3176

J. Electrochem. Soc., Vol. 138, No. 11, November 1991 9 The Electrochemical Society, Inc.

tion of shape change (4). This effect is most likely exacerbated at the end of charge by n o n u n i f o r m current distribution. It is clear that the changes in KOH concentration
resulting during a discharge-charge cycle would be less of
a problem as the bulk concentration of KOH is decreased
and more of a problem as the bulk concentration of the
electrolyte approaches the concentration at which the Ca
zincate structure is not stable, in the range of 28 to 37.5 w/o
KOH (1).

were cycle-life tested in 10 and 20 w/o KOH electrolyte.

T h e results showed that shape change decreased very significantly when the KOH concentration was decreased
from 20 w/o to 10 w/o KOH and when the cells were cycled
in a starved electrolyte condition rather than in a flooded
mode. However, the low-temperature properties of 10 w/o
KOH are not as favorable as the 20 w/o KOH [i.e., 10 w/o
KOH freezes at -9~ (15~ compared to -24~ ( - l l ~ for
20 w/o KOH]. Radiography and chemical analyses of sectioned Zn electrodes after cycling indicated that the
changes in KOH (4) concentration resulting during a discharge-charge cycle may play an important role in determ i n i n g the onset and propagation of shape change.

Effect of temperature.--A study by Gomis et al. (5)

showed that the performance of a NiOOH/KOH/Cd cell
was significantly affected by low-temperature conditions;
the loss in capacity was attributed to the formation of ice
and/or hydrates in the pores of the electrode, especially at
temperatures below -30~ I n their work, they showed a
plot of the crystallization of KOH-H20 solutions as a function of temperature which provides useful insight to this
present study. Very clearly the low-temperature properties
of 10 w/o KOH in this study are not as favorable as the
20 w/o KOH (i.e., 10 w/o KOH freezes at -9~ (15~ compared to -24~ ( - l l ~ for 20 w/o KOH. Schult et al. provided additional information regarding different hydrates
that were capable of forming in KOH solutions at low temperatures. Between 0 and -32~ ice alone forms in the
pores of the electrodes, but below -32~ ice and different
hydrates form. The freezing of electrolyte at low temperatures may be a problem insofar as it may cause damage to
the cell components due to the formation of ice and hydrates. One possible solution to this problem might be to
use additives or a supporting electrolyte to lower the freezing point of the electrolyte. Another possibility is to add to
20 w/o KOH, additives which would suppress the solubility of Z n to levels achieved with 10 w/o, yet retain the freezing characteristics of 20 w/o KOH.

Acknowledgments
The author thanks N. M. Potter of the Analytical Chemistry Department for the Ca and Zn analyses, R. A. Adams
for the radiographs of the Z n electrodes, and S. P. Maheswari for his assistance in carrying out the experimental
studies.
Manuscript submitted Dec. 10, 1990; revised manuscript
received May 24, 1991. This was Paper 74 presented at the
Seattle, WA, Meeting of the Society, Oct. 14-19, 1990.

General Motors Research Laboratories assisted in meeting the publication costs of this article.
REFERENCES
G. Gagnon, This Journal, 133, 1989 (1986).
G. Gagnon and Y.-M. Wang, ibid., 134, 2091 (1987).
R. Witherspoon, Private communication.
G. Gagnon and B. S. Hill, This Journal, 137, 377
(1990).
5. J. P. Gomis, J. C. Jarrousseau, and B. Monneret, in
"Proceedings of the Twenty-Third A n n u a l Power
Sources Conference," Atlantic City, N J, May 20-22,
1969, The Electrochemical Society, Inc., p. 120 (1969).
6. R. W. Schult and W. T. Stafford, Contract No. STL/TR60-0000-0934, Space Technology Laboratories, Inc.,
Los Angeles, CA (1960).
1.
2.
3.
4.

Conclusions
A group of 23.5 Ah cells with calcium hydroxide containing zinc electrodes and nonsintered NiOOH electrodes

E.
E.
R.
E.

The Selective Oxidation of Toluene to Benzaldehyde Applying a

Fuel Cell System in the Gas Phase
Kiyoshi Otsuka, Kiyokazu Ishizuka, Ichiro Yamanaka, and Masaharu Hatano
Department of Chemical Engineering, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152, Japan
ABSTRACT

A fuel cell system was used for the synthesis of benzaldehyde from toluene in the gas phase. The cell system [anode:
Pd-black with added graphite/H3PO4(aq.)/cathode: Pt-black with added graphite] operated at ca. 373 K u n d e r short-circuit
conditions and produced the partial oxidation products benzaldehyde (PhCHO) and benzoic acid (PhCOOH). The addition of chlorides such as HC1, NaC1, MgC12, etc., to the anode remarkably improved the selectivity of the sum of PhCHO
and PhCOOH. In the presence of chlorides, CO2 was not produced at all. Among the chlorides tested, NaC1 is the best additive for the synthesis of PhCHO. Kinetic results on the reaction with the NaCl-added anode have shown that decreasing
temperatures and increasing pre.~sures of the reactants (toluene and 02) favor the oxidation to PhCHO. The oxidation of
toluene u n d e r an externally applied potential showed a product distribution similar to that observed u n d e r short-circuit
conditions. The turnover n u m b e r greater than unity (2.4) indicates catalytic cycling of the Pd in the anode. The current efficiency was improved by cyclic short- and open-circuit operation of the cell. A reaction mechanism assuming a ~-allylbenzyl-Pd2
complex as the reaction intermediate explains the kinetic results and the favorable effect of chloride.
The intermediate complex may be generated through the electrochemical oxidation of Pd and toluene. The subsequent
competitive formations of PhCHO and CO2 from this complex proceed nonelectrochemically.

