Metals catalytic activity, methanol synthesis

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. 

In a new study of a series of binary Cu-ZnO catalysts a correlation was found between methanol synthesis activity and strain in the Cu metal phase.619 Structural defects of Cu resulting from ZnO dissolved in Cu, incomplete reduction, or epitaxial orientation to ZnO are believed to bring about strain, which modifies the Cu surface and, consequently, affects the catalytic activity. The higher amount of water formed in methanol synthesis from a C02-rich feed compared to a CO-rich feed brings about significant catalyst deactivation by inducing crystallization of both Cu and ZnO.620... 

Another contribution to variations of intrinsic activity is the different number of defects and amount of disorder in the metallic Cu phase. This disorder can manifest itself in the form of lattice strain detectable, for example, by line profile analysis of X-ray diffraction (XRD) peaks [73], 63Cu nuclear magnetic resonance lines [74], or as an increased disorder parameter (Debye-Waller factor) derived from extended X-ray absorption fine structure spectroscopy [75], Strained copper has been shown theoretically [76] and experimentally [77] to have different adsorptive properties compared to unstrained surfaces. Strain (i.e. local variation in the lattice parameter) is known to shift the center of the d-band and alter the interactions of metal surface and absorbate [78]. The origin of strain and defects in Cu/ZnO is probably related to the crystallization of kinetically trapped nonideal Cu in close interfacial contact to the oxide during catalyst activation at mild conditions. A correlation of the concentration of planar defects in the Cu particles with the catalytic activity in methanol synthesis was observed in a series of industrial Cu/Zn0/Al203 catalysts by Kasatkin et al. [57]. Planar defects like stacking faults and twin boundaries can also be observed by HRTEM and are marked with arrows in Figure 5.3.8C [58],... 

The question as to what is the active site of Cu-based catalysts in MSR is still unclear and debated in the literature. Similar to the methanol synthesis reaction, either metallic Cu° sites, oxidized Cu+ sites dispersed on the oxide component or at the Cu-oxide interface, or a combination of both kinds of sites are thought to contribute to the active ensembles at the Cu surface. Furthermore, the oxidic surface of the refractory component may take part in the catalytic reaction and provide adsorption sites for the oxygenate-bonded species [126], whereas hydrogen is probably adsorbed at the metallic Cu surface. Similar to methanol synthesis, factors intrinsic to the Cu phase also contribute to the MSR activity in addition to SACu- There are two major views discussed in the literature relating these intrinsic factors either to the variable oxidation state of Cu, in particular to the in situ adjustment of the Cu°/Cu+ ratio at the catalyst s surface [102, 107, 127 132], or to the defect structure and varying... 

The modern methanol synthesis catalyst consists of copper, zinc oxide, and alumina. Copper metal is seen as the catalytically active phase, and ZnO as the promoter. It is well known that the interaction between the two components is essential for achieving a high activity, but the nature of the promoting effect is still a matter of debate. Loss of activity is caused by sintering of the Cu crystallites, and, if the feed gas contains impurities such as chlorine and sulfur, by poisoning. 

Methyl formate has been proposed to be a versatile intermediate in the synthesis of oxygenated base chemicals [128, 129]. One of the most interesting synthetic routes to methyl formate is the reduction of CO2 with hydrogen in the presence of methanol. This reaction is exothermic, and has been referred to as the hydrocondensation of CO2 with methanol. Since the first report of a successful transition metal-catalyzed reaction by a Russian group [130], several other reports have been published. However, the catalytic activity (i.e., the TOF) has not been satisfactory. 

In summary, cluster-derived catalysts have been widely used in various types of CO-based reactions such as Fischer-Tropsch synthesis, methanol synthesis, hydroformylation, carbonylation, and water-gas shift reactions. The catalytic performances of cluster-derived species are evaluated in terms of higher activities and selectivities for lower olefins and oxygenates in CO hydrogenation, compared with those of metal complexes in solution and conventional metal catalysts (Table XIII). 

Various kinds of metal catalysts are reported to be active for methanol synthesis from H2/CO2. Activity of metal catalyst for methanol yield increased with following order, Cu Co=Pd=Re>Ni>Fe Ru=Pt>Os>Ir=Ag=Rh>Au.[8] Needless to say, catalytic activity is much dependent on metal dispersion, additives and type of support. It is apparent, however, Copper is the most active metal species for methanol production. Effect of metal oxide support to 5wt%Cu catalyst was studied. [9]... 

In 1970 the transition metal catalyzed formation of alkyl formates from CO2, H2, and alcohols was first described. Phosphine complexes of Group 8 to Group 10 transition metals and carbonyl metallates of Groups 6 and 8 show catalytic activity (TON 6-60) and in most cases a positive effect by addition of amines or other basic additives [26 a, 54-58]. A more effective catalytic system has been found when carrying out the reaction in the supercritical phase (TON 3500) [54 a]. Similarly to the synthesis of formic acid, the synthesis of methyl formate in SCCO2 is successful in the presence of methanol and ruthenium(II) catalyst systems [54 b]. 

The catalytic activity of a series of M/(3ZnO Zr02) catalysts (where M = Cu, Ag, Au) was evaluated for the synthesis of methanol from CO2 [467]. The catalysts containing Au and Ag were shown to have these metals distributed more uniformly. The catalytic activity was higher for the Cu catalysts, but Au catalysts were shown to be slightly more selective to methanol than the others. 

The nature of the outer-layer of the Cu-Zn based catalysts and the role of the different active sites are still a topic of investigation. Metallic copper is implicated as being the dominant oxidation state of the metal during the reaction. However, the presence of Cu+ is also important as a small amount of oxygen increases the reaction rate.51,66 Shen et al.67 found on ceria supported copper catalyst that in spite of the reductive reaction atmosphere, metallic copper particles on cerium oxide were oxidised during reaction and the catalyst was activated. The formation of the copper oxide species was considered indispensable for the onset of high catalytic activity. Synergy between Cu and ZnO in the catalysis of methanol synthesis... 

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