JOURNAL OF RAMAN SPECTROSCOPY

J. Raman Spectrosc. 2004; 35: 1016–1022

Published online 12 November 2004 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jrs.1235

Study of the adsorption of benzimidazole

and 2-mercaptobenzothiazole on an iron surface
by confocal micro-Raman spectroscopy
G. Wang,1∗ A. Harrison,2 X. Li,1 G. Whittaker,2 J. Shi,1 X. Wang,1 H. Yang,1 P. Cao3 and
Z. Zhang1
1
Department of Chemistry, Shanghai Teachers University, Shanghai 200234, China
2
University of Edinburgh, Edinburgh EH9 3JJ, UK
3
Department of Chemistry, Suzhou University, Suzhou 215006, China

Received 4 November 2003; Accepted 2 May 2004

Benzimidazole (BIMH) and 2-mercaptobenzothiazole (HMBT) dissolved in ethanol were chosen for the
investigation of the interaction between organic molecules and surface atoms of iron or iron oxide by
confocal micro-Raman spectroscopy. Both BIMH and HMBT show enhanced and highly structured spectra
in the 200–1500 cm−1 region when the iron is at a potential of ca −0.7 to −0.9 V in a neutral medium.
BIMH had a weak interaction with the iron surface in a basic medium but it was chemically adsorbed in
a neutral medium. HMBT was chemically adsorbed on the iron via the exocyclic S and N atoms in acidic
and neutral solutions, whereas in basic media it was bound electrostatically. Copyright  2004 John Wiley
& Sons, Ltd.

KEYWORDS: benzimidazole; 2-mercaptobenzothiazole; iron; adsorption; confocal micro-Raman spectroscopy

INTRODUCTION useful tool in such studies, but measurements on solutions

It is well known that the shape of small particles growing
from solution may be controlled by small organic molecules
that bind preferentially to specific crystallite faces. In some
cases the physical and chemical properties of nanoparticles
are altered by a single layer of the organic molecules.1,2 This
approach has been exploited very successfully in the devel-
opment of magnetic recording materials, metal extraction
agents and anti-corrosion compounds, for example. There-
fore, it is useful to investigate the interaction between surface
atoms of the particles and the coating molecules. However,
this presents a significant experimental challenge because
the interface between the surface atoms of nanoparticles and
the coating molecules is usually only a few atoms thick.
X-ray photoelectron spectroscopy is a powerful tool in sur-
face analysis and is mainly used to identify the elemental
composition of the surface species, and perhaps also the
valences of particular atoms. Infrared spectroscopy is also a
Ł Correspondence to: G. Wang, Department of Chemistry, Shanghai
Teachers University, Shanghai 200234, China.
E-mail: ghuaw@shtu.edu.cn
Contract/grant sponsor: Royal Society.
Contract/grant sponsor: The Science and Technique Committee of
Shanghai.
Contract/grant sponsor: Shanghai Rare Society.
or wet samples are usually difficult because of interference
from molecules of solvents such as water. In 1974, Raman
spectroscopy was first applied to investigate the adsorp-
tion mode of pyridine on silver and the surface-enhanced
raman scattering (SERS) effect was observed.3 From then on,
SERS became a significant technique for studying the micro-
scopic mechanism of surface reactions. It has been applied
to investigate the adsorption mode of organic compounds
on copper, silver and gold4 – 7 and anticorrosion agents on
noble metals.8 – 16 However, the analysis of the adsorption
mechanism of organic species on non-noble metals is rel-
atively rare because SERS is relatively ineffective for such
materials. However, in the past 10 years, the development
of confocal micro-Raman spectroscopy has greatly acceler-
ated studies of surface species on the surfaces of non-noble
metallic elements such as nickel and platinum.17 – 19 SERS has
also been tried in the study of pyridine and sulfur-containing
compounds on the surface of iron by depositing iron parti-
cles on the activated silver and silver particles on the iron
surface.20,21 In recent years, our laboratories have observed
the chemical interaction between imidazole and a pure iron
surface using a confocal micro-Raman spectrometer and the
SERS technique and acquired stronger Raman signals of the
surface adsorbate.22,23

Copyright  2004 John Wiley & Sons, Ltd.