The synthesis of benzaldehyde by catalytic oxidation of

toluene with molecular oxygen is of great practical importance, but it is still a difficult reaction to control. The oxides of v a n a d i u m and m o l y b d e n u m are effective for the
partial oxidation of toluene to benzaldehyde (1). There are
some patents claiming other favorable catalysts (Pd with
H3PO4, P d with Fe2(SOD3, or Pd with Sb203 and H3PO4) for
preparation of benzaldehyde (2). However, the selectivity
to benzaldehyde obtained for these catalysts is not very

satisfactory. Therefore, a new catalyst or a novel process

for the selective production of benzaldehyde is strongly
desired.
Recently, we have demonstrated that the synthesis of
acetaldehyde can be conducted using a fuel cell for the oxidation of ethylene and using Pd as the anode (3). This
method could solve a n u m b e r of disadvantages of the
Wacker process for the synthesis of acetaldehyde using
PdC12 and CuC12 as catalysts (3). A similar system could be

Downloaded on 2014-10-17 to IP 141.214.17.222 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

J. Electrochem. Soc., Vol. 138, No. 11, November 1991 9 The Electrochemical Society, Inc.
used for the ~-allyl-type oxidation of olefins such as propylene to acrolein (4-6) or butene to methyl-vinyl-ketone
a n d crotonaldehyde (5). The purpose of this work is to examine wh et h er such a fuel cell system as described above
c a n also be applicable to the selective oxidation of toluene
to benzaldehyde at relatively low temperatures. In this report we describe an electrocatalytic system for the selective synthesis of benzaldehyde as well as the kinetic parameters which determine the rate and the selectivity of
the reactions. Finally, an overall reaction scheme is proposed on the basis of the kinetic results.

Experimental
The diagram of the fuel cell system used for the partial
oxidation of toluene is shown in Fig. 1. A detailed description of the setup has already been described elsewhere (3).
A silica wool disk (2.0 m m thickness and 26 m m diam) containing 0.8 g of H3PO4 (85% aq.) as an electrolyte separates
the anode and cathode compartments. The electrodes
were prepared as follows. A metal black (20 mg), mixed
uniformly with graphite (50 mg) and Teflon powders
(5 mg), was ground with a pestle in a mortar. The mixture
was pressed and shaped into a round wafer (16 m m diam
a n d 0.1 m m thickness) on a hot plate (393 K) with a stainless steel roller. The electrode thus prepared will be denoted as M/Gr.
The Pd black, Pt black, Rh black, Ni powder, and graphite used as electrode materials and the additives (NaC1,
LiC1, MgC12, H2PdC14, and HC1) to the anode or to the electrolyte (H3PO4) were reagent-grade materials obtained
from Wako P u r e Chemical and Soekawa Chemical Cornpanies. The helium and oxygen used were certified standards (purity > 99.9%). Distilled toluene and water were
used for the experiments.

Procedure.--The e x p e r im e n t s were conducted without

an external load (short circuit) in order to produce chemicals exclusively. Toluene vapor was carried with helium
into the anode compartment. Oxygen with water vapor
flowed into the cathode c o m p a r t m e n t (Fig. 1). All the reactions were carried out u n d e r atmospheric pressure in both
compartments. The experiments were usually carried out
under one of two conditions:
(A) Short-circuit for 2 h, temperature 373 K. Anode: toluene pressure =3.0 kPa, total flow rate =4.7 m l S T P 9min-L
Cathode: o x y g e n pressure =85 kPa, H20 vapor pressure
=16 kPa, total flow rate =12 m l S T P 9rain -~.
(B) Short-circuit for 2 h, temperature 353 K. Anode: toluene pressure = 30 kPa, total flow rate = 6.5 m l S T P - min-~.
Cathode: oxygen pressure =85 kPa, H20 vapor pressure
=16 kPa, total flow rate =12 m l S T P - min-L
The vapor pressures of toluene and water were adjusted
by changing the temperature at the saturator for each compound. The kinetic studies were carried out under a constant pressure of water vapor to keep the acid concentration of H3PO4 constant in the membrane. That no leakage
of oxygen through the m e m b r a n e (silica wool disk with

oTll

liTL

3177

<~:
E

4"r--

0
0.02

\
A

'cE
"o

[02

=~
~ 0.01
r'O
:~_
m
E.
L
o

i-

- - i--------- i _ _
.

a--

14--

o
~-~
fm
..

30
60
time on stream

90
/ rain

120

Fig. 2. The kinetic curves of the products and the change in the current with time on-stream of reactant gases. Experimental conditions A.

