Langmuir 1991, 7, 457-459

457

Preparation of Bimetallic Pd-Pt Colloids in Organic Solvent

by Solvent Extraction-Reduction
Kunio Esumi,* Masayoshi Shiratori, Hidenori Ishizuka, Takafumi Tano,
Kanjiro Torigoe, and Kenjiro Meguro
Department of Applied Chemistry and Institute of Colloid and Interface Science,
Science University of Tokyo, Kagurazaka, Shinjuku-ku, Tokyo 162, Japan
Received May 10, 1990. In Final Form: July 3, 1990
Pd-Pt bimetallic colloids were prepared by reduction of their corresponding salts extracted in organic
solvents (cyclohexane, chloroform) with hydrazine or sodium boron hydride. Two extractants were used:
trioctylphosphine oxide (TOPO) and distearyldimethylammonium chloride (DDAC). In both organic
solvents, the particle size of Pd-Pt colloids depended on the feed molar fraction of Pd using hydrazine,
but almost was independent on the feed molar fraction of Pd using boron hydride. The dispersion stability
of Pd-Pt colloids increased as the particle size decreased.

Introduction
The preparation of precious metal colloids has been
studied exten~ivelyl-~
because of their wide use as electrical
materials and their many applications, such as catalysts.
Most of the work, however, has been limited to an aqueous
solution in the presence of surfactants or water-soluble
polymers as a protective colloid.
Recent work has focused on preparation of metal colloids in organic solvents. Some workers4v5have made stable
metal colloids in alcohol by adding polymer as a stabilizer,
while several groupsG8 have prepared metal colloids by
depositing metal atoms into organic solvents at low
temperature, which leads to atom clustering moderated
by solvation. We have developed a new methodgJOfor
preparation of metal colloids in organic solvents that uses
a solvent extraction; many metal salts are soluble in water
and they can be easily transferred into organic solvents
with extractants by means of solvent extraction. The
extracted metal salts are reduced by reductants, resulting
in the formation of metal colloids in the organic solvent.
We have obtained platinum and gold colloids9J0in organic
solvents by using the above technique, where the average
diameters of platinum and gold are 2.0 and 6.8 nm,
respectively. Thus prepared metal colloids can be applied
in nonaqueous solvent, a more useful medium for carrying
out organic reactions than water.
In this work, we extended this extraction method for
preparation of organo bimetallic colloids of Pd-Pt. The
prepared colloids were characterized by means of electron
microscopy, electron probe for microanalyses, and UVvis spectrophotometry.
(1)Turkevich, J.; Stevenson, R. C.; Hiller, J. Discuss.Faraday SOC.
1951, 11, 55.
(2)Takiyama, K. Bull. Chem. SOC.Jpn. 1958, 31, 944.
(3) Wilenzick, R. M.; Russell, D. C.; Morriss, R. H.; Marshall, S. W.
J . Chem. Phys. 1967,47, 533.
(4) Hirai, H.; Ohtaki, M.; Kamiyama, M. Chem. Lett. 1986, 269.
(5) Rampino, L. D.; Nord, F. F. J. Am. Chem. SOC.1941,63, 2745.
(6) Cardenas-Trivino, G.;Klabunde, K.; Dale, E. B. Langmuir 1987,
3, 986.
(7) Kimura, K.; Bandow, S. Bull. Chem. SOC.Jpn. 1983, 56,3578.
(8) Andrews, M. P.; Ozin, G. A. J. Phys. Chem. 1986,90,2929.
Jpn. 1988,
(9) Meguro, K.; Torizuka, M.; Esumi, K. Bull. Chem. SOC.
61, 341.

(10) Meguro, K.; Tano, T.; Torigoe, K.; Nakamura, H.; Esumi, K. Colloids Surf. 1988/89, 34, 381.