 Adsorption of benzimidazole and 2-mercaptobenzothiazole on iron 1017

In this work, benzimidazole (BIMH) and 2-mercapto-

benzothiazole (HMBT) were chosen as target molecules
to investigate the interaction of organic molecules with
elemental iron or iron oxide, these molecules have already
been studied in detail on elemental silver and gold, because
their nitrogen and sulfur atoms are strong electron donors
to iron and iron oxide. Our principal aim was to establish
a foundation for future investigations of the interaction of
organic molecules with iron or iron oxide nanoparticles.

EXPERIMENTAL
BIMH and 2-HMBT (Analysis grade, Shanghai Chemical,
Shanghai, China) were dissolved in 95% ethanol at a
concentration of 0.1 mol dm
3 . KClO4 was added to the
neutral solution as a supporting electrolyte. NaOH and
H2 SO4 were added to the solutions when an acidic or basic
medium, respectively, was required. Iron (99.95% purity,
Shanghai Chemical) was prepared as a working electrode
(vs SCE) in an electrochemical system so that a suitable
potential could be applied to the iron. The procedure of
roughening the iron surface has already been described in
detail elsewhere.22
The Raman equipment was a confocal micro-Raman
spectrometer (Super LabRam II system, Dilor, France).
Excitation was effected with 632.8 nm radiation from a
13 mW He–Ne laser. The confocal hole was set at 500 µm so
as to filter out the signal coming from solutions as much as
possible and the slit was set to 100 µm. The laser beam was
focused on the iron surface by an Olympus long working
length objective (ð50 lens). Calibration was done with an
accuracy of š2 cm
1 using the 519 cm
1 line of silicon as a
Figure 1. Raman spectra of BIMH obtained from neutral
reference.
solution (a) and on the iron surface at potentials of
1.3 (b),

1.1 (c),
0.9 (d),
0.7 (e) and
0.5 V (f). Asterisks denote
RESULTS AND DISCUSSION signals from ethanol.

Although BIMH and HMBT are similar in structure, there is

a difference in adsorption behavior on iron. Environmental
factors such as the pH of the solution and the electrical
potential of the iron can also affect the behavior of these
molecules.
Benzimidazole
The Raman spectra obtained from the neutral and basic
solutions at different potentials from
1.3 to
0.5 V are
presented in Figs 1 and 2, respectively. The characteristic
bands of the spectra from the solutions and the iron surface
at
0.9 V in neutral and
1.3 V in basic media are listed in
Table 1.
Use of the confocal technique effectively weakens the
Raman scattering signal coming from the solvent and species
in the solution, making it much easier to see the Raman scat-
tering signal from the surface when the laser beam is focused
there. Figure 1(a) is the Raman spectrum of BIMH solution
and Fig. 1(b)–(f) show the spectra obtained from iron surface.
It can be seen that the spectrum obtained from BIMH solu-
tion shows strong bands characteristic of ethanol (marked
with asterisks) in addition to bands due to BIMH, whereas
those obtained from the iron surface show no significant
signal from ethanol. The vibrational modes of BIMH from
spectra taken on the iron surface are different from those in
solution, and their intensity changes with the potential of
the iron, indicating that these molecules are associated with
the surface. It is known that the nitrogen atom on the imida-
zole ring has an unshared electron pair that can be donated
to the available orbitals of iron atoms. The occurrence of
an Fe–N bending mode at 190 cm
1 demonstrates the for-
mation of a chemical bond between iron and BIMH and a
shift to 642 cm
1 of the N–H out-of-plane bending mode of
pyrrole from 623 cm
1 reaffirmed the formation of chemical
bonds. This is because when the pyridine nitrogen atom
denotes its unshared electron pair to the available orbital
of the iron atom, the electron density on the imidazole ring

Copyright  2004 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2004; 35: 1016–1022
1018 G. Wang et al.