H3PO4 aq.) occurred was confirmed by analyzing the effluent gas from the anode compartment. However, water
vapor in the cathode (16 kPa) diffused considerably to the
anode (8.5 kPa) through the membrane. Toluene and products (PhCH2OH, PhCHO, PhCOOH) dissolved in the membrane. Thus a little leakage of these co m p o u n d s to the
counter-compartment could not be avoided during the reaction.
The effluents of reactant and product gases were analyzed by an on-line gas chromatography at different predetermined intervals. All the effluent products were condensed in a cold trap at 195 K or dissolved in an aqueous
phosphoric acid solution (16 m m o l 9d m 3). The products
thus collected were analyzed by gas or liquid chromatography. The products dissolved in the m e m b r a n e were also
analyzed after the reaction. The current or the open-circuit
potential across the cell was monitored with a multimeter
(Hewlett-Packard 3468A). In some cases, the reaction was
carried out u n d er externally applied potential using a
power supplier (Kikusui PAB18). The rates and the selectivities toward the products were calculated on the basis of
the toluene (C7) converted, i.e., the rate of formation of CO2
was divided by seven.

Results
The anode effective for the partial oxidation.--Under ex-

Pd- electrode
(anode)

H3PO~ in
sitica wool

Pf - electrode
(cathode)

Fig. 1. Diagram of the fuel cell reactor for the partial oxidation of
toluene.

perimental conditions A, various metals (Pd black, Pt

black, Rh black, and Ni fine powder) have been tested as
the anode material e m b e d d e d in the graphite (MJGr). The
Pt/Gr was always used as the cathode. The Pt/Gr, Rh/Gr,
and Ni/Gr as the anodes produced only CO2. The Pd/Gr
was a unique anode effective for the partial oxidation of
toluene. The kinetic curves and the current observed for
the Pd/Gr are plotted in Fig. 2. Because the analysis of the
benzoic acid was only possible after the reaction, the formation rate of benzoic acid is given as the average value
calculated from the a m o u n t accumulated in an exit trap of

Downloaded on 2014-10-17 to IP 141.214.17.222 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

J. Electrochem. Soc., Vol. 138, No. 11, November 1991 9 The Electrochemical Society, Inc.

3178

Table I. The effect of additives in the H3PO4-membrane.

Additives a

C.P. b
/I~F

EMF
/mV

CO2

None
NaC1
H2PdC14
HCI
Na2SO4

219.4
259.4
237.8
260.8
179.6

620
563
608
560
e

1.04
1.20
1.32
1.48
0.80

Products/p.mol
PhCHO
PhCOOH
0.46
1.44
1.27
1.53
0.24

0.33
0.52
0.59
c

:::k

100o-

~"~"~.o-t--

-0
QI

i.J
e7

50

(lJ

Experimental conditions A.
a Amount of additives 10 i~mol (3 ~mol for H2PdC14).
b Charge passed.
Not determined.

50

QJ

/o

r
t./

0
20

t h e r e a c t o r i n 2 h. T h e r e s u l t s in Fig. 2 s h o w t h a t t h e P d / G r
p r o d u c e s b e n z a l d e h y d e ( d e n o t e d as P h C H O h e r e a f t e r ) a n d
b e n z o i c acid ( P h C O O H ) w i t h a s u m m e d s e l e c t i v i t y
( P h C H O + P h C O O H ) h i g h e r t h a n 50%. H o w e v e r , t h e rate,
t h e selectivity, a n d t h e c u r r e n t efficiency (ca. 10%) for t h e
f o r m a t i o n o f P h C H O are v e r y low. T h e e l e c t r o m o t i v e force
(EMF) u n d e r o p e n - c i r c u i t c o n d i t i o n s m e a s u r e d j u s t b e f o r e
t h e b e g i n n i n g o f t h e r e a c t i o n i n Fig. 2 w a s 620 inV.

