6288 J. Phys. Chem.

C 2007, 111, 6288-6295

Charge-Transfer Interaction of Poly(vinylpyrrolidone) with Platinum and Rhodium

Nanoparticles
Yuri Borodko,† Simon M. Humphrey,†,‡,| T. Don Tilley,†,‡ Heinz Frei,§ and
Gabor A. Somorjai*,†,‡
Chemical and Materials Sciences DiVisions, Lawrence Berkeley National Laboratory, 1 Cyclotron Road,
Berkeley, California 94720, Department of Chemistry, UniVersity of California, Berkeley, California 94720,
and Physical Biosciences DiVision, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley,
California 94720
ReceiVed: December 19, 2006; In Final Form: February 1, 2007

The vibrational spectra of platinum and rhodium nanoparticles (2.4-7 nm) capped with poly(vinylpyrrolidone)
(PVP) were investigated by deep UV-Raman and Fourier transform infrared (FTIR) spectroscopy. Raman
spectra of PVP/Pt and PVP/Rh showed selective enhancement of CdO, C-N, and CH2 vibrational modes of
the pyrrolidone ring as a result of donor-acceptor interactions between polymer functional groups and surface
metal atoms. This was observed in the UV-Raman spectra of PVP-capped metal nanoparticles by in-situ
measurements in both reduced and oxidized states. Charge-transfer interactions between the polymer donor
groups and surface Pt atoms in the first layer of the PVP/Pt system changed reversibly as a function of metal
oxidation state (Pt(II) and Pt(0)), induced by heating under a flow of H2 or O2. In contrast, the UV-Raman
spectra of PVP/Rh were not reversible upon heating at 150 °C in an atmosphere of O2, H2/N2, or N2; in this
case, fragments of thermal decomposition of PVP on Rh were detected. Furthermore, it was demonstrated
that UV-Raman spectroscopy (244 nm) is a highly sensitive tool to study the effect of surface oxide layers
on chemically enhanced surface-enhanced Raman spectroscopy (SERS). In the case of PVP/Al, a nonreducible
oxide layer of Al2O3 blocked the involvement of conducting electrons from making bonding interactions
with pyrrolidone rings.

Introduction
Poly(vinylpyrrolidone) (PVP) has been used extensively as
a macroligand for stabilizing metallic nanocrystals with different
shapes1 and as flexible membrane around metallic colloids. In
some instances, the PVP has been shown to influence the
selectivity of catalytic reactions.2 The application of PVP/Pt and
PVP/Rh nanoparticles in low-temperature catalytic reactions has
recently offered promising new opportunities to create tailored
catalytic systems. However, very little is known about the
structure and nature of the chemical interaction between PVP
and metallic nanoparticles at the molecular level. Several
experimental techniques have been used to explore the PVP/Pt
and PVP/Rh interfaces.3 Recently, we have shown that deep
UV-Raman spectroscopy can be advantageous for probing the
interaction between PVP and Pt nanoparticles because of
substantial intensity enhancement for certain vibrational modes
as a result of resonance Raman and surface chemical enhance-
ment effects.4 By combining Fourier transform infrared (FTIR)
and Raman methods, it is possible to differentiate between
vibrational modes arising from unbound pyrrolidone rings and
those with direct interactions with surface atoms of the metal
nanoparticles.
In this paper, we present results that demonstrate a correlation
between the extent of interaction of PVP donor groups with
* To whom correspondence should be addressed.
† Chemical and Materials Sciences Divisions, Lawrence Berkeley
National Laboratory.
‡ University of California.
§ Physical Biosciences Division, Lawrence Berkeley National Laboratory.
| Present address: University Chemical Laboratory, University of
Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K. and St. John’s
College, Cambridge CB2 1TP, U.K.
10.1021/jp068742n CCC: $37.00 © 2007 American Chemical Society
Published on Web 04/07/2007
the nanoparticle surface and the oxidation state of surface metal
atoms. In-situ UV-Raman spectroscopy (244 nm) has allowed
for a comparison between the behaviors of Pt and Rh systems,
indicating that the PVP-metal interaction is sensitive to the
surface electronic structure (oxidation state). Substantial dif-
ferences were observed in the characteristic bonding interactions
of PVP-capped Pt and Rh nanoparticles. This has been proven
by in-situ measurements of band intensities of PVP/Pt in both
reduced and oxidized states. The evolution of new bands in their
Raman spectra, observed upon subjecting the samples to various
redox gas treatments at elevated temperatures, offers information
regarding suitable pretreatment methods for application as
catalysts. It is also apparent from studies of PVP on Al foil
that chemically enhanced SERS is effectively blocked by a
native surface oxide dielectric layer.