would transfer, in part, to the iron atom, which attracts the

electron pair on the pyrrole N—H bond further towards the
nitrogen atom and makes the N—H bond shorter, resulting
in a higher wavenumber of the N–H vibration.
A more negative potential (
1.3 V) is unfavorable to
association of BIMH molecules with iron. However, the
significant increase in the intensity of BIMH vibrational
modes at potentials more positive than
1.3 V implies
that more molecules are found on the iron surface. The
enhanced in-plane vibrations of the molecules, for instance
as evidenced by enhanced CH modes at 1298 and 1304 cm
1 ,
and ring stretches at 1352 and 1365 cm
1 , show that the
molecules are perpendicular or tilted towards the surface.
The 1075 cm
1 band [Fig. 1(d)], which is concealed by
ethanol bands in the spectrum taken in solution, could be
clearly observed, illustrating the advantages of the confocal
micro-Raman spectrometer.
In the spectrum obtained from the solution, two C–H
in-plane bending modes of BIMH appeared at 950 and
Figure 2. Raman spectra of BIM
obtained from basic solution 1303 cm
1 . After the BIMH was adsorbed on the iron surface,
(a) and on the iron surface at potentials of
1.3 (b),
1.1 (c), the 950 cm
1 mode shifted to higher wavenumber and

0.9 (d),
0.7 (e) and
0.5 V (f). Asterisks denote signals from split into two bands at 997 and 1023 cm
1 . Meanwhile, the
ethanol. 1303 cm
1 mode split into bands at 1298 and 1304 cm
1 . In
addition, a faintly visible unknown mode appears at about
Table 1. Vibrational wavenumbers (
/cm
1 ) of benzimidazole 5 cm
1 higher from the 642 cm
1 NH mode [Fig. 1(d) and (e)].
adsorbed on iron and in bulk solution These changes seem to be indicative of the formation of two
different complexes on the iron surface. In the case that
Neutral pH 13 there are some ionized iron atoms on the surface under
Approximate description In On In On the experimental condition, the bands at 997 and 1298 cm
1
of vibrationsa solution irond solution irone could be assigned to a complex of BIMH coordinated with
iron atoms, while features at 1023 and 1304 cm
1 could be
Ring stretch (Im)b 1366 1365 1359 assigned to a complex with iron ions.
Ring stretch (Im)b 1353 1352 In basic medium, the intensities of the BIMH spectra on
i.p. CH deformation (Im) 1303 1304 the iron surface [Fig. 2(b)–(f)] hardly changed as the potential
i.p. CH deformation (Im) 1298 was changed, and all of them except two in-plane CH vibra-
i.p. Bz ring deformation 1270 1280 1263 1263 tional modes at 989 and 1073 cm
1 are weaker than those
1258 obtained from bulk solution [Fig. 2(a)], which implies fewer
Ring stretch (Im) 1242 BIMH molecules on the iron surface under basic conditions.
i.p. CH deformation (Bz) 1075 1073 No Fe–N stretching or N–Fe–N bending was observed in
i.p. CH deformation (Im) 1023 the low-wavenumber region of 180–400 cm
1 , indicating a
i.p. Bz ring deformationb 1007 1007 999 999 weaker interaction between BIMH and iron atoms. In the
i.p.CH deformation (Im)b 950 997 945 989 region from 1200 to ¾1400 cm
1 more ring stretching and
i.p. Bz ring deformationb 934 CH deformation bands are expected in terms of the observa-
i.p. ring bendingb 777 778 767 767 tion from neutral solution. However, it shows only a Bz ring
Ring torsion (Im)b 637 deformation mode at 1263 cm
1 and a very weak Im ring
o.p. NH deformationb 623 642 620 stretch mode at ca 1359 cm
1 . There may be poor adsorption
Fe–N bendingc 190 of BIMH on the iron surface under these conditions.
a
Assignments taken from Ref. 10 except where indicated. i.p. D In addition, it was unexpected that the N–H out-of-
in-plane; o.p. D out-of-plane. plane bending mode occurred in the spectrum [Fig. 2(a)];
b
Assignments taken from Ref. 24. this indicates that benzimidazole still exists in a protonated
c
Assignments taken from Ref. 25. form even at pH 13 in ethanol.
d
The potential of the iron is
0.9 V.
e
The potential of the iron is
1.3 V. 2-Mercaptobenzothiazole
The HMBT molecule has three atoms available for coordina-
tion, N1 and S3 atoms in the ring and the exocyclic S10 atom.