Effect of additives.--We h a v e r e p o r t e d t h a t t h e a d d i t i o n
of c h l o r i d e s s u c h as NaC1, H2PdC14, a n d HC1 to t h e m e m brane improves the rate and the selectivity of the format i o n of a c e t a l d e h y d e f r o m o x i d a t i o n of e t h y l e n e w h e n
u s i n g a fuel cell r e a c t o r r e s e m b l i n g Fig. 1 (5). T h e r e f o r e , w e
e x p e c t t h a t t h e s e a d d i t i v e s m a y also e x e r t a f a v o r a b l e
effect o n t h e p a r t i a l o x i d a t i o n o f t o l u e n e . H e n c e a n u m b e r
o f d i f f e r e n t a d d i t i v e s (3-10 i~mol) w e r e d i s s o l v e d in t h e
H3PO4 m e m b r a n e . T h e r e s u l t s o b t a i n e d u n d e r e x p e r i m e n tal c o n d i t i o n s A are s h o w n i n T a b l e I. T h e E M F m e a s u r e d
j u s t b e f o r e t h e s t a r t o f t h e e x p e r i m e n t s are l i s t e d o n t h e
t h i r d c o l u m n o f T a b l e I. A d d i t i o n s of c h l o r i d e s w e r e f o u n d
to i n c r e a s e t h e c h a r g e p a s s e d a n d t h e f o r m a t i o n r a t e s o f
t h e p r o d u c t s o f i n t e r e s t , e s p e c i a l l y t h e r a t e o f P h C H O form a t i o n . T h e s u l f a t e (Na2SO4), o n t h e o t h e r h a n d , e x e r t e d a
n e g a t i v e effect, s u g g e s t i n g t h a t t h e e n h a n c i n g ability is
specific to c h l o r i d e s or c h l o r i n e a n i o n s .
T h e a d d i t i o n o f c h l o r i d e s to t h e P d / G r a n o d e r a t h e r t h a n
t h e H3PO4 m e m b r a n e e n h a n c e d t h e e f f e c t e v e n m o r e . A s
will b e d e s c r i b e d later, r e a c t i o n c o n d i t i o n s B are b e t t e r
t h a n A for t h e s e l e c t i v e s y n t h e s i s o f P h C H O . T h e r e f o r e ,
the effect of additives impregnated in the graphite anode
h a s b e e n e x a m i n e d u n d e r c o n d i t i o n s B. T h e s e r e s u l t s are
s h o w n in T a b l e II. T h e m o s t s t r i k i n g a s p e c t o f T a b l e II is
t h a t t h e a d d i t i o n o f c h l o r i d e i n c r e a s e s t h e r a t e of P h C H O
formation remarkably, but almost completely retards the
f o r m a t i o n o f CO2. T h e r e f o r e , t h e s e l e c t i v i t y to p a r t i a l oxid a t i o n [ P h C H O + P h C O O H + PhCH2OH(trace)] b e c o m e s
a l m o s t 100% for t h e p r o d u c t s o b s e r v e d i n t h e e f f l u e n t gas.
T h e a d d i t i o n o f c h l o r i d e s i n c r e a s e d t h e c u r r e n t efficiency
of t h e s u m o f P h C H O a n d P h C O O H d r a m a t i c a l l y to 54-61%
f r o m 6% ( w i t h o u t additives). A m o n g t h e c h l o r i d e s t e s t e d ,
t h e N a C l - a d d e d a n o d e s h o w e d t h e m o s t f a v o r a b l e effect
o n t h e f o r m a t i o n o f P h C H O as well as o n t h e c u r r e n t efficiency. T h e a d d i t i o n of s o d i u m f l u o r i d e or a c e t a t e d i d n o t

=L

/
0

BH

O-'-'-O
~'-& -----~ ~

O
A,

50

.,C02

100

150

amount of NoC[ / ;Ltmot

Fig. 3. The effect of NaCI added. Experimental conditions B.

show such a dramatic enhancement in the rate and current

e f f i c i e n c y o f t h e f o r m a t i o n o f P h C H O ( T a b l e II). T h e s e res u l t s s h o w a g a i n t h a t t h e e n h a n c i n g ability is specific to
c h l o r i d e s . T h e a d d i t i o n o f c h l o r i d e s w a s f o u n d to d e c r e a s e
t h e E M F , b u t t h e f l u o r i d e or a c e t a t e d i d n o t e x e r t s u c h a n
effect.

Dependence on the amount o f NaCL--Figure 3 i n d i c a t e s

the quantity of each product, the charge passed, and the
c u r r e n t e f f i c i e n c y o f t h e s u m o f P h C H O a n d P h C O O H as
f u n c t i o n s of t h e a m o u n t o f NaC1 a d d e d to t h e P d / G r a n o d e .
T h e e x p e r i m e n t s w e r e c a r r i e d o u t u n d e r c o n d i t i o n s B. T h e
o p e n - c i r c u i t p o t e n t i a l (EMF) d e c r e a s e d w i t h t h e a m o u n t of
a d d e d NaC1 f r o m 530 m V (NaC1 = 0 t~mol) to 310 m V
(NaC1 = 150 ~mol). T h e r a t e o f P h C H O f o r m a t i o n inc r e a s e d s h a r p l y w i t h a rise i n t h e a m o u n t of NaC1 u p to
70 ~tmol, b u t d e c r e a s e d b e y o n d t h i s a m o u n t . No CO2 w a s
o b s e r v e d w h e n m o r e t h a n 50 ~ m o l o f NaC1 w a s a d d e d . T h e
c u r r e n t efficiency for t h e p a r t i a l o x i d a t i o n p r o d u c t s
( P h C H O a n d P h C O O H ) r e a c h e d a p l a t e a u (ca. 60%) at NaC1
a d d i t i o n >70 t~mol. T h e r e s u l t s in Fig. 3 s h o w t h a t 70 t~mol
is t h e o p t i m u m a m o u n t of NaC1 a d d e d to t h e P d / G r a n o d e

Table II. The effect of additives in the Pd/Gr anode.

Additives a

/ixF

EMF
/mV

COa

None
NaC1
NaF
NaOAc
NaNO3
LiCI
MgC12
CuC12
SmCI~

99.5
117.1
107.7
100.8
113.2
87.8
58.8
72.8
71.8

530
393
547
506
e
456
418
367
450

0.73
<0.01
0.90
0.82
0.53
<0.01
<0.01
<0.01
<0.01

C.P.

