Langmuir 1992,8, 2455-2460

2455

Surfactant-Intercalated Clay Films Containing Metal

Phthalocyanines
James F. Rusling, Maryam F. Ahmadi, and Naifei Hut
Department of Chemistry, Box U-60,University of Connecticut,
Storrs, Connecticut 06269-3060
Received February 24,1992.I n Final Form: June 24, 1992
We previously showed that clay-surfactant films containing metal phthalocyanines catalyze electrochemical reductive dechlorinations. Cobalt(I1) phthalocyanine (CoIIPc)was a much better catalyst than
the corresponding iron complex. This paper reports studies of these catalytic films by spectroscopic,
X-ray, and electron microscopic methods. Scanning electron microscopy cross sectional images of films
of didodecyldimethylmmonium bromide, clay, and CoIIPc were considerably different from the stacked
layers observed for pure composites. Previously observed phase transitions are characteristic of surfactant bilayers. The general morphology of these films appears to feature a heterogeneous mixture of CoIIPc
crystals and surfactant bilayers intercalated between clay layers. Electronic spectra and X-ray diffraction
patterns suggest that iron phthalocyanine (FeIIPc)is present in oxidized forms in these films. CoIIPc films
are better dechlorination catalysts partly because CoIIPc remains intact in the films, while FeIIPc is
decomposed.

Introduction
Ordered composites of clay and surfactants can be made
by reacting cation exchanging clay colloids with insoluble
amphiphilic cations. Films can be cast onto solid surfaces
from suspensions of these composites in organic solvents.
Surfactant films intercalated between linear ionic polyme13293 have been prepared by similar methods. Gel-toliquid crystal phase transitions for surfactant composite
films occur at temperatures close to those of bilayer
suspensions of the same surfactants. These results combined with X-ray diffraction and electron microscopy
studies suggest that the films are arranged in stacked surfactant bilayers intercalated between clay or polymer
layers. 1-3
Preparation and casting of composites as described
above are a convenient way to prepare ordered multiple
bilayer films of Surfactants with structures and properties
related to biomembranes. Films with thicknesses in the
micrometer range containing thousands of bilayers are
easily prepared. Permeability is controlled by the phase
of the
Neutral, water soluble solutes pass through
the films in the liquid crystal state but are blocked when
the films are brought to the solidlike gel phase. In addition
to controlling permeability, other possible applications
include coatings for piezoelectric5 or amperometric senS O ~ S , ~supports
J
for ordering biological macromoleculesld
+ On leave from Beijing Normal University, Beijing, China.
(1) Okahata, Y.; Shimizu, A. Langmuir 1989,5,954-959.
(2) (a) Shimomura,M.; Kunitake, T. Polym. J.1984,16,187-190. (b)
Kunitake,T.;Tsuge,A.; Nakashima,N. Chem. Lett. 1984,1783-1786. (c)
Nakmhima, N.; Kunitake, M; Kunitake, T.; Tone, S.; Kajiyama, T.

and inorganic complexes,1cand membranes for controlling

vectorial electron transport.8
We recently evaluated clay-surfactant films containing
redox mediators for electrochemical catalysis. Composite
films of didodecyl- and dioctadecyldimethylammonium
bromide (DDAB and DODAB) and clay cast on pyrolytic
graphite electrodes acted as barriers toward hydrophilic
multivalent ions6but incorporated hydrophobic ions and
neutral molecules from aqueous solutions. Clay-surfactant films containing neutral metal phthalocyanines
catalyzed reductive dechlorination of trichloroacetic acid?
Cobalt(I1) phthalocyanine was a much better catalyst in
the composites than the corresponding iron complex.
Charge transport rates were excellent when the films were
in liquid crystal phases but poor in solidlike gel states.
Gel-to-liquid crystal phase transitions were detected by
voltammetry6 and differential scanning calorimetry.
Clay-surfactant films containing metal phthalocyanines
showed excellent stability in catalytic applications and
were usable for a month or more. In this paper, we report
results of several types of experiments to characterize
composite films containing metal phthalocyanines: (i)
square wave voltammetry to establish redox properties of
the films; (ii) electronic absorption spectroscopy, which
provides insight into microenvironment, and oxidation
and aggregationstatesof the catalyst; (iii) scanning electron
microscopy (SEM) and energy dispersive X-ray (EDX)
analyses, which provide insight into film morphology,
structure, and catalyst distribution; (iv) X-ray powder
diffraction providing the d-spacing of the composites.