Copyright  2004 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2004; 35: 1016–1022

However, their coordination ability will be strongly affected
by the pH of the solution. Figures 3, 4 and 5 depict the
Raman spectra obtained from neutral, basic and acidic solu-
tions, respectively, and iron surfaces at different potentials.
The characteristic bands of the spectra from the solutions
and the iron surface at
0.9 V in neutral,
0.7 V in basic and

0.5 V in acidic media are listed in Table 2.
Figure 3(a) obtained from the solution shows a strong
ethanol spectrum but a weak HMBT spectrum. The Raman
spectrum obtained from the iron surface at
1.3 V shows
both weak ethanol and HMBT vibrational modes, indicating
very few ethanol and HMBT molecules on the iron surface
at such a negative potential. However, it seems certain
that HMBT has been adsorbed on the iron surface, from
the occurrence of the Fe–N mode at 198 cm
1 , Fe–S at
275 cm
1 and CH at 304, 384 and 405 cm
1 and the clear
enhancement of the Bz mode at 500 cm
1 , CS at 601 and
Figure 3. Raman spectra of HMBT obtained from neutral
solution (a) and on the iron surface at potentials of
1.3 (b),

1.1 (c),
0.9 (d),
0.7 (e) and
0.5 V (f). Asterisks denote
signals from ethanol.
Copyright  2004 John Wiley & Sons, Ltd.
Adsorption of benzimidazole and 2-mercaptobenzothiazole on iron 1019
Figure 4. Raman spectra of HMBT obtained from basic (pH 13)
solution (a) and on the iron surface at potentials of
1.3 (b),

1.1 (c),
0.9 (d),
0.7 (e) and
0.5 V (f). Asterisks denote
signals from ethanol.
711 cm
1 and CH at 1014 and 1131 cm
1 at more positive
potentials [see Fig. 3(c)–(e)]. CH deformation modes in
the low-wavenumber region are expected from the six-
membered benzene ring. Their appearance is probably due to
the characteristic molecular structure of HMBT. It is known
that the CH deformation modes of neat benzene do not
exist at these low wavenumbers. However, the benzene
ring of HMBT lost its high structural symmetry, owing to
the effect of the close neighbor five-membered ring. The
theoretical calculation shows that thiol and thione forms
of HMBT have four CH deformation modes in the range
from 250 ¾ 450 cm
1 .11 It is difficult to observe them even
on Ag or Au surfaces. Under suitable conditions stronger
chemical interaction will take place between the nitrogen
and the iron atom because iron can receive an unshared
electron pair from nitrogen in its 3d orbital. BIMH also
has a benzene ring either, but does not show the same
phenomenon. The reason may be a somewhat smaller effect
of N(1) and N(3) of the imidazole ring on the symmetry
of benzene ring compared with the N(1) and S(3) atoms of
HMBT.24
J. Raman Spectrosc. 2004; 35: 1016–1022
1020 G. Wang et al.
Figure 5. Raman spectra of HMBT obtained from acidic (pH 3)
solution (a) and on the iron surface at potentials of
1.3 (b),

1.1 (c),
0.9 (d),
0.7 (e) and
0.5 V (f). Asterisks denote
signals from ethanol.
The N–H bending mode at 682 cm
1 indicates the
existence of the thione form of HMBT. The S atom on the
thiazole ring was expected to have a weak coordination
ability since the lone electron pair on this atom participates
in the resonance structure of the molecule, resulting in a
decrease in electron density on the S atom and a decrease in
electron-donating power. The formation of chelate structures
is not probable because of their high strain energy.26 To find
the most probable coordination site, the bands of HMBT on
the iron surface were compared with those in solution. In
Fig. 3(d) (at
0.9 V), the bands due to the C2 N1 vibrations
at 1040 cm
1 and the C2 S3 vibrations at 711 cm
1 shifted to
higher wavenumber by about 6 and 9 cm
1 , respectively,
compared with those observed in solution. The C2 S10
vibration mode at 601 cm
1 shifted to lower wavenumber
by about 10 cm
1 . All these phenomena indicate that HMBT
adsorbs on the iron surface via the exocyclic S atom. In
Copyright  2004 John Wiley & Sons, Ltd.
this case, the formation of an Fe—S bond weakens the C2 S10
bond, reducing the double bond character to something more
like a single bond whilst also strengthening the C2 N1 bond
and the C2 S3 bond.12
The fact that the CH out-of-plane vibration at 863 cm
1
was very weak, whereas the CH in-plane vibration at
1131 cm
1 was much stronger [Fig. 3(d)] than that in solution
indicates that HMBT is oriented either perpendicular or tilted
relative to the surface according to SERS surface selection
rules.11 This perpendicular style of binding is maintained
while the potential changed from
1.1 V [Fig. 3(c)] to

