Raney nickel cathode

Very little systematic work has been conducted with Raney-nickel cathodes. Junghans reported on electrocatalytic hydrogenation of steroids, and he stresses that electrohydrogenation with Raney nickel yields higher selectivities (tram- vs cis-hydrogenation) than the usual catalytic hydrogenations (202, 203). 

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. 

Cold rolling, Raney-nickel-coated cathodes, 40 114... 

Cathode Nickel may be an alternative for platinum metals in alkaline solutions due to its low hydrogen overvoltage and catalytic activity. The activity is especially high at the very fine dispersed Raney nickel , which is available from a layer of a nickel alloy on the cathode surface by dissolving the alloy metal (aluminum or zinc) in alkaline solution prior to use (e.g. [23, 24]. Raney nickel usually is not stable against oxygen and self-ignition in air may be possible). 

An advanced cell configuration for underwater application has been developed using high-surface-area Raney nickel anodes loaded at 120 mg/cm (1-2% Ti) and Raney silver cathodes loaded at 60 mg/cm containing small amounts of Ni, Bi, and Ti (6). 

A significant cost advantage of alkaline fuel cells is that both anode and cathode reactions can be effectively catalyzed with nonprecious, relatively inexpensive metals. To date, most low cost catalyst development work has been directed towards Raney nickel powders for anodes and silver-based powders for cathodes. The essential characteristics of the catalyst structure are high electronic conductivity and stability (mechanical, chemical, and electrochemical). 

Trigeminal trihalides are completely reduced by catalytic hydrogenation over palladium [62] and Raney nickel [63], and partially reduced to dihalides or monohalides by electrolysis using mercury cathode [57 ], by aluminum... 

The most effective cathode surface for the electrocatalytic hydrogenation of alkenes is based on Raney nickel [147], Preparation of the surface involves elec-... 

Surfaces of finely divided nickel also promote the formation of aniline. A practical route to tlie preparation of electrodes coaled with a finely divided metal involves electroplating nickel onto a cathode from a solution containing a suspension of finely divided Raney nickel (Ni 50% A1 50%) or Devarda copper alloy (Cu 50% A1 45% Zn 5%), Some alloy particles stick to the cathode surface which is then activated by leaching out the aluminium using hot aqueous sodium hydroxide... 

Numerous methods for the synthesis of salicyl alcohol exist. These involve the reduction of salicylaldehyde or of salicylic acid and its derivatives. The alcohol can be prepared in almost theoretical yield by the reduction of salicylaldehyde with sodium amalgam, sodium borohydride, or lithium aluminum hydride by catalytic hydrogenation over platinum black or Raney nickel or by hydrogenation over platinum and ferrous chloride in alcohol. The electrolytic reduction of salicylaldehyde in sodium bicarbonate solution at a mercury cathode with carbon dioxide passed into the mixture also yields saligenin. It is formed by the electrolytic reduction at lead electrodes of salicylic acids in aqueous alcoholic solution or sodium salicylate in the presence of boric acid and sodium sulfate. Salicylamide in aqueous alcohol solution acidified with acetic acid is reduced to salicyl alcohol by sodium amalgam in 63% yield. Salicyl alcohol forms along with -hydroxybenzyl alcohol by the action of formaldehyde on phenol in the presence of sodium hydroxide or calcium oxide. High yields of salicyl alcohol from phenol and formaldehyde in the presence of a molar equivalent of ether additives have been reported (60). Phenyl metaborate prepared from phenol and boric acid yields salicyl alcohol after treatment with formaldehyde and hydrolysis (61). 

Microscopic and spectroscopic investigations (SEM and XPS) reveal the relatively fast change of the chemical composition of nickel sulfide coatings upon the onset of cathodic hydrogen evolution (74). Indeed, at 90°C all nickel sulfide phases are reduced to porous nickel within several days to a week s time. They lose some catalytic activity with time with an increase in overvoltage between 0.15 and 0.3 V after continuous operation for 1 year. It is clear that the catalyst after I week is already no longer nickel sulfide but some type of Raney nickel. Thus far the initial catalytic activity of the NiS, coating is of little relevance. The respective results and data are due to be published by the present authors (73). 

Although at least four different technologies [cold rolling, flame spraying, Zn and A1 melt dipping, cathodic deposition of Ni/Zn precursor alloys (76)] have been described, only cold rolling and cathodic deposition of precursor alloys are used for commercial production of Raney-nickel-coated cathodes. 

Fig. 12. Morphology of Raney-nickel-coated cathodes for hydrogen evolution from caustic electrolytes (a) surface of Ni-Zn precursor coatings, (b) surface of Raney-nickel coating prepared by caustic leaching of the Zn content of the precursor, (c) cut through a Raney-nickel coating.

Obviously the contribution of the pore walls—according to the current density distribution—to cathodic hydrogen evolution becomes negligible beyond 10 fim pore depth so that for a perfect, undivided Raney-nickel coating of 100 fim thickness, only 7 to 8% utilization is anticipated. This is the reason why the fissures and cracks, the so-called tertiary structure of the catalyst, formed in Raney-nickel coatings by the leaching process are so important for improving its utilization. 

Fig. 14. Comparison of the current-voltage curves of a smooth nickel cathode and two different Raney-nickel-coated cathodes posessing comparable loading and effective surface (a) smooth nickel. Raney nickel prepared from two different precursors (b) plasma-sprayed NiAh, (c) NiAU cold rolled together with Mond nickel.

Raney-nickel catalysts are barely sensitive to catalyst poisoning (as are Pt-activated cathodes), e.g., by iron deposition, but they deteriorate due to loss of active inner surface because of slow recrystallization—which unavoidably leads to surface losses of 50% and more over a period of 2 years. A further loss mechanism is oxidation of the highly dispersed, reactive Raney nickel by reaction with water (Ni + 2H20 — Ni(OH)2 + 02) under depolarized condition, that is, during off times in contact with the hot electrolyte after complete release of the hydrogen stored in the pores by diffusion of the dissolved gas into the electrolyte. 

Anodic hydrogen oxidation and even more cathodic oxygen reduction is kinetically hampered at low temperature, so that anodic hydrogen oxidation in AFCs, PEMFCs, and PAFCs demands catalysts of highest activity, that is, platinum metals and platinum in particular. Also Raney nickel is used in... 

Fig. 16. Schematic presentation of the morphological features of gas diffusion electrodes for fuel cells of (A) PTFE-bonded and Pt-activatcd Hi anodes and O2 cathodes used for Oi reduction in acidic and alkaline fuel cells (a) support, (b) hydrophobic gas diffusion layer, (c) hydrophilic electrode layer, (d) electrolyte, (e) magnified schematic of PTFE-bonded soot electrode, (f) adjacent hydrophobic layer, (g) microporous soot particles, (h) gas channels (mesopores), (k) PTFE particles, (I) flooded micro- and mesopores, (B) Schematic presentation of the morphology of PTFE-bonded Raney-nickel anodes used in alkaline fuel cells ol the Siemens technology.

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