Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 12, pp. 1871−1878.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © T.G. Nikiforova, O.A. Datskevich, V.V. Maleev, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 12, pp. 1983−1990.
Palladium Catalysts on Porous Nickel Substrates
for Alcohol Fuel Cells
T. G. Nikiforova, O. A. Datskevich, and V. V. Maleev
St. Petersburg State University, St. Petersburg, Russia
Received March 26, 2012
Abstract—Parameters characterizing the active surface of catalytic palladium layers formed from mixed glycinate-
chloride and ammonia complexes of palladium(II) were determined. Cyclic voltammetry on a rotating disc electrode
was used to study the catalytic activity of nickel substrates and palladium layers in the reaction of methanol and
ethanol oxidation in an alkaline medium. It was shown that electrodes with palladium deposited from mixed glyc-
inate-chloride solutions have a higher catalytic activity that those formed from ammonia palladium(II) complexes.
Recently, a considerable attention has been given to
studies aimed to develop alcohol fuel cells, and primarily
direct ethanol fuel cells. Ethanol is a replenishable and
highly attractive kind of fuel because it can be produced
in large amounts from biomass and is less toxic than
methanol [1, 2].
It has been found that palladium catalysts supported
by various substrates [3–10] and also binary or ternary
palladium-containing catalysts [11–20] exhibit a good
activity in ethanol oxidation in alkaline solutions.
A considerable attention is paid when developing new
palladium catalysts to the nature and state of a substrate
onto which palladium is deposited and to the method
by which this is done. Of particular interest in this case
are substrates with a large roughness factor and good
Nickel can serve as a support for palladium catalysts.
Published results of studies indicate that nickel exhibits
a catalytic activity in oxidation of alcohols in alkaline
solutions [21–23] and improves the activity of catalysts
for alcohol fuel cells when used as a support for
catalysts, a component of binary and ternary catalysts,
and an oxide [11–14, 24–35].
As shown in [36, 37], fabrication of palladium
catalysts by electrochemical reduction of various
complex compounds of palladium(II) is rather
convenient for deposition of small controlled amounts
of palladium. In this case, various materials can play the
role of a conducting substrate. Deposition of palladium
onto dispersed carbon supports yields catalytic layers
 whose activity decreases in the course of operation
due both to the shedding of the dispersed layer and to the
gradual agglomeration of metallic palladium particles.
Porous nickel electrolytically formed by various methods
described in the literature has been used previously as
a substrate for deposition of palladium nanoparticles
. It has been shown that the highest activity catalyst
is obtained on porous nickel substrates fabricated by the
procedure described in .
In this study, we examined and characterized catalytic
palladium layers with varied content of palladium,
electrochemically deposited from acid solutions (pH
3–4) containing mixed glycinate-chloride complexes
of palladium(II) and from alkaline solutions (pH 12.8)
containing ammonia complexes of palladium(II) onto
porous nickel substrates fabricated by the method from
. The catalytic activity of porous nickel substrates
and catalytic palladium layers supported by these
substrates was studied in the reactions of methanol and
ethanol oxidation in alkaline aqueous solutions.