Experimental Section
Synthesis of Shape-Controlled Platinum Nanocrystals by
Reduction in Ethylene Glycol. Platinum cubes (9.4 ( 0.6 nm,
80%) were synthesized by adding 0.5 mL of 2 × 10-3 M AgNO3
solution in ethylene glycol (EG) to refluxing EG, followed by
stepwise addition of poly(vinylpyrrolidone) and H2PtCl6‚6H2O
solutions in EG. The mixture was heated under reflux for an
additional 5 min, precipitated with acetone, and collected by
centrifugation. The supernatant was decanted, and samples were
redispersed into ethanol and again were precipitated twice before
finally being dispersed in ethanol or chloroform. A more detailed
description of the experimental procedure can be found else-
where.5
Synthesis of Shape-Controlled Rhodium Nanocrystals.
Rh-PVP seed particles were synthesized via reduction of ClRh-
Interaction of Poly(vinylpyrrolidone)
Figure 1. TEM images of (a) PVP stabilized cubic Pt nanoparticles,
(b) Rh nanoparticles with multipod structure, and (c) cuboctahedra
structure with corresponding size histograms (bar ) 50 nm).
(PPh3)3 precursor by B2H6 in benzene and subsequent ligand
exchange reactions.6 Seeded growth methods were used to
prepare larger Rh particles, as described in detail previously:6
Rh-PVP seeds in EG were stirred at 120 °C in the presence of
excess PVP, during the timed addition of desired amounts of
RhCl3 in EG solutions. Upon cooling, products were purified
by precipitation from hexane/isopropanol and were isolated by
centrifugation. Additional cycles of redispersion in EtOH and
precipitation with hexane were employed to remove excess
polymer.
Transmission Electron Microscopy (TEM) Measurement
of PVP/Pt and PVP/Rh. TEM analysis was carried out with a
model Tecnai 12 transmission electron microscope operated at
100 kV acceleration voltages. A diluted solution of the purified
sample was applied onto a 200-mesh Formvar/carbon-coated
Cu grid and was dried in air. A representative TEM image of
Pt-PVP 8.7 nm cubic platinum nanoparticles prepared in EG
is shown in Figure 1a. TEM images of Rh-PVP multipods and
Rh-PVP 6 nm cuboctahedra prepared in EG at 120 °C (bar )
50 nm) are shown in Figure 1b and 1c, respectively.
Spectroscopic Characterization. FTIR-DRIFT (diffuse
reflection infrared Fourier transform) spectra were measured on
a Nicolet Nexus-670 spectrophotometer with integrated diffuse
reflectance optics (Spectra-Tech Collector II). It was found that
improved spectra could be obtained from a thin layer of PVP/M
(M ) Pt, Rh) prepared by evaporation of chloroform or ethanol
solutions onto a reflective surface such as aluminum or gold
foil. Since the layer thickness can be adjusted to render the
sample partially IR transparent, we were able to optimize the
J. Phys. Chem. C, Vol. 111, No. 17, 2007 6289
Figure 2. Overview of the UV-Raman system: (A) principal optical
scheme; (B) XY-moving sample holder; (C) optical cell for in-situ study
in the temperature range of 25-200 °C. Legend: L ) lens, S ) sample,
M ) motor, W ) window, V ) valve, and H ) heater.
ratio of diffuse-to-specular reflectance and obtain spectra of
similar quality compared to those measured in transmission
mode. A temperature/vacuum chamber Spectra-Tech 0030-101
was used for in-situ FTIR measurements in H2/Ar (10% H2)
flow.
The deep-UV-Raman spectroscopy system is shown in
Figure 2A. A continuous wave (cw) intracavity doubled argon
ion laser operating at 244 nm was used as the excitation source.