0.7 V [Fig. 3(e)] since the relative intensities of all observed
vibrational modes of the spectra show no obvious changes
compared with those at
0.9 V.
In general, the surface coverage of neutral molecules
rises to a maximum near the PZC of the metal and, when the
potential is swept through a suitable range, the molecules will
desorb gradually and the intensity of the Raman spectrum
will decrease accordingly.27
When the potential of the iron is held at
0.5 V [Fig. 3(f)],
the relative intensity of the HMBT spectrum is very similar
to but slightly stronger than that in solution, implying
weakened adsorption and the same disorder of the molecules
on the surface as those in the solution. The appearance of
ethanol vibrational modes (marked with an asterisk) shows
that ethanol molecules start to be adsorbed on the surface of
iron as HMBT is desorbed.
In a basic medium, HMBT exists as the unprotonated
form (MBT
) as no SH and NH bands were observed
in the 2500–2800 and 600–700 cm
1 regions, respectively.
Therefore, as expected, a more negative potential of the
iron is unfavorable to the adsorption of HMBT. At
1.3 V
there are practically no HMBT bands visible, and then a
few bands of HMBT and ethanol appear and are gradually
enhanced as the potential becomes more positive, becoming
most distinct at
0.7 V, which is more positive than that
in neutral solution. This means that ethanol and HMBT co-
exist on the iron surface. At
0.5 V, the intensity of the
bands decreased again. As the electrostatic attraction should
cause stronger adsorption of MBT
on the iron surface at a
more positive potential, the decreased intensity of the HMBT
bands at
0.5 V is probably due to the generation of an
Fe3 O4 layer on the iron surface. The notable broad band
seen in the spectrum at 670 cm
1 [Fig. 4(f)] is characteristic
of Fe3 O4 .28 An interesting phenomenon is the occurrence
of Fe3 O4 bands accompanying complete disappearance of
ethanol bands, but the HMBT bands still exist although
they have been weakened. They might be considered as the
signals coming from a fresh Fe3 O4 film on the surface. This
needs further investigation as the SERS effect of an oxide has
not yet been reported.
In basic solution, HMBT was still adsorbed on the surface
via its exocyclic sulfur atom because the C2 S10 stretch band
showed a lower wavenumber by ca 10 cm
1 than that in
solution (from 607 to 597 cm
1 ) although the S–Fe band was
J. Raman Spectrosc. 2004; 35: 1016–1022
 Adsorption of benzimidazole and 2-mercaptobenzothiazole on iron 1021

Table 2. Vibrational wavenumbers (
/cm
1 ) of 2-mercaptobenzothiazole adsorbed on iron and in solutions of pH 3, neutral and
pH 13

Neutral pH 13 pH 3
Approximate description
of vibrationsa In solution On ironb In solution On ironc In solution On irond

