Silica supports formation

As in the case of graphite-supported catalysts, some metal particles were also encapsulated by the deposited carbon (Fig. 4). However, the amount of encapsulated metal was much less. Differences in the nature of encapsulation were observed. Almost all encapsulated metal particles on silica-supported catalysts were found inside the tubules (Fig. 4(a)). The probable mechanism of this encapsulation was precisely described elsewhere[21 ]. We supposed that they were catalytic particles that became inactive after introduction into the tubules during the growth process. On the other hand, the formation of graphite layers around the metal in the case of graphite-supported catalysts can be explained on the basis of... 

This paper describes the catalytic activity of nickel phosphide supported on silica, alumina, and carbon-coated alumina in the hydrodesulfurization of 4,6-dimethyldibenzothiophene. The catalysts are made by the reduction of phosphate precursors. On the silica support the phosphate is reduced easily to form nickel phosphide with hi catalytic activity, but on the alumina support interactions between the phosphate and the alumina hinder the reduction. The addition of a carbon overlayer on alumina decreases the interactions and leads to the formation of an active phosphide phase. 

The effect of precursor-support interactions on the surface composition of supported bimetallic clusters has been studied. In contrast to Pt-Ru bimetallic clusters, silica-supported Ru-Rh and Ru-Ir bimetallic clusters showed no surface enrichment in either metal. Metal particle nucleation in the case of the Pt-Ru bimetallic clusters is suggested to occtir by a mechanism in which the relatively mobile Pt phase is deposited atop a Ru core during reduction. On the other hand, Ru and Rh, which exhibit rather similar precursor support interactions, have similar surface mobilities and do not, therefore, nucleate preferentially in a cherry model configuration. The existence of true bimetallic clusters having mixed metal surface sites is verified using the formation of methane as a catalytic probe. An ensemble requirement of four adjacent Ru surface sites is suggested. 

Thermal reduction at 623 K by means of CO is a common method of producing reduced and catalytically active chromium centers. In this case the induction period in the successive ethylene polymerization is replaced by a very short delay consistent with initial adsorption of ethylene on reduce chromium centers and formation of active precursors. In the CO-reduced catalyst, CO2 in the gas phase is the only product and chromium is found to have an average oxidation number just above 2 [4,7,44,65,66], comprised of mainly Cr(II) and very small amount of Cr(III) species (presumably as Q -Cr203 [66]). Fubini et al. [47] reported that reduction in CO at 623 K of a diluted Cr(VI)/Si02 sample (1 wt. % Cr) yields 98% of the silica-supported chromium in the +2 oxidation state, as determined from oxygen uptake measurements. The remaining 2 wt. % of the metal was proposed to be clustered in a-chromia-like particles. As the oxidation product (CO2) is not adsorbed on the surface and CO is fully desorbed from Cr(II) at 623 K (reduction temperature), the resulting catalyst acquires a model character in fact, the siliceous part of the surface is the same of pure silica treated at the same temperature and the anchored chromium is all in the divalent state. 

Pt particles remain highly dispersed in the reaction mixture during mesostructure formation. All measurements including XRD, SAXS, and TEM indicate a well-ordered silica structure. N2 physisorption measurement indicated high surface areas (523-661 m g ) and meso-sized pores (112-113 A) for the silica supports produced in the presence of different Pt particles. 

Figure 2.20. Transformation of silica supported dinitrosyl complexes of nickel(II) leading to formation of nitrogen dioxide and its final stabilization on the support. The picture shows the molecular structure and the spin density contours calculated with BP/DNP method of the involved species, and evolution of the X-band EPR spectra of the NiN02 Si02 complex due to spillover of the ligand (adopted from [71]).

The work of Kikuchi et al. (123) with silica-supported catalysts also shows the high tendency of iron (370°-400°C), cobalt (330o-360°C) and nickel (330°-370°C) to catalyze fragmentation (of n-pentane) to methane. This work also showed that with cobalt and nickel, the extent of methane formation tended to decrease with increasing hydrogen partial pressure. Some data are listed in Table XII. 

Alstrup, I. and Tavares, T., Kinetics of carbon formation from CH4-H2 on silica-supported nickel and Ni-Cu catalysts, /. Catal., 139, 513,1993. 

Ethanol can be derived from biomass by means of acidic/enzymatic hydrolysis or also by thermochemical conversion and subsequent enzymatic ethanol formation. Likewise for methanol, hydrogen can be produced from ethanol with the ease of storage/transportation and an additional advantage of its nontoxicity. Apart from thermodynamic studies on hydrogen from ethanol steam reforming,117-119 catalytic reaction studies were also performed on this reaction using Ni-Cu-Cr catalysts,120 Ni-Cu-K alumina-supported catalysts,121 Cu-Zn alumina-supported catalysts,122,123 Ca-Zn alumina-supported catalysts,122 and Ni-Cu silica-supported catalysts.123... 

For several silica-supported catalysts in condensed phase, including the SAPC system, the rates are disappointing. This can be assigned to slow mass transfer, and perhaps to incomplete rhodium hydride formation as we have discussed and observed. The sol-gel catalyst is relatively fast and is sometimes only a few times slower than the homogeneous one. Since only limited ways of preparation were tested, there is probably more scope for sol-gel catalysts. Space-time yields are promising at the present state of affairs. 

Another study on the preparation of supported oxides illustrates how SIMS can be used to follow the decomposition of catalyst precursors during calcination. We discuss the formation of zirconium dioxide from zirconium ethoxide on a silica support [15], Zr02 is catalytically active for a number of reactions such as isosynthesis, methanol synthesis, and catalytic cracking, but is also of considerable interest as a barrier against diffusion of catalytically active metals such as rhodium or cobalt into alumina supports at elevated temperatures. 

Several groups have reported deactivation of silica-supported cobalt catalysts. Holmen and coworkers19 30 have reported increased deactivation due to added (external) water in the feed to silica-supported Co catalysts. Kogelbauer et al 1 reported the formation of silicates. Catalysts recovered from FTS as well as catalysts deactivated by steam-treatment both showed fractions of non-reducible cobalt in TPR. The presence of metallic cobalt was a prerequisite for the silicate formation. 

Structures of immobilized rhodium complexes on the sihca support have been proposed on the basis of the data obtained from C, P and Si MAS-NMR. NMR spectra of the rhodium-modified solid materials confirmed that trimethylsiloxide ligand was removed from the rhodium coordination sphere during the immobilization process. Formation of a new covalent bond between the rhodium organo-metallic moiety and the silica support occurs, probably with evolution of trimethylsilanol, which is rapidly converted into disiloxane (Me3Si)20. The presence of this molecule in the solution obtained after the silica surface modification process was confirmed by GCMS analysis. 

As for heterogeneous olefin polymerization catalysis, the activity of rare-earth metal catalysts may be also enhanced in organic transformations by the use of silica supports or other carriers [7]. Indeed, several catalytic C-C and C-X (with X = H/D, Si, O) bond formation reactions as weU as functional group transformations witness to the potential of SOLn/AnC-based heterogeneous catalysts for fine chemical synthesis. 

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