Experimental Section
Chemicals and Solutions. Didodecyldimethylammonium

kano, I(.J. Chem. Soc., Chem. Common. 1990,443-444.

(3) (a) Okahata, Y.; Enna, G.; Taguchi, K.; Seki, T. J. Am. Chem. SOC.
1986,107,5300-5301. (b) Okahata, Y.; Enna, G. J.Phys. Chem. 1988,
92,4646-4551. (c) Okahata,Y.; Enna, G.; Takenouchi,K. J.Chem. SOC.,
Perkin Tram. 2 1989,835-843.

bromide (DDAB, 99+ % ), dioctadecyldimethylammonium bromide (DODAB, 99+%), and iron and cobalt phthalocyanine
(97+ % ) were from Eastman Kodak. Cetyltrimethylammonium
bromide (CTAB, hexadecyltrimethylammonium bromide) was
Fisher certified grade, 99.8%. Solvents were spectroscopic grade.
All other chemicals were reagent grade. Bentonite clay (Bentolite H)was from Southern Clay Producb and had a cation
exchange capacity of 80 mequivI100 g.
Apparatus and Procedures. A Bioanalytical Systems BAS100electrochemistrysystem was used for Osteryoung-typesquare

Texter, J., Eds.; Plenum: New York, in press.

(8) Gratzel, M.HeterogeneousPhotochemicalElectronTransfer;CRC

Press: Boca Raton, FL, 1989.

Macromolecules1986,18,1515-1516. (d)Higashi,N.; Kajiyama,T.;Kunitake, T.; Praee, W.; Ringadorf, H.; Takahara, A. Macromolecules 1987,
20,29-33. (e) Nakashima, N.; Eda, H.; Kunitake, M.; Manabe, 0.;Na-

(4) Fendler, J. H. Membrane Mimetic Chemistry; Wiley: New York,

1982.
(5) Okahata, Y.; Ebato, H. Anal. Chem. 1991,63, 203-207.
(6) Hu, N.; Rueling, J. F. Anal. Chem. 1991,63, 2163-2168.
(7) Rusling, J. F.; Hu, N.; Zhang,H.; Howe, D.; Miaw, C.-L.; Couture,
E. In Electrochemistry in MicroheterogeneousFluids; Mackay, R. A.,

0743-7463/92/2408-2455$03.00/00 1992 American Chemical Society

Ruling et al.

