Catalyst preparation particle forming

The induction of steric effects by the pore walls was first demonstrated with heterogeneous catalysts, prepared from metal carbonyl clusters such as Rh6(CO)16, Ru3(CO)12, or Ir4(CO)12, which were synthesized in situ after a cation exchange process under CO in the large pores of zeolites such as HY, NaY, or 13X.25,26 The zeolite-entrapped carbonyl clusters are stable towards oxidation-reduction cycles this is in sharp contrast to the behavior of the same clusters supported on non-porous inorganic oxides. At high temperatures these metal carbonyl clusters aggregate to small metal particles, whose size is restricted by the dimensions of the zeolitic framework. Moreover, for a number of reactions, the size of the pores controls the size of the products formed thus a higher selectivity to the lower hydrocarbons has been reported for the Fischer Tropsch reaction. 

Catalyst preparation to a solution of Cu(N03)2.3H20 (I6g ) in 150 ml H2O, 30% NH4OH was added till dissolution of the hydroxide initially formed. To the clear solution 20 g of alumina (Riedel-De-Haen), pH 4.5, surface area 200 m2/g, particle size 70-290 mesh, were added. The suspension was stirred for 10 minutes and diluted, very slowly,to 2L volume, stirred for 30 minutes and filtered off. 

PtRu catalysts with controlled atomic ratios were prepared by adjusting the nominal concentrations of platinum and ruthenium salts in the solution, whereas different mean particle sizes could be obtained by adjusting some electric parameters of the deposition process, e.g., ton (during which the current pulse is applied) and toff (when no current is applied to the electrode), as determined by different physicochemical methods (XRD, EDX, and TEM) [40], Characterization by XRD led to determine the crystallite size, the atomic composition and the alloy character of the PtRu catalysts. The atomic composition was confirmed using EDX, and TEM pictures led to evaluate the particle size and to show that PtRu particles formed small aggregates of several tens of nanometers (Figure 9.10). 

Another non-conventional preparative route to bimetallic catalysts has been developed where metal atoms (vapors) have been trapped at low temperature in solvating media. (A review has recently appeared).(17) By solvating two metals at the same time (eg. Co in toluene and Mn in toluene), followed by warming, bimetallic clusters/particles form. In the presence of a catalyst support, surface -OH groups can have a dramitic affect on the structure of the small bimetallic cluster produced. For example, with Co and Mn, a layered structure of MnOx covered by Co° in a particle of about 25 A was formed.(iS) With Fe and Co combinations, a layer of FeOx followed by Fe°Co° alloy and a surface rich in Co° was formed. (19)... 

Although typical catalyst preparation procedures vary slightly from one laboratory to another, the "conventional approach" is to deposit a metal salt on a support, convert this salt to the oxide, and then reduce to the metallic state. When two metals are simultaneously so treated and reduced, bimetallic clusters may form. However, it cannot be assumed that bimetallic clusters are produced since monometallic separate particles may predominate. In fact, it is perhaps the unusual case where bimetallics do form since there are many possible paths, both thermodynamic and kinetic, that can lead to (1) separate monometallic s, (2) one metal not reduced, (3) thermal segregation of bimetallic precursor particle, and/or (4) volatilization or migration of one metal. 

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