0743-7463191f 2407-045~$02.50
f0

Experimental Section
Materials. PdCl2 and H2PtCb were supplied by Tanaka
Kikinzoku Kogyo K.K. As extractants, trioctylphosphineoxide
(TOPO)and distearyldimethylammonium chloride (DDAC)were
used as received. The TOPO was obtained from Wako Pure
Chemical Industries, Ltd., and DDAC from Tokyo Kasei Industries, Ltd. As reductants, dehydrated hydrazine and sodium
boron hydride, commercially available in extrapure grades, were
used. The other chemicals were of extrapure grades. The water
used in this experiment was purified by means of the Milli-Q
water purification system.
Procedure. The extraction procedure was as follows. PdCl2
or HzPtCb was dissolved in water and added to an organic solvent
containing an extractant. In the case of TOPO, 0.6 mmol dm-3
of HCl was used to enhance the extractionratio. Then, the mixed
solution was shaken at 25 "C for 12 h to attain an equilibrium
of extraction. After the extraction, respective extracted PdCl2
and HzPtCb organic solutionswere mixed to make variousmixed
ratios of them, and then their solutions were directly reduced by
addition of areductant at room temperature. The added amount
of the reductant was about 3 times that of the extracted salts.
The particle size was determined by means of transmission
electron microscopy with a Hitachi H-800 microscope. The
magnificationof the electron microscope was 30000-100000. The
particle size distribution and average diameter were obtained by
counting particles on the basis of these enlarged electron
micrographs.
The elemental ratio of particles was determined by means of
electron probe microanalyzer (EPMA).
The UV-vis spectra of colloids in organic solventwere measured
with a UV-vis spectrophotometer (220A, Hitachi Co.).
The extraction ratio from aqueous solution to organic solvent
was determined from the difference between the initial and the
final concentrations before and after extraction in the aqueous
solution by means of a UV-vis spectrophotometer.
The stability of colloids thus prepared in the organic solvent
was evaluated from the absorbance at 500 nm after centrifuging
the colloids under a condition of 3000 rpm for 10 min. Here, a
high absorbance indicates a high dispersion stability.
Results and Discussion
Four different systems were studied: TOPO-cyclohexane-hydrazine, TOPO-cyclohexane-NaBH4, DDACchloroform-hydrazine, and DDAC-chloroform-NaBH4.
The extraction ratios from 0.5 mmol dm-3 of respective
metal salts in an aqueous solution to cyclohexane by TOPO
were 80% for HzPtC16 and 60% for PdC12, while those to
0 1991 American Chemical Society

Esumi et al.

458 Langmuir, Vol. 7,No. 3, 1991

Pt

ln

oAo

450

550

650

Wave length I nm

Figure 1. Absorption spectra of Pd-Pt colloids prepared in a

TOPO-cyclohexane-hydrazine system.
chloroform by DDAC were nearly 100%. Feed molar
fractions of Pd employed were 0,0.25,0.50,0.75, and 1.00
under total feed concentration of 0.3 mmol dm-3 and total
volume of 20 mL.
When the feed solutions were reduced with a reductant,
the respective reaction ratios of both Pd and Pt in various
feed solutions were almost the same, and about 98% with
hydrazine and about 81% with NaBH4. Accordingly, the
P d / P t ratios for the bimetallic colloids should be the same
as that of feed solution. Actually, the P d / P t ratios
estimated by EPMA were almost the same as those of the
feed solutions.
In order to confirm whether prepared colloids are
bimetallic or individual ones, the UV-vis spectra of colloids in organic solvent were measured (Figure 1). Figure
1shows that respective spectra do not exhibit characteristic
absorption bands, but the absorbancesof the Pd-Pt system
are different from those of Pd and Pt alone in the TOPOcyclohexane-hydrazine system. The other systems showed
a similar trend to that for the TOPO-cyclohexane-hydrazine system. These spectra are almost the same as
those prepared by Turkevich et al. in aqueous solutions,ll
suggesting that bimetallic colloidal particles of Pd-Pt are
formed in the organic solvents.
A typical EPMA result of the Pd-Pt colloids is given in
Figure 2. By measuring X-ray photon counts vs energy,
one can tell which elements are present and in what
amounts. Figure 2 shows that Pd and Pt are present in
the colloids, so the possibility seems to be ruled out that
the samples are mixtures of individual Pd and Pt colloids.
A similar microanalysis of Pd-Au colloidal particles was
carried out by Michel and Schwartz12who reported that
the composition of these colloids can be determined by
analytical electron microscopy.
Figure 3 demonstrates that the mean diameters of PdPt colloids prepared in TOPO-cyclohexanehydrazine and
DDAC-chloroform-hydrazine are in the range of 15 and
30 nm, showing a maximum diameter a t feed molar
fractions of Pd between 0.5 and 0.75, while those in TOPOcyclohexane-NaBH4 and DDAC-chloroform-NaE3H4 systems are almost independent of feed molar fraction of Pd
and range between 5 and 9 nm. Apparently, the mean
particle size is affected by the reductant; reduction by
hydrazine provides larger particle size than by NaBH4. It
is likely that since NaBH4 is a stronger reductant than
(11) Miner, R.S.,Jr.; Namba, S.;Turkevich, J. Proceedings ofthe 7th
International Congress on Catalysis; Seiyama, T., Tanabe, K., Eds.;
Kodansha: Tokyo, 1981; p 160.
(12) Michel, J. B.;Schwartz, J. T. Preparation of Catalysts IV; Delmon, B., Grange, P., Jacobs, P. A., Poncelet, G., Eds.; Elsevier Science
Publishers: New York, 1987; p 669.