2456 Langmuir, Vol. 8,No. 10, 1992

wave voltammetry (SWV). The working electrode was a basal
plane pyrolyticgraphite (HPG-99,Unioncarbide) disk (geometric
A = 0.2 cm2). Electrodes were prepared by sealing a disk into
polypropylene pipet tips as described previouslf or by sealing
to glass tubes with heat shrinkable tubing. Pyrolytic graphite
(PG) electrodes were rough polished with 600-grit S i c paper on
a metallographic polishing wheel prior to coating.
Surfactant-clay composites were prepared by reacting clay
colloids and surfactant in aqueous suspension as described
previously.6 Purified, freeze-dried composite was suspended in
chloroform (2 mg mL-1) for preparing films. Metal phthalocyanine (MPc) solutions in chloroform (10 mM) were mixed 1:l
with the composite suspension. For voltammetry and SEMI
EDX, 120 pL of the composite MPc suspension was deposited
with a micropipet onto a 0.2 cm2 pyrolytic graphite disk.
Chloroformwas evaporated overnight in air. Dry film thicknesses
by SEM were 20-30 pm?
The three-electrode cell for SWV included the pyrolytic
graphite (PG) working electrode, a platinum wire counter
electrode, and a saturated calomel electrode (SCE) as reference.
Ohmic drop of the cell was about 90 % compensated by the BAS100. Experimenta were thermostated at 25.0 f 0.1 OC. All
solutions were purged with purified nitrogen to remove oxygen
before SWV.
Absorption spectroscopy was done using Perkin-Elmer Model
h3B or Milton Roy Spectronic 3000 Array UV-Vis spectrophotometers. The reference for composite films was usually a plain
glass slide. For visible spectroscopy,MPc-compositesuspensions
were prepared as above, but with 1r M MPc to obtain measurable
absorbance spectra. An 80-pL portion of the suspension was
cast onto a masked 0.5-cmZarea of a glass microscope slide and
chloroform was evaporated in air overnight. Dry thickness was
estimated at ca. 10 pm by SEM.
Scanning electron micrscopy (SEM) and energy dispersive
X-ray analysis (EDX) were done with an Amray 1810microscope
using a tungsten filament. DDAB films for SEM/EDX analysis
were coated on PG electrodesusing the same preparation methods
as for electroanalysis. The entire electrode assembly was fiied
on the mounting stage of the SEM with electrical connection
through the connecting wire. For cross-sectionalviews, composite
coatings were prepared on very thin disks of pyrolytic graphite
and freeze fractured after immersion in liquid nitrogen. Prior
to analysis by SEM, 5 nm of gold was coated onto samples with
a Model SC 500 sputter coater (Bio-Rad). EDX was done using
a Phillips North America PV-9800 EDAX system. Beam
diameter was 2 pm.
X-ray diffraction studies were done with a Scintag XDS 2000
powder diffractometer using a Cu Ka source at 45 kV and 40 mA.
Scan rate was 0.5 deg/min. Films for X-ray diffraction were
prepared on glass microscope slides from chloroform dispersions
with compositions described above. Before analyses, the dry
films were soaked in 0.1 M KBr for 2-3 h, washed with water,
and stored in a closed desiccator with a small amount of water
in the bottom to maintain hydration.

Results
Electrochemistry. Squarewave voltammetrywas used
to measure reduction and oxidationpotentials of the metal
phthalocyanines in the films. For the film containing
cobalt phthalocyanine (CoPc),the first reduction peak at
about -420 mV (all vs SCE)corresponds to the reversible
CdIPclCoIPc-redox couple as reported previously6 (Figure
la). Ita shape reflects overlapped peaks due to adsorption
of CoPc on the electrode. By comparison with peak
potentials reported for CoIIPc in organic solventa,9JO the
second reduction peak at about -1350 mV most likely
corresponds to the Co1Pc-/Co1Pc2-couple. No oxidation
peak was observed for CoIIPc. The current increase at
700 mV (Figure lb) is probably caused by oxidation of
bromide ions.
(9)Lever, A.B.P.; Licoccia, S.;Magnell, K.; Minor, P. C. Adu. Chem.
Ser. 1982,No. 201, 231-251.
(10) Ruling, J. F.;Owlia, A. J. Electroanab Chem. Interfacial Electrochem. 1987,234,297.

0.001
-100

'

'

"

'

'

"

'

'

700

300

"

1100

'

"
1500

-E, mV v8 SCE

-0.25 1

-0.05
0.00
700

500

100

300

E, mV v8 SCE

Figure 1. Square wave voltammograms at 250 Hz,25 mV pulse

height for CoPcclay-DDAB films on PG disks in 0.1 M KBr:
(a) cathodic scan; (b) anodic scan.
0.30

-0.16

-0.10

400

800
-E, mV VI

1200
SCE

'

700

1600

500

3 00

100

-100

E, mV v8 SCE

Figure 2. Squere wave voltammograms at 250 Hz,25 mV pulse

height for FePcclay-DDAB films on PG disks in 0.1 M KBr:
(a) cathodic scan; (b) anodic scan.

Two reduction peaks were found for films to which iron

phthalocyanine (FePc) had been added (Figure 2). The
peak at -580 mV is in the potential range for an FeuPc
reduction. The peak at -1260 mV, by comparison with
literature?JO is in the same range as a Fe1Pc-/Fe*Pc2couple. An oxidation peak for FePc films was observed
at 100 mV (Figure 2b).