A custom-designed (Omega Optical) UV long pass edge filter
effectively blocked plasma lines below 246 nm. A 37-mm focal
length fused silica lens allowed focusing of the laser on a ∼500
µm spot on the surface of the sample. Backscattered light was
collected with the same lens, was collimated, and was directed
to the entrance slit of a Spex 1877C triple spectrometer that
was optimized for performance in the deep-UV region. Some
spectra were taken with an additional band-pass filter in front
of the spectrometer to further reduce the intensity of elastically
scattered radiation. Spectra were recorded with a liquid N2-
cooled, UV-enhanced CCD camera. The instrument dispersion
is 2.1 cm-1/pixel; the typical resolution of 8-12 cm-1 was
controlled by the slit width of the dispersion stage of the triple
spectrometer.
Deep UV irradiation of PVP is known to induce intra- and
intermolecular cross-linking of the polymer chains.7 To eliminate
modification or decomposition of PVP/M samples under intense
UV irradiation, a custom-designed rotating sample holder with
variable speed in the range of 600-2000 rpm was used. This
apparatus was also equipped with a second motor for lateral
translation (240 rpm). In this manner, the laser was xy-rastered
over the entire sample, decreasing the UV exposure in a given
spot by 103 when compared with a static sample holder (Figure
2B). No detectable photodegradation of samples was observed
in this configuration over a period of 90 min. The measurements
of Raman spectra under in-situ conditions were performed in
detachable hermetically sealed flow cells, where samples were
heated in the temperature range 20-200 °C in a flow of H2/N2,
O2, or N2 (Figure 2C). A triple spectrometer Spex-1877C CCD
detector can detect simultaneously only the restricted spectral
region of about 1600 cm-1 under similar conditions. Thus, we
were unable to compare directly intensities of the PVP carbonyl
stretch, its first overtone, and C-H stretches. To allow for
correct representation of intensities, normalization of Raman
peak intensities for measurements performed on heated samples
in different atmospheres was achieved using the molecular
6290 J. Phys. Chem. C, Vol. 111, No. 17, 2007 Borodko et al.

Figure 3. UV-Raman spectra of pure PVP-55K in different aggregate

states: (A) powder; (B) layer on Al foil; (C) solution in H2O; (D) survey Figure 4. Comparison of UV-Raman spectra of (A) pure PVP and
spectrum of PVP/Al in the range of 100-3600 cm-1. (B) PVP/Pt in the region 1300-3550 cm-1.

SCHEME 1: Diagrammatic Representation of the

nitrogen line at 2331 cm-1 as the external standard. The
PVP/M (M ) Pt, Rh) System for a Nanoparticle of
concentration of N2 for independent measurements was held
Unspecified Shape
constant by purging the sample flow-cell with ultrahigh purity
N2 (99.999%, Airgas Corp.) before and after each spectrum was
recorded. The reference lines of gaseous molecular oxygen at
1557 cm-1 and nitrogen at 2331 cm-1 were used to normalize
Raman spectra (in air) recorded over limited ranges between
100 and 3800 cm-1 as is typical for spectroscopy with CCD
detectors.
To prepare samples for Raman studies, solutions of PVP/Pt
in chloroform and PVP/Rh in ethanol or dichloromethane were
evaporated onto 30-mm diameter Al foil substrates. Typical
collection times were 5-30 min using 3-5 mW of 244-nm
excitation energy. An oil-free Alcatel Drytel 34 turbopump
station was used for sample evacuation. GRAMS/AI software
from Thermo Galactic was used for processing UV-Raman and
FTIR-DRIFT spectra. adjoining spectra recorded by the CCD detector was achieved
by using the intensities of the N2 and O2 lines at 2331 and 1557
Results and Discussion
cm-1, respectively, thus allowing for quantitative comparison
Effect of Reduction and Oxidation on UV-Raman Spec- of intensities of CdO and C-H bands of pure PVP (Figure
tra of PVP/Pt. The Raman spectra of pure PVP in different 3D) and of PVP/Pt. The UV-Raman spectra of pure PVP and
aggregate states did not show substantial changes. Assignments PVP-capped Pt nanocrystals differ noticeably (Figure 4).
