Contents Palladium

Zhao Z, Carpenter MA, Xia H, Welch D (2006) All-optical hydrogen sensor based on a high aUoy content palladium thin film. Sens Actuators B 113 532-538... 

Prepare a solution of 41 g. of anhydrous palladium chloride (1) in 10 ml. of concentrated hydrochloric acid and 25 ml. of water (as in A). Add all at once 60 ml. of 6iV-sulphuric acid to a rapidly stirred, hot (80°) solution of 63 1 g. of A.R. crystallised barium hydroxide in 600 ml. of water contained in a 2-htre beaker. Add more 6iV-sulphuric acid to render the suspension just acid to htmus (5). Introduce the palladium chloride solution and 4 ml. of 37 per cent, formaldehyde solution into the hot mechanically stirred suspension of barium sulphate. Render the suspension slightly alkaline with 30 per cent, sodium hydroxide solution, continue the stirring for 5 minutes longer, and allow the catalyst to settle. Decant the clear supernatant hquid, replace it by water and resuspend the catalyst. Wash the catalyst by decantation 8-10 times and then collect it on a medium - porosity sintered glass funnel, wash it with five 25 ml. portions of water and suck as dry as possible. Dry the funnel and contents at 80°, powder the catalyst (48 g.), and store it in a tightly stoppered bottle. 

PGM Concentration. The ore mined from the Merensky Reef in South Africa has a maximum PGM content of 8.1 g/1, of which 50—60% is platinum, and 20—25% palladium. The PGMs are in the form of a ferroplatinum alloy, or as their sulfides, arsenides, or teUurides. The aim of the concentration process is to separate from the ore a cmde metal concentrate, having a PGM content of 60%. The majority of other metals, such as nickel and copper, are separated out at this stage for further refining. 

Alloys based on Ag—Pd have been used for a number of years and are available from most gold alloy manufacturers (148). The palladium content is 22—50 wt % silver content is from 35 to 66 wt %. Minor amounts of Zn, In, or Sn are often present to increase fluidity. Both In and Sn form intermetaUic compounds with both Pd and Ag and, therefore, some of the commercial alloys are susceptible to age hardening (149). These alloys are somewhat difficult to fabricate and require meticulous processing. They may also produce a greenish discoloration when they are fused with porcelain veneers. Nevertheless, clinical experience generally has been satisfactory, and cost is the primary criterion for use. 

The checkers reduced the palladium chloride, in three batches, in a 500-ml. bottle. The bottle was not shaken, but the contents were rapidly stirred under a pressure of 1.1 atmospheres of hydrogen. The reduction of each batch required about 5 hours. 

Replacement of halides with deuterium gas in the presence of a surface catalyst is a less useful reaction, due mainly to the poor isotopic purity of the products. This reaction has been used, however, for the insertion of a deuterium atom at C-7 in various esters of 3j -hydroxy-A -steroids, since it gives less side products resulting from double bond migration. Thus, treatment of the 7a- or 7j5-bromo derivatives (206) with deuterium gas in the presence of 5% palladium-on-calcium carbonate, or Raney nickel catalyst, followed by alkaline hydrolysis, gives the corresponding 3j3-hydroxy-7( -di derivatives (207), the isotope content of which varies from 0.64 to 1.18 atoms of deuterium per mole. The isotope composition and the stereochemistry of the deuterium have not been rigorously established. 

Chitosan (Fig. 27) was deposited on sihca by precipitation. The palladium complex was shown to promote the enantioselective hydrogenation of ketones [80] with the results being highly dependent on the structure of the substrate. In the case of aromatic ketones, both yield and enantioselectiv-ity depend on the N/Pd molar ratio. Low palladium contents favored enan-tioselectivity but reduced the yield. Very high conversions were obtained with aliphatic ketones, although with modest enantioselectivities. More recently, the immobilized chitosan-Co complex was described as a catalyst for the enantioselective hydration of 1-octene [81]. Under optimal conditions, namely Co content 0.5 mmolg and 1-octene/Co molar ratio of 50, a 98% yield and 98% ee were obtained and the catalyst was reused five times without loss of activity or enantioselectivity. 

In order to probe the influence of Au and KOAc on the vinyl acetate synthesis chemistry, four different catalysts were synthesized. All of these catalysts were prepared in a manner exemplified in prior patent technology [Bissot, 1977], and each contained the same palladium loading in an egg-shell layer on the surface of a spherical silica support. The palladium content in the catalyst was easily controlled by adjusting the solution strength of palladium chloride (PdClj) added to the porous silica beads prior to its precipitation onto the support by reaction with sodium metasilicate (Na SiOj). The other two catalyst components (Au and KOAc) were either present or absent in order to complete the independent evaluation of their effect on the process chemistry, e.g., (1) Pd-i-Au-hKOAc, (2) Pd-i-KOAc, (3) Pd-hAu, and (4) Pd only. 

In preparing this chapter, the authors surveyed a vast literature seeking studies with original findings, convincing explanations, and probable useful applications. Merely solid studies were downplayed, as their results are more or less predictable. Whenever possible, studies of palladium complexes were placed in their broader context, with minimal dilution of the content of this chapter. 

X-Ray studies confirm that platinum crystallites exist on carbon supports at least down to a metal content of about 0.03% (2). On the other hand, it has been claimed that nickel crystallites do not exist in nickel/carbon catalysts (50). This requires verification, but it does draw attention to the fact that carbon is not inert toward many metals which can form carbides or intercalation compounds with graphite. In general, it is only with the noble group VIII metals that one can feel reasonably confident that a substantial amount of the metal will be retained on the carbon surface in its elemental form. Judging from Moss s (35) electron micrographs of a reduced 5% platinum charcoal catalyst, the platinum crystallites appear to be at least as finely dispersed on charcoal as on silica or alumina, or possibly more so, but both platinum and palladium (51) supported on carbon appear to be very sensitive to sintering. 

Figure 7. Carbon and oxygen content of 0.12 nm palladium acetate film, measured by Rutherford backscattering spectroscopy, as a function of 2 MeV He+ ion dose.

Hence, the decision to use a heated substrate with simultaneous evaporation of the component metals as an aid to homogenization requires consideration of whether or not it might have an adverse effect, i.e., causing preferential nucleation of one component, which interdiffusion may not be able to remedy. It was believed (60) that in preparing Pd-Rh alloys by simultaneous deposition on a substrate at 400°C, rhodium nucleated preferentially and that crystallites grew by the addition of palladium (and rhodium) atoms. The diffusion of palladium atoms into this kernel formed a phase with 88 =t 5% Rh (phase II). The outer shell of the crystallite, phase I, was in effect a solid solution deficient in rhodium compared with the overall film composition, and the Rh content of phase I therefore increased as the Rh flux was increased. 

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