Langmuir, Vol. 8, No. 10, 1992 2467

Clay-Surfactant Films Containing CdIPc

Table I. Electronic Absorbance Peakr for Metal

Phthalocyanines in Different Media
A,
values, nm
cobalt phthalocyanine iron phthalocyanine
medium4 (A*)*
DMSO (1.0)
658
596
653 630 590
CHzClz (0.82)
665
706 657 552
benzene (0.59)
667
599
708
674
hexane (4.08)
671
746 709 680
tetradecane (-0.08) 670
596
706 660

0.10

0.054

0.1 M CTAB

668
670
668

clay/DDAB
clay/DODAB
WAVELENGTH (nm)
0.mo

609
639
638

707
146
748

606
603

616
681
682

594
592

4 Enough metal phthalocyanine was added to make each solution

1 pM. In the most hydrophobic solvents, some particles remained
which were removed by filteringbeforethe spectra weretaken. Taft
r* parameters from ref 12.

Films
COPC

CoPc

FePc

0.060

6901

u'
I _

0.040

670

'

5 0 0 5 5 0 ~ " 7 5 0 8 0 0 8 5 0

WAVELENGTH (nm)

650
-0.30

0.10

0.50

0
0

0.90

1.30

-*
II
Figure 4. Influence of Taft's A* solvent parameter on maxima
of longest wavelength peaks of metal phthalocyanines in various
solvents. A* values are given in Table I. Maxima for CoPc in
DDAB- and DODAB-clay films are arbitrarily located on the
linear regression line for the CoPc solution data.

WAVELENGTH (nm)

Figure 3. Visible absorbance spectra of (A) 1 pM ConPc in

DMSO (B) 1 pM ConPc in 0.1 M aqueous CTAB, (C) ConPc in
clay-DDAB film.

UV Spectra. Electronic spectra of metal phthalocyanines in the visible region reflect their state of aggregation.11 In DMSO, the peak for CoPc at 658 nm and a
small peak at 596 nm are attributed to the monomer
(Figure 3A).1J1
Peaks for association dimers of metal phthalocyanines
are generally found as shoulders on the short wavelength
side of the main monomer peak." When CoPc is dissolved
in aqueous micellar 0.1 M cetyltrimethylammonium
bromide (CTAB), a relatively large peak attributed to
dimer is found at 609 nm along with the monomer peak
at 668 nm (Figure 3B). This is presumably because the
~~

(11) (a) Schelly, 2.A.; Farina, R. D.; Eyring, E. M.J. Phya. Chem.
1970,74,617-620.(b)Schelly,2.A.; Huward, D. J.; Hemes, P.; Eyring,
(c) Gruen, L.C.; Blagrove,
E. M.J. Phya. C h m . 1970,74,3*3042.
R. J. A u t . J. Chem. 1972,25,2553-2558;1973,26,319-323. (d) Boyd,
P.D. W.; Smith, T. D. J. Chem. SOC.,Dalton Tr0n.s. 1972,839-843.(e)
Farina, R. D.; Halko, D. J.; Swinehard, J. H. J. Phya. Chem. 1972,76,
2343-2348. (0Abel, E. W.; Pratt, J. M.;Whelan, R. J. Chem. SOC.,Dalton Trans. 1976,509-514. (g) Yang, Y.;Ward, J. R.; Seiders, R. P. Inorg.
Chem. l986,24,1765-1769.

water-insoluble CouPc is solubilized in restricted hydrophobic regions of the micelles at concentrations which
drive the formation of dimers. Composite clay surfactant
filmscontaining CoPc had prominent monomer peaks near
669 nm with a relatively small dimer peak at about 639
nm (Figure 3C).
Spectra of CouPc were recorded in dimethyl sulfoxide
(DMSO), methylene chloride, tetradecane, hexane, and
benzene, as well as in composite clay films of DDAB and
DODAB (Table I). The main monomer peak showed a
definite shift toward longer wavelengths as solvent polarizability decreased. A linear plot was obtained when
,A
of the monomer peak was plotted against Taft's polarizability/dipolarityl2parameter x* (Figure 4). When
,A of CoPc in DDAB and DODAB composites are placed
on this regression line, a value of T* = 0.1 is found. This
is about midway between values for tetradecane and diethyl ether.
In DMSO, spectra of FePc were similar to those of CoPc,
with a monomer peak close to 653 nm and a dimer shoulder
at about 630 nm (Figure 5A, Table I). However, in less
polar solvents, in 0.1 M CTAB, and in the composite films
(Figure 5B), broad peaks were observed at wavelength
about 700 nm (Table I). After a day or more, spectra
obtained from methylene chloride and DMSO solvents
showed the increasing development of these peaks. The
positions of the longest wavelength peaks for freshly
(12)(a)Taftsolvent polarity indiceswere derivedbased on wavelength
shifta in absorption spectra for indicator solutes in a wide range of
solventa.'*b The A* parameter is an indicator of solvent polarity and
Abraham, M.H.;
polarizability. (b) Kamlet, M.J.; Abboud, J. L.-M.;
Taft, R. W. J. Org. Chem. 1983,48,2877.