of Raman and FTIR spectra were presented in previous work.4 Steric considerations suggest that the number of pyrrolidone
As can be seen in Figure 3, traces A-D, the UV-Raman spectra rings interacting with the nanoparticle surface must be small in
of PVP are very similar whether in (A) powder form, (B) comparison with noninteracting rings (Scheme 1). However, the
deposited on Al-foil, or (C) dissolved in water. The position of selective enhancement of Raman intensities for vibrational
the carbonyl stretch of pure PVP varied in the region 1680- modes associated with chromophoric groups adsorbed on the
1652 cm-1 depending on the quantity of adsorbed water.8,9 metal surface is sufficiently large to result in an intense spectrum
Intensities of the CH2 bending vibration at 1440 cm-1 and C-H of the surface-coordinated groups. In the FTIR spectrum of PVP/
stretch at 2930 cm-1 are larger than the carbonyl stretch at 1660 Pt, there is no such distinction between the cross section for
cm-1 (Figure 3D). This is characteristic of normal (i.e., bonded and nonbonded carbonyl groups. In the Raman spectrum,
nonresonance enhanced) Raman spectra of pure PVP, as a dominant intense line appears at 1605 cm-1 with a shoulder
obtained previously by laser excitation at 244 nm,4 488 nm,8 at 1635 cm-1. The ratio of integral intensities I(CdO):I(C-H)
632.8 nm,10 and 1064 nm.9 Normalization of the signals from is now larger than for pure PVP. It is particularly remarkable
Interaction of Poly(vinylpyrrolidone)
SCHEME 2: Model for the PVP/Pt Interaction in
Reduced and Oxidized States
that for PVP/Pt the intensity of the first carbonyl CdO overtones
(at 3200 and 3280 cm-1) is comparable with intensities of the
fundamental modes. This is in agreement with the theoretical
prediction for adsorbed molecules on a metal surface that exhibit
a combination of resonance Raman and strong charge-transfer
interaction SERS. In such instances, the overtone intensity in
the Raman spectrum may be as strong as for the fundamental
modes.11 The number of bound amide groups is relatively small
and undetectable in our infrared experiments. The observation
of surface enhancement of some vibrational modes of PVP/Pt
is due to donation of an electron lone pair on the carbonyl group
into an unoccupied orbital of the platinum nanoparticle surface.
It was previously shown that on the surface of Pt nanoparticles
above 2 nm in size, only a monolayer of PtO was formed, which
is reducible by H2 in the range 50-100 °C.12 Pt nanocrystals
in an oxidized state (Pt(II)) have surface platinum ions with d8
low-spin configuration and therefore may act as acceptors of
lone pair electrons from carbonyl groups into vacant d-orbitals.
In contrast, surface platinum atoms in the reduced state (Pt(0))
will repel the lone pair electrons of a carbonyl group (Scheme
2). Thus, the interaction between PVP and Pt at an oxidized
surface is stronger than on reduced nanocrystals; this is reflected
by changes in the intensities of the Raman spectrum of adsorbed
PVP.
The spectra shown in Figure 5 indicate that consecutive
treatment of the same PVP/Pt sample exposed to flowing H2/
N2 and O2 induced visible changes of the integrated intensities
of Raman doublet lines at 1605 and 1635 cm-1. As can be seen
in Figure 5, heating a preoxidized sample of PVP/Pt (5a) in
flowing H2/N2 at 90 °C resulted in an intensity decrease of the
Figure 5. The effect of consecutive redox treatment of PVP/Pt on the
intensity of the carbonyl line: (a) initial sample; (b) reduction of initial
sample under flow of H2/N2 (5% H2) at 90 °C for 40 min; (c)
consecutive oxidation in air at 90 °C for 15 min.
J. Phys. Chem. C, Vol. 111, No. 17, 2007 6291
Figure 6. Effect of reduction of PVP/Pt on Raman intensities of the
C-H stretch and first CdO overtone: (a) initial (preoxidized) sample
of PVP/Pt; (b) after reduction in H2/N2 flow at 90 °C for 40 min.
TABLE 1: Intensities of Resonance Raman Bands of
PVP/Pt Attributed to Carbonyl-Stretching Vibrations after
Consecutive Redox Treatment in H2, O2, and N2
oxidation state integral intensity CdO consecutive treatments
1 ox 100 initial in air, 25 °C
2 red 65 flow H2/N2 (5% H2)
90 °C for 40 min
3 ox 110 air, 90 °C for 15 min
4 red 90 flow H2/N2 (5% H2)
130 °C for 20 min
5 ox 120 air, 90 °C for 50 min
6a neutral 100 flow N2
150 °C for 30 min
a
Initial sample of PVP/Pt (1) was heated in N2 flow.