Products/t~mol
PhCHO
1.05
15.55
1.09
1.18
2.68
9.67
6.02
3.12
6.18

c,a.

PhCOOH

/%

0.30
1.48
0.32
0.48
0.30
1.63
1.31
0.54
1.01

6.0
60.7
5.8
7.5
11.1
55.3
54.4
21.8
42.8

Experimental conditions B.
a Amount of additives 70 ~mol (40 ~mol for MgC12 and CuC12, 20 ~mol for SmC13).
b Current efficiency.
c Not determined.
Downloaded on 2014-10-17 to IP 141.214.17.222 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

J. Electrochem. Soc., Vol. 138, No. 11, November 1991 9 The Electrochemical Society, Inc.

3179

EL-

::l

QJ

100

~ o ~

100

.~
.M

~9

dr~
QJ

o/~

~,300

M-,'4,,--

50

~m 200
r

~100

50

r--

cJ

_ o / ~
, 0 1

r-

&_

tJ

2.0

20

C02

E
E

=L
-b

1.C
n

10

t-

t ~ s _

60

-0~0.

--z~
80

~
~0 A - - O-- C 02
90
100
110
reaction fempereJ'ure / ~

~3

A/
80

100
/ ~

120

reaction fernperafure

Fig. 5. The effect of reaction temperature. Experimental conditions

A.

Fig. 4. The effect of reaction temperature. Experimental conditions

B.

for synthesis of P h CH O u n d e r these experimental conditions. Addition of excess NaC1 (>70 ~mol) decreased the
electric conductance of the electrode, and thus also decreased the current and the rate of PhCHO formation.

Effect oftemperature.--The temperature effect on the reaction has been e x a m i n e d using the NaC1 (70 ~mol) added
to the Pd/Gr under experimental conditions B. The results
are demonstrated in Fig. 4. The formation of CO2 was not
observed at temperatures lower than 363 K. However, CO2
formation cannot be neglected at >383 K. The formation of
PhCHO i m p r o v e d remarkably with decreasing reaction
temperature. The current efficiency also improved at
lower temperatures. The observed E M F (380 -+ 15 mV) did
n o t change with reaction temperature within the experimental error.
The effect of t em p e r a t u r e on CO2 formation can be seen
more clearly when the reaction has been carried out under
experimental conditions A using the H3PO4-membrane
added with 10 ~tmol of NaC1. The results are shown in
Fig. 5. A decrease in temperature decreases the rate of CO2
formation. In contrast, the yields to PhCHO a n d PhCOOH
are improved considerably with decreasing temperatures,
in agreement with the results in Fig. 4. The remarkable
temperature effect on CO2 formation suggests a large activation energy for the deep oxidation of toluene to CO2.

Oxidation under applied potentiaL--For the data of the

NaCl-added anode in Table II, the product distribution including benzyl alcohol (PhCH2OH) and the turnover number (T.N. = a mole of the converted toluene per mole of Pd
anode) are indicated in Table III in the row for Run No. 1.
The turnover n u m b e r was far less than unity. In order to
confirm the electrocatalytic role of the Pd anode, the reaction has been carried out with a potential applied between
the anode and cathode. Run No. 2 in Table III is the result
for the Pd/Gr anode added with 70 txmol of NaC1 under an
applied potential of 500 mV for 450 min. The weight of Pdblack in the Pd/Gr anode was reduced to 2.1 m g (20 ~tmol)
for this experiment. Run No. 3 is for the graphite added
with H~PdC14 (20 ~mol) under the same applied potential
for 360 min. The other experimental conditions for Runs
No. 2 and 3 are the same as those of Ru n No. 1. The results
in Table III show that, although the deep oxidation cannot
be avoided under the applied potential condition, the distributions of the partial oxidation products are very similar for three runs (No. 1, 2, 3). This observation strongly
suggests that the reaction m ech an i sm and the role of palladium are essentially the same for these three experiments
(Runs No. 1, 2, and 3). Hence the initial state of palladium
(Pd ~ or pd2+), with or without an externally applied potential, does not change the fundamental reaction profile. The
turnover n u m b e r s observed in Runs No. 2 and 3 exceeded
unity. This shows that the palladium works as an electrocatalyst.

Effects of toluene and oxygen pressures.--The quantities

Oxidation of toluene by cyclic short- and open-circuit operation.--Figure 8 shows the changes of the rate of PhCHO

of products, the charge passed, and the current efficiency

of the sum of P h C H O and P h C O O H are plotted in Fig. 6 as
functions of the partial pressure of toluene in the anode
compartment. The e x p e r im e n t s were carried out using
Pd/Gr added with 70 ~mol of NaC1 under conditions B.
The increase in toluene pressure enhances the rate of
PhCHO formation. The effect of oxygen in the cathode
c o m p a r t m e n t is indicated in Fig. 7. Here, also, the formation of P h C HO is enhanced by an increase in the oxygen
pressure. No appreciable increase in the EMF
(380 -+ 15 mV) as observed with increasing pressure of toluene or oxygen.

