Catalysts nickel black

CATALYSTS Chlorotrisftriphenylphos-phine)rhodium(I). (S)-a-(R)-2-Di-phenylphosphinoferrocenyl ethyldl-methylamine. Hydridotrisftriisopropyl-phosphine)rhodium(I). Iridium black. 2,3-0-Isopropylidene-2,3-dihydroxy-l,4-bis(diphenylphosphino)butane. Lindlar catalyst. Nickel-Alumina. Palladium catalysts. Raney nickel. Rhodium oxide-Platinum oxide. 

Hydrogenation catalyst. Iridium black is a highly selective hydrogenation catalyst. Yamamoto and Sham used this catalyst to effect the remarkably stereoselective (>98%) hydrogenation of 1 to 2. Mixtures of stereoisomers are obtained when 1 is hydrogenated with palladium on charcoal or Raney nickel. 

Fig. 12.1. The different stages in the hydrogenation of nickel oxide to a nickel black catalyst.

Reduction of nickel acetate with sodium hydride gave a nickel black catalyst that was active for the selective hydrogenation of acetylenes and dienes to the monoolefins. It was also capable of promoting the hydrogenation of carbonyl... 

X-ray photoelectron (XPS) studies of nickel boride, nickel phosphide, Raney nickel and Urushibara nickel showed that the electron density on the nickel was a function of the other metal present in these catalysts. 28J29 Boron, aluminum (Raney nickel) and zinc (Urushibara nickel) all increased the electron density on the nickel while phosphorous was an electron acceptor. Comparing the electron densities on the nickel in these catalysts with that on a nickel black prepared by the thermal decomposition of nickel formate (D-Ni) gave the series Ni-B > Ni-Al > Ni-Zn > D-Ni > Ni-P. 

A parameter, Aq, was defined as the relative change in electron density on nickel resulting from electron transfer between nickel and the second element as compared with that on nickel black. Table 12.2 shows the Aq values for these different nickel catalysts. 29 That for the P-1 nickel boride25 is the most negative and that for the NiP-1 nickel phosphide is the most positive. In Fig. 12.5 is shown the relationship between the areal turnover frequencies for the hydrogenation of styrene over these catalysts and their Aq values. 29 These data... 

Hydrazine is a highly reactive reducing agent that forms shock-sensitive, explosive mixtures with many compounds. It explodes on contact with barium oxide, calcium oxide, chromate salts, and many other substances. On contact with metal catalysts (platinum black, Raney nickel, etc.), hydrazine decomposes to ammonia, hydrogen, and nitrogen gases, which may ignite or explode. 

Black nickel oxide is used as an oxygen donor in three-way catalysts containing rhodium, platinum, and palladium (143). Three-way catalysts, used in automobiles, oxidize hydrocarbons and CO, and reduce NO The donor quaUty, ie, the abiUty to provide oxygen for the oxidation, results from the capabihty of nickel oxide to chemisorb oxygen (see Exhaust control, automotive). 

Unfortunately, investigations with ionic liquids containing high amounts of AlEtCl2 showed several limitations, including the reductive effect of the alkylaluminium affecting the temperature stability of the nickel catalyst. At very high alkylaluminium concentrations, precipitation of black metallic nickel was observed even at room temperature. 

Fig. 15. Kinetics of the ethylene hydrogenation on Ni and 0-Ni-hydride film catalysts m denotes mass of films, which as known is connected with the thickness and crystallite sizes of the films involved. Blank points—rate of reaction proceeding on Ni film catalysts black points—rate of reaction proceeding on nickel previously exposed to the atomic hydrogen action, i.e. transformed to some extent into /3-Ni-hydride.

In addition, Lagowski and Simons showed (80) that the black, nickel-containing substances produced by the cocondensation of nickel atoms and alkynes are active, homogeneous catalysts for the oligomerization of terminal acetylenes under mild conditions. Table XVIII shows the yields of the oligomerization of propylene by these catalysts. 

The results obtained with nickel raised the question whether the relation found between rate of exchange and particle size holds also for other metals of group VIII. We therefore carried out the benzene-D2 reaction on some iridium catalysts widely differing in particle size. We chose iridium because we knew from earlier experiments that iridium black gives a very characteristic cyclohexane isotopic distribution pattern with a maximum for C6H4Ds, whereas the patterns of Ni, Ru, Pd, and Pt show a maximum for the d6 compound. 

Chiral amines were always considered important targets for synthetic chemists, and attempts to prepare such compounds enantioselectively date back to quite early times. Selected milestones for the development of enantioselective catalysts for the reduction of C = N functions are listed in Table 34.1. At first, only heterogeneous hydrogenation catalysts such as Pt black, Pd/C or Raney nickel were applied. These were modified with chiral auxiliaries in the hope that some induction - that is, transfer of chirality from the auxiliary to the reactant -might occur. These efforts were undertaken on a purely empirical basis, without any understanding of what might influence the desired selectivity. Only very few substrate types were studied and, not surprisingly, enantioselectivities were... 

The same catalysts which permit the addition of elementary hydrogen to a double bond are able to accelerate the opposite process—dehydrogenation, or elimination of hydrogen—when the temperature is altered. Thus cyclohexane is decomposed into benzene and hydrogen when passed over nickel or palladium black at about 300° (Sabatier, Zelinsky). The equilibrium... 

In aqueous medium, the reduction of nickel(II) acetate with NaBFLt produces nickel boride66. This fine black precipitate, designated P-1 nickel, is a more active catalyst than Raney nickel for double-bond hydrogenations. The P-1 nickel catalyst produces less double-bond migration than standard Raney nickel, it is not pyrophoric and is more readily prepared than Raney nickel. 

In ethanol nickel(II) acetate treated with NaBFLt produces a nearly colloidal black suspension63. Variation of the solvent in the preparation of the nickel catalyst results in an amorphous nickel boride catalyst67,68. This P-2 nickel catalyst is much more sensitive to the double-bond structure69,70. In the hydrogenation of the strained double bonds of nor-bomadienes, P-2 nickel shows high selectivity (95%) and low isomerization characteristics (equations 20 and 21). 

The reduction is usually made in a multi-compartment electrochemical cell, where the reference electrode is isolated from the reaction solution. The solvent can be water, alcohol or their mixture. As organic solvent A,A-dimethyl form amide or acetonitrile is used. Mercury is often used as a cathode, but graphite or low hydrogen overpotential electrically conducting catalysts (e.g. Raney nickel, platinum and palladium black on carbon rod, and Devarda copper) are also applicable. 

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