CdO band (5b). However, after subsequent heating of the same
sample in air or pure O2, the carbonyl line intensity increased
again (Figure 5c). The intensities of the C-H stretch and Cd
O first overtone are also sensitive to redox treatment (Figure
6). The relative changes of resonance Raman line intensities of
PVP/Pt are summarized in Table 1. Heating PVP/Pt at 150 °C
in N2 did not affect the spectrum. Redox treatments were
reversible, although the intensity of Raman lines of both reduced
and oxidized samples gradually increased (with the exception
of the peak at 1605 cm-1, see below). This suggests that the
structure of the capping PVP becomes denser after high-
temperature treatment as a result of PVP cross-linking, thereby
increasing the number of contacts between adjacent pyrrolidone
rings at the Pt surface. It is of interest that the shape of the
carbonyl line has a doublet structure with components at 1605
cm-1 and 1635 cm-1: the origin of these lines may be related
to the existence of two different Pt surface sites that may result
in two types of PtrOdC bonds with different carbonyl
stretches. The lack of complete recovery of the 1605 cm-1 band
upon reoxidation indicates that this bonding mode is only
partially regained. However, an increase of the intensity at 1605
cm-1 was induced by sonication of the PVP/Pt sample in ethanol
for 15 min at 150 W power (Figure 7). We can only speculate
on the reason for the intensity increase of the peak at 1605 cm-1
by this procedure, which includes the possibility of removal of
residual surface species from the redox-treated Pt nanoparticles.
Effect of Reduction and Oxidation on UV-Raman Spec-
tra of PVP/Rh. The UV-Raman spectrum of PVP/Rh exhibits
strong lines at 1590 and 1645 cm-1, while the FTIR spectrum
shows only a single broad band centered at 1684 cm-1 (Figure
8). No noticeable differences were detected in the Raman spectra
for Rh nanoparticles of varying shapes (cuboctahedra or
6292 J. Phys. Chem. C, Vol. 111, No. 17, 2007
Figure 7. UV-Raman spectra of (a) initial PVP/Pt (redispersed in
EtOH); (b) the same sample after sonication in EtOH (150 W, 15 min).
Figure 8. (a) FTIR and (b) UV-Raman spectra of the same sample
of PVP/Rh. FTIR spectrum of PVP/Rh is identical to the spectrum of
pure PVP while the UV-Raman of PVP/Rh exhibits new lines,
characteristic of chemically enhanced SERS.
multipods, see Figure 1b, 1c). The Raman spectrum of PVP/
Rh closely resembles the chemically enhanced SERS spectrum
of PVP/Pt, which has peaks at 1605 and 1635 cm-1. For PVP/
Rh, the ratio of integrated intensities I(CdO):I(C-H) > 1,
which was also observed for PVP/Pt. This indicates resonance
and chemically enhanced SERS for pyrrolidone rings adsorbed
on the Rh surface. The FTIR spectra of PVP/Rh and pure PVP
are essentially identical.
PVP/Rh samples were dispersed in ethanol or in dichlo-
romethane. The solubility of PVP/Rh is high in both solvents.
It was of interest to study the differences between the Raman
spectra of samples prepared by evaporation from polar coor-
dinating or noncoordinating solvents. The resulting UV-Raman
spectra are shown in Figure 9. Comparison of the peak intensity
ratios for the characteristic bands at 1590 cm-1 and 1430 cm-1
and of the ratio of the CdO overtone and adjacent C-H
stretching bands for the PVP/Rh samples prepared from EtOH
and CH2Cl2 reveals significantly more intense bands for the
latter. This observation suggests that a greater number of
interactions occur between the pyrrolidone carbonyl groups and
the Rh surface when CH2Cl2 is used to prepare samples. This
may occur because of the formation of a thicker surface layer
of RhOx in ethanol, which behaves as an insulating barrier that
restricts the overall number of interactions of the type RhrOd
C. A layer of alcohol-derived oxidation products (aldehydes,
for example) may also be present on the Rh surface.
Heating of PVP/Rh in flowing H2 induced changes in the
shape and intensity of the amide band in contrast to the observed
behavior of PVP/Pt. Increasing the temperature from 25 °C to
Borodko et al.
Figure 9. SERS UV-Raman spectra of PVP/Rh redispersed in (a)
EtOH or (b) CH2Cl2. (A) The ratio of the intensity of the carbonyl
stretch at 1590 cm-1 to δ(CH2) at 1430 cm-1 indicates that the number
of interactions between amide groups and Rh in the sample prepared
in CH2Cl2 is higher than in the sample prepared in EtOH. (B)
Enhancement of the first CdO overtone for PVP/Rh sample dispersed
in CH2Cl2 relative to EtOH.