Rwling et al.

2468 Langmuir, Vol. 8, No. 10, 1992

BCINTA,ci/US&

88.21 14.11 29.43 22.01

800.0

560.0

480.0
400.0
320.0

240.0
WAVELENQTM (nm)

17.66 14.72 12.62 11.04

160.0
80.0

0.0

IN: mjn205n5.ni I D : COPS

DATE: 2 / 5 / 9 2
TIME: 9:15

88.21

em

700

750

41.14 29.43 2 2 . 0 7

600.0j1

480 .O -

ow

8%

420.0-

WAVELENGTH (nm)

Figure 5. Visible absorbance spectra of (A) 1 WM FeIIPc in

DMSO; (B) FePc-clay-DDAB film.

S T L P : 0.030

17.66 14.12 12.62 11.01

9
1.51060

Wt:

9.82

8.84

60

pol

so
40

30

basal macine.A
clay alone
10.2 f 0.4
composite alone
25.5 f 0.5
composite + CoPc
23.8 f 0.8
composite + FePc
29.1 f 0.6
0 See Experimental Section for preparation and compositions.
28,dea
8.66
3.46
3.14
3.03

100

t70

Table 11. X-ray Diffraction Results for DDABClay

Composite Films

film additivea

8.84

BCINTAO/USA

PT: 3.600

540.0BW

9.82

20

prepared solutions of FePc gave no correlation with the

solvent parameter a* (Figure 4).
X-ray Diffraction. The lowest angle 28 reflection for
clay colloid films intercalated with surfactants can be used
to obtain the interlayer basal spacing through the Bragg
relation.12J5 These small angle peaks were observed for
clay-DDAB composites with and without MPcs (Table
11). These peaks were rather broad, suggesting a degree
of disorder in the films. Values for hydrated films were
roughly within experimentalerror of each other. The basal
spacings for unhydrated films were much smaller.
Although only one peak at 28 3.46O was found for the
pure clay-DDAB composite, a series of additional peaks
occurred in the 4-10 region when MPcs were present in
the films. For CoPc films, the first peak marked 23.8 A
gives the clay basal plane spacing of the film (Figure 6a).
Peak between 28 4O and loo in the CoPc film pattern are
at nearly identical positions to those found for CoPc
powder (Figure 6b). We conclude that there are crystals
of ConPc in the film. The FePc composite film clear1
shows the basal plane reflection peak marked 29.1
(Figure 7a). However, peaks between 28 4O and loo are
different from those in the X-ray spectrum of Fe*IPc
powder. We conclude that these additional peaks in the
FePc films are not caused by crystals of FenPc.
ScanningElectron Microscopy/EnergyDispersive
X-ray Analyris. SEM images of the films before use in
aqueous solution appeared distinctly different from those
of films that had been soaked in aqueous solutions. Thus,

AT

(13) Shi, C.; Ruling, J. F.;Wang, Z.;Willis, W. S.; Winiecki, A. M.;

Suib, 5. L. Langmuar 1989,5, 650.