formation and of the current as a function of time onstream of toluene vapor for the e x p e r i m e n t of Run No. 1 in
Table III. The rate of PhCHO formation and the current
decrease with time on-stream of the reactant. This is a
c o m m o n trend observed for all the experiments under
short-circuit condition. The current efficiency calculated
for the sum of PhCHO, PhCOOH, and PhCH2OH of Run
No. 1 in Table III was 61%, which is far less than 100%. The
current efficiencies observed for the experiments described so far (Fig. 2-8, Tables I-III) were all less than 61%,
suggesting the formation of significant by-products during
fuel cell oxidation. It is found that if the circuit has been

Downloaded on 2014-10-17 to IP 141.214.17.222 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

J. Electrochem. Soc., Vol. 138, No. 11, November 1991 9 The Electrochemical Society, Inc.

3180
I.I_

O~

=C

IJ_

=L
0

OJ

100

100

i/)
i/1

t-

50

50

r
L
I

100

50

tu

._~

50

,-'4,.-

~J

of

100
t,--

' 0 ~

e-

'

,4.-,
r"
ll/
r
r

2O

20

=l
J

e ~

E
::L

-I,--

10
0

i/i

-l-l.J

lO

"ID

i'

CHO

t._
~0---------0

OH

00

'

A,

A--z

10
20
30
pressure of foluene /

t-u

A-~------.A
50
100
pressure of oxygen / kP~

Fig. 7. The effect of oxygen pressure. Experimental conditions B.

/+0
kPo,

Fig. 6. The effect of toluene pressure. Experimental conditions B.

'

z~

O - - O - - rPN_
0

we have not succeeded in identifying this complex, we

propose that it could be a ~-allyl-benzyl-Pd2 co m p l ex similar to the one (a) identified by Roberts and Klabunde (7)
It

shorted before, the formations of PhCHO and CO2 continue even after opening the circuit. Figure 9 shows the
change in the formation rate of P h C H O with time onstream during cyclic shorted and open-circuit operation.
The partial pressure of reactants and the flow rate for the
experiments of Fig. 9 were the same as those of conditions
B. The circuit was shorted for 5 or 10 min, starting at zero,
1, 2, 3, and 4 h (indicated by shaded areas) in Fig. 9. The unshaded areas in Fig. 9 give the results observed under the
open-circuit conditions. Although the rate of PhCHO formation decreases sharply with time on-stream, the formation continues for about 60 min after opening the circuit.
The amounts of the products formed in 5.2 h were 20.4, 4.0,
and <0.01 ~mol for PhCHO, PhCOOH, and CO2, respectively. The total charge passed during short-circuiting of
the cell in Fig. 9 was 113 ~tF. F r o m these values, we can establish that the current efficiency for the sum of PhCHO
and PhCOOH becomes as high as 93%. These observations
suggest that the oxidation of toluene by the cyclic shorted
and open-circuit operation can avoid undesirable side reactions.

(a)

If the oxidation of toluene proceeds via a complex such as

(a), the presence of chloride must enhance the reaction
rates. This is what we observed in Tables I and II. As previously described, the addition of NaC1 to the anode instead
of to the m e m b r a n e (H~PO4) improved the yield of PhCHO.
The explanation is probably that the reaction intermediate

"~= 0.3

"~

8
Clio

Discussion

Reaction intermediate.--The H3PO4 m e m b r a n e with

10 ~mol of NaC1 turned from colorless to dark yellow after
the reaction u n d er the experimental conditions of Table I.
T h i s discoloration did not occur under the open-circuit
conditions. Moreover, the colored c o m p o u n d was not
formed in the absence of toluene. When the colored compound, after being extracted with the mixture of
H3PO4(aq.) and acetonitrile, was reduced by NaBH4, Pd ~
was observed as a precipitate. These observations suggest
the formation of a toluene-Pd 2 c o m p l e x during the fuelcell oxidation of toluene in the presence of NaCI. Although

0.1

"~

~o

~o.-~..~

C02
00-,',

2 '~

--

,a

20

,A

z~

60

time on sfreom

A,

!,,

80

100

-~-'0

120

rnin

Fig. 8. The kinetic curve of PhCHO formation and the current change
with time on-stream of reactant gases. Experimental conditions B.

Downloaded on 2014-10-17 to IP 141.214.17.222 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

3181

J. Electrochem. Soc., Vol. 138, No. 11, November 1991 9 The Electrochemical Society, Inc.
Table III. Distributions of products observed under short-circuit or applied potential conditions.
Run
no.

Time
/min

C.P.
/~F

CO2

PhCHO

1
2
3

120
450
360

117.1
659.8
693.0

<0.01
2.96
2.44

15.55
28.32
39.90

Produets/~tmol
PhCOOH
1.48
2.41
4.38

PhCH2OH

C.E.
/%

T.N.

0.20
1.37
2.04

60.7
19.8
28.0

0.1
1.6
2.3

Experimental conditions B.
Run no. 1: Short circuit, (Pd-black + NaC1)/Gr anode.
Run no. 2:0.50 V applied, (Pd-black + NaC1)/Gr anode.
Run no. 3:0.50 V applied, (H2PdC14)/Gr anode.
formed on the anode was not dissolved into the membrane.