140 °C in H2/N2 flow resulted in enhanced integrated intensity
of the amide stretch at 1645 cm-1 (Figure 10A). In the Pt case,
heating of the PVP/Pt sample in H2 led to an overall decrease
in intensity of the amide stretch because of loss of PtrOdC
type interactions (Figure 5a). Subsequent treatment of the PVP/
Rh sample in O2 at 150 °C for 40 min resulted in no pronounced
change in the spectrum (Figure 10B). These results show that
interactions between Rh and PVP do not show the same response
to H2 or O2 treatment in the temperature range 25-150 °C
compared to PVP/Pt. Heating of the as-synthesized sample of
PVP/Rh in air at 150 °C for 25 min also resulted in a net
intensity increase of the band at 1645 cm-1 but did not influence
the component at 1590 cm-1 (Figure 11, panel 1). When PVP/
Rh samples prepared from ethanol solution were heated in a
flow of N2 at 150 °C for 30 min, a marked increase of intensity
for both the carbonyl stretch at 1645 cm-1 and the first overtone
at 3275 cm-1 was observed (Figure 12B). In contrast, heating
PVP/Pt in an atmosphere of N2 at 150 °C did not induce any
intensity changes in the Raman spectrum. The in-situ UV-
Raman studies of PVP/Rh treated in flowing H2, O2, and N2 all
show increased intensities of the CdO stretch at 1645 cm-1.
Moreover, this change is not reversible upon consecutive
hydrogen and oxygen treatment cycles in the temperature range
25-150 °C. Previously, it was shown by X-ray photoelectron
spectrometry (XPS) measurements that hydrogen treatment of
naked Rh nanoparticles in the temperature range 25-150 °C
reversibly altered the electronic structure of the surface layer
and thickness of surface RhOx, where Rh(III) is gradually
reduced toward Rh(0).13 If reduction of Rh ions with coordinated
amide groups were to take place, marked changes in the position
or intensity of amide-stretching bands would be easily detected.
Interaction of Poly(vinylpyrrolidone)
Figure 10. (A) UV-Raman spectra of PVP/Rh heated in flowing H2/
N2 (5%H2): (a) initial sample at 30 C; (b) the same sample after heating
at 90 °C for 15 min; (c) heating at 140 °C for 20 min. The intensity of
the band at 1645 cm-1 increases, whereas the line intensity at 1590
cm-1 remains approximately constant. (B) (d) Subsequent oxidation
of the sample in O2 at 150 °C for 40 min did not induce any pronounced
changes in the resulting spectrum.
The lack of any such reversible changes in the spectra of H2 or
O2-treated PVP/Rh may be interpreted in terms of higher
stability of surface-coordinated compounds in PVP/Rh compared
to PVP/Pt in the temperature range 25-150 °C. Furthermore,
we assume that the increase intensity of the band at 1645 cm-1
caused by heating of PVP/Rh in H2, O2, and N2 is a result of
thermal degradation of PVP, accompanied by the release of
pyrrolidone moieties. Most probably, pyrrolidone rings that bind
in a bridging, side-on fashion are more strongly adsorbed on
the nanoparticle surface than units which are only singly
coordinated. Hence, the line at 1590 cm-1 may be assigned to
a carbonyl-stretching vibration of capping PVP while the line
at 1645 cm-1 may be attributed to the carbonyl stretch of
individual pyrrolidone rings generated by thermal decomposi-
tion. The release of side-on pyrrolidone rings in the course of
thermal degradation of pure PVP has been previously studied.14
Above the glass-transition temperature of PVP (85 °C), thermal
degradation proceeds through the release of pyrrolidone rings
and the formation of polyenic sequences (Scheme 3).
Recently, it was demonstrated that thermal degradation of
PVP/Pt occurs at a temperature near 100 °C, far below that of
pure PVP.4 It is believed that released pyrrolidone moieties near
the Pt and Rh surface are chemisorbed as bridging ligands. Using
a classical coordination chemistry model15 for metallic nanoc-
rystals capped by monodentate and bridging (bidentate) ligands,
an increase in temperature is expected to result in gradual
saturation of the accessible Rh surface sites by bridging ligands
(Figure 12). In support of this interpretation, it is known that
R-pyrrolidone as a bridging ligand stabilizes many polynuclear
platinum compounds featuring Pt2+ or Pt3+.16 Some Rh tetra-
J. Phys. Chem. C, Vol. 111, No. 17, 2007 6293
Figure 11. (A) SERS UV-Raman spectra of PVP/Rh: (a) Initial
sample at room temperature in air and (b) after heating in air at 150
°C for 25 min. (B) (a) Initial sample at room temperature in N2
atmosphere and (b) the same sample after heating in N2 at 150 °C for
30 min with expansion of 2500-3500 cm-1 region in (c).