10
0

10

Figure 6. X-ray diffraction powder pattern for (a) CoPcclayDDAB film and (b) CoPc powder.
all SEM and EDX experimenta were done on samples
that had been previously soaked in aqueous 0.1 M KBr,
then air-dried, to closer approximate the condition of the
films previously used for electrochemical catalysis.
SEM images of the top of the films were very different
for composites with and without MPcs (Figure 8). Films
containing MPcs appeared to include crystalline structures. These structures were different for CoPc films,
which appeared as a collection of needlelike crystals, than
for FePc films. The FePc composite filma appeared more
amorphous, but a few needlelike crystals could be men.
The above morphologies were confirmed by crosssectional SEM images of the films after freeze fracture.
The pure clay surfactant composite films showed (Figure
9a) a layered structure similar to that reported for other
surfactant
However, cross sections of the
CoPc f i i appeared as crystals (Figure9b). Cross sections
of the FePc compositefilms revealed a rather thick layered
structure with a few needlelike structures (Figure 9c).
EDX of composite films detected silicon, aluminum,
and the metal from MPcs. Traces of potassium and
chlorine were also found, but no bromine was detected.
Analyses at different apota on the sample surface revealed
a relatively constant Al/Si ratio consistent with the
aluminosilicate clay as the source for these two elementa.
For CoPc films, this ratio had a 13% relative standard
deviation. In contrast, the Co/Si ratio varied considerably
from spot to spot and had a relative standard deviation
of 63 7%. This suggesta a heterogeneous distribution of
CoPc in the film.
The Al/Si ratio in FePc films measured by EDX had a
reproducibility of about 10%. The Fe/Si ratio had a

hngmuir, Vol. 8, No. 10, 1992 2459

Clay-Surfactant F i l m Containing CdIPc

-1

88.27 44.14 2gk43 22.,07 17.,66 14:72 12.62

2000.0

1800.0

9.82

8.84

loa
90

1600.0

11.04

80

1400.0

70

540.0.

480.0420.0
360.0-,~~
300 .O

Figure 7. X-ray diffraction powder pattern for (a) FePc-clayDDAB film and (b) FePc powder.

standard deviation of 26% Iron may be distributed more

homogeneously in its composites than is CoPc.

Discussion
Cobalt PhthalocyanineCompositeFilms. Electronic
spectra and electrochemistry of the films to which CoIIPc
was added are consistent with the presence of CoHPc.In
organic solventa, the main monomer peak of CoIIPc shows
a linear correlation with the Taft polarizability/dipolarity
parameter A*. In the films, the monomer peak appears
at values close to those in the nonpolar solvents (cf. Figure
4). Results suggest that the molecules responsible for the
spectrum are present in a relatively nonpolar environment,
which, however, is somewhat more polar than a tetradecane environment. The fact that no oxidation peak is
observed for CoIIPc in the film is consistent with the
presence of weak axial ligands which stabilize CorlPc
toward oxidation.9
The UV spectrumin 0.1 M CTAB micelles reflects heavy
dimerization of CoIIPc. The spectra of CorlPcin the films
have a large monomer peak and only a small dimer peak.
Thus, the degree of dimerization of CorlPc in the films
seems relatively small compared to CTAB micelles.
X-ray diffraction results are consistent with a structure
featuring surfactant intercalated between the clay layers.
The interlayer spacing is increased greatly in the surfactant clay films compared to pure clay films (Table 11).
This spacing, however, is somewhat smaller than the 30
A found previously for DDAB-montmorillonite clay
composites.1 The observed spacing in our films, made
with a different clay with a 40 % smaller cation exchange

Figure 8. SEM top views of (a, top) clay-DDAB film and (b,
bottom) CoPc-clay-DDAB film.

capacity, was on the order of 15-20A after subtracting 9.8

A for the thickness of the clay layers from the values in

Table 11.
The X-ray diffraction patterns suggest the presence of
crystallized CorlPcin the films. This is confirmed by the
SEM images which clearly show crystals. EDX spot
analyses suggesting heterogeneous distribution of Co in
the films is also consistent with the presence of crystals.
SEM cross-sectionalviews of the pure clay-DDAB films
clearly show the layered structure observed previously for
polymerized surfactant bilayer composites.2dBk The layered structure is obscured when CoPc is present in the
films.
Iron PhthalocyanineComposite Films. The voltammetric oxidation peak at 100 mV vs SCE for these films
showed that the iron present is quite easily oxidized.
Electronic spectra in DMSO reflect the presence of
monomer and dimer of Fer1Pc.l0J1However, in less polar
solvents, much broader peaks at longer wavelengths are
observed which showed no correlation with the Taft A*
solvent parameter.
Iron(I1)phthalocyaninetetrasuEonatedissolved in water
is irreversibly oxidized by air.14 FeIIPc suspended in
organic solvent is oxidized by air to a dimeric p-oxo species
with an FerlLO-Ferrllinkage.15 Voltammetry of this dimer
in pyridine revealed a single-electron oxidation peak at
0.47 V vs SCE and two one-electron reduction peaks at
(14) McLendon, G.; Martell, A. E. Inorg. Chem. 1977,16, 1812.
(15) Ercolani, C.; Gardini, M.; Monacelli, F.; Pennesi, G.; h i , G.
Inorg. Chem. 1983,22,2584.