Energy I keV

Figure 2. Typical EPMA result of Pd-Pt colloids prepared in

a TOPO-cyclohexane hydrazine system.
E

0.5

Molar fraction of Pd

Figure 3. Effect of feed molar fraction of Pd on mean particle

diameter of Pd-Pt particles for four systems: (e) DDACTOPO-cyclohexane-hydrazine; ( 0 )
chloroform-hydrazine; (0)
DDAC-chloroform-NaBH,; ( 0 )TOPO-cyclohexaneNaEH4.

P
0

05

Molar fraction of W

Figure 4. Change in absorbance of Pd-Pt colloids as a function

of feed molar fraction of Pd: ( 0 )DDAC-chloroform-hydrazine;
(0)TOPO-cyclohexane-hydrazine; ( 0 ) DDAC-chloroformNaBH,; ( 0 )TOPO-cyclohexane-NaBH,.
hydrazine, NaBH4 produces a larger number of nuclei,
resulting in a smaller mean particle size. Further, with
regard to the extractant, the usage of TOPO renders
particle size of Pd-Pt smaller than that of DDAC. This
result may be interpreted in terms of the different nature
of interaction between extractant and metal salt: TOPO
interacts with metal ions through coordinate bonds, while
DDAC forms complexes by electrostatic interaction. Since
a coordinate bond is generally stronger than an electrostatic
bond, it is reasonable to assume that the reduction of metal

Bimetallic Pd-Pt Colloids in Organic Solvent

Langmuir, Vol. 7, No. 3, 1991 459

ions proceeds much more easily in the case of DDAC than

with TOPO, due to favorable attack to metal ions by the
reductant. Therefore, the particle size of Pd-Pt in a DDAC
system becomes a little larger than that in a TOPO system.
The stability of the colloids prepared is shown in Figure
4. TOPO-cyclohexane-NaBH4 and DDAC-chloroformNaBH4 systems provide a higher stability in the whole
feed molar fraction range than TOPO-cyclohexane-hydrazine and DDAC-chloroform-hydrazine systems. In the
former systems, the colloids were still dispersed for more
than one month after the preparation, whereas in the latter
systems, they precipitated within a few days. Since the
mean particle size in the former systems is considerably
smaller than those in the latter systems, this stability is
likely to be predominantly governed by the particle size.

Summary
Pd-Pt bimetallic colloids were prepared by reduction
of their corresponding salts extracted in organic solvents
with hydrazine or sodium boron hydride. Trioctylphosphine oxide (TOPO) and distearyldimethylammonium
chloride (DDAC) were used as extractants. In TOPOcyclohexane-hydrazine and DDAC-chloroform-hydrazine
systems, the particle size of Pd-Pt ranged in 20-30 nm
and depended on the feed molar fraction of Pd, while in
TOPO-cyclohexane-sodium boron hydride and DDACchloroform-sodium boron hydride systems they ranged
in 5-8 nmand were independent on the feed molar fraction.
The dispersion stability of Pd-Pt colloidal particles
increased with decreasing particle size.