Reaction m e c h a n i s m . - - W e propose that the experimental observations described above can be explained in
terms of the reaction m e c h a n i s m demonstrated in Fig. 10.
Here, we assume that the electrochemical oxidations of
toluene and Pd~ form the reaction intermediate A, a ~-allylbenzyl-Pd 2 complex, in step 1. Since the reaction proceeds even in the absence of C1- (Fig. 2), c o m p le x A is not
necessarily identical to the one given by structure (a). The
re dox potential of P d ~ ~ Pd~ is m o v e d cathodically in the
presence of C1- (8). Therefore, the formation of the reaction
intermediate A should be enhanced in the presence of
chlorides.
The ~r-allyl-benzyl species in c o m p le x A is oxidized by
the central Pd 2 cation, producing PhCHO (probably
through PhCH2OH) and Pd~ in step 2. Further oxidation of
PhCHO in step 3 gives PhCOOH. It is to be noted that COs
is proposed to be produced in step 4 competitively with
the formation of PhCHO, i.e., CO2 is probably not produced through deep oxidation of P h C H O or PhCOOH.
This assumption is based on the observations in Fig. 11.
The kinetic curves in Fig. 11 were observed for the H~PO4m e m b r a n e with 10 p~mol of NaC1 added under reaction
conditions A. The kinetic curves after opening the circuit
at 1 h indicate that the rate of PhCHO formation increases,
in contrast to a steady decrease in the formation rate of
CO2. If CO2 is formed through the oxidation of PhCHO, the
change in the formation rate of CO2 should follow that of
PhCHO. The quite different kinetic curves for the two
products under open-circuit conditions strongly suggest
that the P h C HO and CO2 are formed independently by different active species. However, it seems strange that the
rate of P h C HO formation increases after opening the circuit. To explain this observation, we assume the contribution of a different oxidized species of palladium (tentatively denoted as palladium oxide, P d = O) in step 4. The
P d = O is assumed to be generated electrochemically in
step 1'. After opening the circuit, the accumulated intermediate A is c o n s u m e d via steps 2 and 4. The concentra-

tion of P d = O should decrease with the formation of COs

under open-circuit conditions. Therefore, the competition
between steps 2 and 4 favors step 2 with reaction time, resulting in an increase in the formation rate of PhCHO. The
formation of the products u n d er open-circuit conditions
(Fig. 9 and 11) supports the hypothesis that steps 2 and 4
are not electrochemical reactions.
The dramatic decrease in the selectivity towards COs formation by addition of chloride (Table II) can be explained
as follows. The electrochemical oxidation of palladium
metal to c o m p l e x A through step 1 would specifically be
accelerated in the presence of chloride. Consequently, the
formation rate of P d = O in step 1' must be reduced, causing the dramatic decrease in the rate of CO2 formation in
step 4. The large current observed at the early stage of the
reaction u n d er short-circuit conditions shows that the
electrochemical reactions, i.e., the oxidations of Pd~ and
toluene in step 1, are fast compared to the subsequent
nonelectrochemical steps 2 and 4.
The sharp decrease in the formation rates of the products during the reaction (Fig. 2 and 8) may be ascribed to
side reactions of the accumulated complex A. The side reaction could be oligomerization of the benzyl species or
further oxidation of the produced oligomers with P d = O.
In fact, the gas and liquid chromatographic analyses of the
products dissolved in the m e m b r a n e showed several small
peaks, probably due to these by-products, but they are not
yet identified. The side reaction products may retard the

H20

pd ~

~3,

2H+,2e -

Pd=O

(I')

H20
(1)

L:iigand

2H + ' ~ e - ~ /

( 0 7 H2PO~" etc )

L..
'F~ 0.3

(A)

E
=L

pd 2+

\ 0.2
c
o

%
s
~0.I
~6
2
~0

C02
".

"0_
I
2
3
time on s~-ream / h

Fig. 9. Oxidation of toluene with cyclic short and open-circuit operations. Experimental conditions B. Shaded; short circuit. Unshaded; open
circuit.

(3)[
COOH

0
Fig. 10. Reaction scheme.

Downloaded on 2014-10-17 to IP 141.214.17.222 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).

J. Electrochem. Soc., Vol. 138, No. 11, November 1991 9 The Electrochemical Society, Inc.

3182
";'c _ __,eshort

,,
,,9
C3J

.-tO

><

1
;'-.~'~'~

All the EMF values measured at different experimental

conditions in this work varied by less than 620 mV. As described earlier, the addition of chloride decreased the EMF
(Tables I and II). The decrease depends on the amount of
NaC1 added (Fig. 3). As described earlier, the remarkable
increase in the selectivity to PhCHO with the addition of
NaC1 followed the decrease in the EMF. The EMF observed for the anode added with 70 i~mol of NaC1 was
380 _+ 15 mV, which did not change appreciably with temperature or partial pressure of toluene and oxygen. As described above, toluene and products (PhCH2OH, PhCHO,
PhCOOH) dissolved in the membrane; thus a cross-leakage of these c o m p o u n d s occurred during reaction. Therefore, we cannot avoid a chemical short of these compounds. This must inevitably make the observed EMF
lower than the theoretical value (E~ Since the reaction
system was so complicated, we cannot discuss the effect of
various kinetic factors in connection with the EMF observed. To make this possible, it is absolutely necessary to
avoid cross-leakage, to simplify the system, and to measure the potential of both electrodes using a reference electrode under various experimental conditions.

open

/
x

. . . .