Rusling et al.

2460 hngmuir, Vol. 8, No. 10, 1992

Table 111. Results of EDX Spot Analyses of Clay-DDAB

films
atomic ratios
mot no.

1
2
3
4
5
6
mean i 8

1
2
3
4
5

6
mean i s

Figure 9. SEM cross-sectional views of (a, top) clay-DDAB

film, (b, middle) CoPc-clay-DDAB film, and (c, bottom) FePcclay-DDAB film.

-0.59 V and -0.95 V.I6 In 96 % sulfuric acid or as powders,

the two crystalline forms of the p-oxo dimers gave
absorbance maxima at 695 nm, a wavelength considerably
longer than that of the FerlPc monomer. These p-oxo
dimers are irreversibly oxidized by oxygen.15
The electrochemical behavior of the p-oxo dimer is
qualitatively similar to what we observe for the composite
FePc film. Quantitative comparison is difficult since the
(16)Bottomley,L.A.; Ercolani, C.; Gorce, J.-N.;Penneai, G.;h i , G.
Inorg. Chem. 1986,25,2338.

CoPc Film
AlISi
0.238
0.160
0.186
0.195
0.183
0.198
0.193 f 0.026 (*13%)
FePc Film
AIISi
0.215
0.231
0.234
0.193
0.230
0.186
0.215 f 0.021 (&lo%)

CoISi
1.48
0.088
1.9
42
5
2
2.86
3.58
2J6f 1-29(163%)
FeISi
0.91
1.56
1.02
0.84
0.92
1.27
1.09 f 0.28 (i26%)

experiments on the dimer were done in pyridine,lGa strong

axial ligand which would have considerable influence on
the redox potentials. Thus, the observed oxidation and
reduction peaks in the films could come from FePcspecies,
p-oxo dimer, or other products of FePc oxidation. However, the spectra in nonpolar organic solvents and in the
composite films clearly show large, broad electronic
absorbance bands at wavelengths longer than that of the
FerlPcmonomer. This peak forms rapidly when FeIIPc is
dissolved in nonpolar solvents and its slow growth with
time was observed in DMSO and methylene chloride. This
behavior is consistent with the observed destabilization
of the FeIIPc oxidation state by weak axial ligand^.^
We conclude that the FerrPcoriginally placed in the
composite films is a t least partly oxidized, probably
through formation of the p-oxo dimer and perhaps further
oxidation of this species. This conclusion is supported by
the X-ray diffraction data, which show that the peaks in
the 4-10' 28 region are not due to FeIIPc crystals.
Conclusions
The morphology of clay-DDAB composite films is
clearly changed by the presence of CoIIPc. The gross
structure appears as a collection of CoIIPc crystals, rather
than the stacked layers observed in the pure composite.
However, gel-to-liquid crystal phase transitions were
clearly observed in electrochemical catalysis at transition
temperatures close to those found for DDAB bilayer
suspension^.^*^ This suggests the presence of surfactant
bilayers. However, the basal plane spacing of the clay at
about 15-20 A, is considerably smaller than the 33.4 A
required to accommodate two extended DDAB chains
normal to the aluminosilicate layers. Thus, considerable
tilting' and self-intercalation of the hydrocarbon chains
must be considered. The general picture that suggests
itself is a rather heterogeneous mixture of CoIIPc crystals
and DDAB bilayers.
Our results suggestthat composite filmscontaining ConPc are better catalysts than those containing FeIIPc partly
because CorlPcremains intact in the films while FeIrPcis
present in irreversibly oxidized forms.

Acknowledgment. This work was supported by U.S.

PHS Grant No. ES03154awarded by the National Institute
of Environmental Health Sciences. We thank E. J. Neth,
Yanfei Shen, and S. Suib for help with X-ray and SEM
analyses and David Howe for helpful discussions.
Registry No. DDAB, 3282-73-3;CoIIPc, 3317-67-7;FeIIPc,
132-16-1.