SH stretch 2644 2648

CC stretch 1489 1489
CC stretch 1463 1463 1456 1457
NCS ring stretch 1398 1421 1389 1393
1336
CC stretch 1287 1278 1278 1277
NCS ring stretch 1247 1244 1243 1144
i.p. CH deformation 1133 1131 1129 1129 1032 1130
SCS antisymmetric stretch 1084 1087 1077 1075 1077 1079
CN deformation 1034 1040
CH deformation 1015 1014 1020 1017 1014 1012
CH deformation 933 934
o.p. CH deformation 864 852
C2 S3 stretch 702 711 706 704 706 707
NH deformation 682
C2 S10 stretch 610 601 607 597 608 606
Bz ring deformation 501 500 505 502 497 499
CH deformation 405
Bz ring deformation 395 395 389 386 393 391
CH deformation 384 377 375
CH deformation 304 303
CH deformation 293 293
Fe–S stretch 275 278
Fe–N stretch 198 200
a
Assignments taken from Refs 11 and 12.
b
The potential of the iron is
0.9 V.
c
The potential of the iron is
0.7 V.
d
The potential of the iron is
1.3 V.

not observed in Fig. 4. Features at 386 and 502 cm
1 [Fig. 4(e)]
are the benzene ring bending modes. The wavenumber of
these modes was essentially the same as that in solution,
indicating that the -electron of the benzene ring did not
bond significantly with the iron atom.21
Overall from Fig. 4, the relative intensities of the HMBT
bands coming from both solution and the surface do
not reveal a distinct difference, hence it seems that the
arrangement of the molecules on the iron is not as orderly as
that under neutral conditions.
From the above mentioned discussion, the molecules of
HMBT are electrostatically adsorbed mainly by exocyclic S
on the iron surface under the experimental conditions.
Figure 5 shows the Raman spectra of HMBT in an acidic
medium. The presence of an S–H vibration at 2644 cm
1 and
the absence of an N–H vibration in the region 600–700 cm
1
proves that HMBT exists in the thiol form. The potential
applied to the iron hardly affects the intensity of the HBMT
bands. It reveals, however, a strong band assigned to an
Fe–S stretching mode at 278 cm
1 [Fig. 5(b)] and shifted
to a higher wavenumber of 287 cm
1 as the potential is
changed from
1.3 to
0.7 V. A possible explanation for
the shift of the Fe–S stretch is that the more positive the
potential, the stronger is the bond between the exocyclic
sulfur atom and the surface; this is known as the Stark effect
in electrochemistry.29,30
The Fe–N band at 200 cm
1 demonstrates that the
nitrogen atom of HMBT also participates in chemical bonding
with iron atoms. Further, a slightly enhanced benzene
bending mode at 391 cm
1 , a C2 S3 stretch at 707 cm
1 and
a CH in-plane bending mode at 1130 cm
1 suggest a slight
increase in the amount of HMBT on the surface.
In the range 1200–1500 cm
1 , HMBT on the iron surface
shows several CC and NCS stretch modes regardless of the
pH of the solution, as can be seen in Fig. 6, which is generally
in agreement with the results from a silver surface7,11,13
except for a large blue shift in neutral and a red shift in
basic conditions of the 1398 cm
1 mode. The CC stretch at

Copyright  2004 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2004; 35: 1016–1022
1022 G. Wang et al.
Figure 6. Raman spectra in the range 1200–1500 cm
1 of
HMBT from neutral solution (a) and on the iron surface in
neutral (b), basic (c) and acidic media (d).
1489 cm
1 is enhanced only in neutral conditions and not
in the other conditions. Also, an unknown mode appears at
1336 cm
1 , which has not been reported before, from the iron
surface under neutral conditions.
CONCLUSIONS
Both BIMH and HMBT the region 200–1500 cm
1 show
enhanced and highly structured spectra when the iron is at
a potential of ca
0.7 to
0.9 V in a neutral medium. BIMH
was chemically adsorbed on the iron surface via its cyclic
N atom in a neutral medium. HMBT was adsorbed mainly
via exocyclic S and N atoms in acidic and neutral media. As
HMBT exists in the form MBT
in solution at pH 13, the main
interaction should be electrostatic attraction between MBT

ions and iron atoms. In addition, the Raman signal of HMBT
Copyright  2004 John Wiley & Sons, Ltd.
observed at
0.5 V in basic solution might come from the
oxide in the form of a fresh Fe3 O4 film on the iron surface.
Acknowledgements
We gratefully appreciate financial support by the Royal Society
(UK), the Science and Technique Committee of Shanghai and the
Shanghai Rare Society.
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