried in an oven overnight at 373 K. Prior to the reaction the catalyst was calcined in situ in a flow of N2 (BOC, 02 free N2) at 10 cm3 min"1 for 2 hours at 723 K. 

With nickel/alumina catalysts (cf. 4 ) preparation by coprecipitation or by the decomposition of a high dispersion of nickel hydroxide on fresh alumina hydrogel, yields nickel aluminate exclusively. On the other hand, when, as in impregnation, larger particles of nickel compound are deposited, the calcination product is a mixture of nickel oxide and nickel aluminate. The proportion of nickel oxide increases when occlusion of the impregnation solution leads to a very nonuniform distribution (49). 

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