"e..-

z~

l i m e on stream

Fig. 11. The kinetic curves of the products after opening the circuit.
Experimental conditions A.
electrochemical oxidations as well as the nonelectrochemical formation of P h C H O (step 2). When the circuit
was shorted for a short time (5-10 min) to prevent the accumulation of c o m p l e x A, the side reactions were depressed,
increasing the current efficiency of PhCHO and PhCOOH
(Fig. 9). As described earlier, the rate of partial oxidation to
PhCHO and PhCOOH increases, but the rate of CO~ formation decreases, as reaction temperatures are decreased
(Fig. 4 and 5). The increase in the rate of partial oxidation
can be ascribed to the decrease in the rate of unfavorable
side reactions. Hence, the latter reactions must have larger
activation energies w h e n compared to the partial oxidation. If we can accelerate the formation rate of PhCHO
(step 2), the absolute rate of PhCHO formation, as well as
the decrease in the rate with reaction time, will be improved remarkably under short-circuit conditions. Further
study is now under way to accelerate the rate of nonelectrochemical reaction step 2.

Manuscript submitted Dec. 17, 1990; revised manuscript

received J u n e 7, 1991.

The Tokyo Institute of Technology assisted in meeting the

publication costs of this article.
REFERENCES
1. G. I. Golodets, "Heterogeneous Catalytic Reactions Involving Molecular Oxygen," p. 667, Elsevier, Amsterdam (1983).
2. J. Kwiatek, J. H. Murib, and C.K. Brush, US Pat.,
3,946,067 (1976); H. Miyake, Jap an Pat. 48-13335
(1973); K. Murao, T. Nakanome, and T. Yamaura,
J a p a n Pat., 53-5132 (1978); T. Onoda, K. Wada, and S.
Fuji-i, J a p a n Pat., 54-151937 (1979).
3. K. Otsuka, Y. Shimizu, and I. Yamanaka, This Journal,
137, 2076 (1990).
4. G. R. Stafford, Electrochim. Acta, 32, 1137 (1987).
5. K. Otsuka, Y. Shimizu, I. Yamanaka, and T. Komatsu,
Cat. Lett., 3, 365 (1989).
6. K. Otsuka, Y. Shimizu, I. Yamanaka, and T. Komatsu,
Shokubai (Catalyst), 31, 48 (1989).
7. J. S. Roberts and K. J. Klabunde, J. Organomet. Chem.,
85, C13 (1975); J. Am. Chem. Soc., 99, 2509 (1977).
8. "Lange's H a n d b o o k of Chemistry," J. A. Dean, Editor,
McGraw-Hill, N ew York (1985).

EMF.--The electromotive force under standard conditions (E~ for the oxidations of toluene are shown below (8)
PhCH3 + 02
--* PhCHO + H20,
E ~ = 0.85 V
PhCH3 + 3/2 02 --* PhCOOH + H~O, E ~ = 0.98 V
PhCH3 + 9 Oa --~ 7CO2 + 4H20,
E ~ = 1.09 V

A Comparison of the Electrochromic Behavior and the

Mechanical Properties of W03 and NiOx Thin Film Electrodes
F. Decker,* R. Pileggi, S. Passerini, and B. Scrosati*
Dipartimento di Chimica, Universit~ Roma 'La Sapienza,' Rome, Italy
ABSTRACT
The charge-discharge cycles of WO3 and NiO~. thin film electrodes in a Li
carbonate electrolyte have been
followed in situ with a laser beam system that allows the simultaneous m easu r em en t of film transmittance and stress.
Quantitative relationships have been established between film thickness, absorbance variation, mechanical compression,
and charge inserted. The applications to electrochromic devices are discussed.
Tungsten oxide, WO~, is a well-known electrochromic
material which colors cathodically by the insertion of Li
ions (1, 2). Nonstoichiometric NiOx, on the other hand, is
an electrochromic material that bleaches cathodically,
again by the insertion of Li ions (3-4). These two materials
are c o m p l e m e n t a r y for optical absorption, and an efficient
electrochromic w i n d o w can be built combining WO3 and
NiO~ electrodes (3, 4). The color changes in WO3 are usually associated with an intervalence absorption band
* Electrochemical Society Active Member.

caused by small polarons introduced by the lithium donor

atoms (5). The origin of the color changes in NiOx has not
yet been fully explained, but a m i x t u r e of dark Ni~O4 and
transparent NiO has been proposed to occur in the oxide
films produced by reactive dc magnetron sputtering of
nickel (6). A similar intervalence absorption band could
exist in such samples, and would disappear with lithium
insertion due to the suppression of the 3+ oxidation state
of Ni. However, the electrochemical and the optical properties of both materials in nonaqueous electrolytes, such
as solutions of lithium perchlorate in propylene carbonate,

Downloaded on 2014-10-17 to IP 141.214.17.222 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).