Figure 12. (A) Illustration of partial PVP decomposition, resulting in
pyrrolidone monomers at the nanoparticle surface. (B) The two types
of pyrrolidone rings bonding to metal nanoparticles: (I) as a mono-
dentate ligand; (II) as a bridging ligand (monomeric pyrrolidone).
nuclear compounds with bridging ligands have also been isolated
and structurally characterized.17 Pyrrolidone units can form
strong coordinating bonds via amine-N and carbonyl-O donors,
which bridge adjacent metal atoms on the nanoparticle surface,
as observed in “platinum blue”16 and “rhodium blue”17 coor-
dination compounds. As shown by X-ray crystallographic
analysis between bridging amidate ligands, the R-pyrrolidinonate
is structurally best suited to bridging two adjacent Pt atoms.18
UV-Raman of PVP/Al and the Effect of Conductive
Electrons on Chemically Enhanced SERS. To test the
influence of the dielectric barrier on UV-Raman spectroscopy
of PVP adsorbed onto metal surfaces, layers of PVP (55 kMW)
of varying thickness were deposited on an aluminum foil with
an intrinsic surface layer of Al2O3. As can be seen in Figure
13, the spectrum of thicker PVP layers is quite regular. However,
the spectra of thin layers show a new intense line at 1600 cm-1
6294 J. Phys. Chem. C, Vol. 111, No. 17, 2007
SCHEME 3: Proposed Mechanism for Degradation of
PVP Polymer to Yield Bridging Pyrrolidone Monomer
Moieties and Unsaturated Polymer Backbone Groups
which may be assigned to a shifted carbonyl stretch because of
the presence of the amide functional group (in addition to the
expected nonbound carbonyl stretch at 1664 cm-1). A charge-
transfer interaction between a moderate electron acceptor such
as Al(III) and an electron lone pair donor such as a carbonyl
group results in a red shift in the CdO stretch to 1600 cm-1.
The ratio of peak intensities of the CH2 bending and carbonyl-
stretching modes observed is typical for “normal” Raman
(Figure 13A), and no intensity increase was observed for the
first overtone of CdO (Figure 13B). This provides evidence
that the resonance Raman spectrum of PVP/Al was detected
but without influence of chemically enhanced SERS. The FTIR
spectrum of PVP/Al does not have any new additional bands
when compared to pure PVP. In air, unprotected aluminum foil
has a protective, nonreducible Al2O3 surface layer with an
Figure 13. UV-Raman spectra of PVP layers with different thickness
deposited on Al foil. The thickness of PVP layers decreases from i to
iii. The ratio of PVP thickness for samples i and iii is about 102. For
the Raman spectra of a thin PVP layer on Al foil, a new red-shifted
line was observed at 1600 cm-1 (A) but no visible changes were
detected in the C-H stretch region (B).
Borodko et al.
TABLE 2: Carbonyl Stretch Frequencies (cm-1) of Pure
PVP, PVP/Pt, PVP/Rh, and PVP/Al
monodentate bridging free
PVP 1664
PVP/Pt 1605 1635 1664
PVP/Rh 1590 1645 1664
PVP/Al 1600 1664
intrinsic thickness of approximately 2.5 nm.19 This underlines
the high sensitivity of UV-Raman spectroscopy in probing the
nature of the chemical bond between an amide group chemi-
sorbed to Pt or Rh nanoparticles on Al foil. The number and
position of carbonyl lines depends on the relative strength of
bonding and the type of interaction with the metal surface, singly
bonded or bridging. The carbonyl stretch frequencies are
summarized in Table 2.
An essential feature is the apparent influence of conductive
electrons on the intensity increase that is observed for PVP
Raman lines associated with chromophoric groups adsorbed on
the metal surface. In the case of PVP/Pt and PVP/Rh, UV-
Raman spectroscopy has detected selective enhancement of line
intensities for amide vibrations that may be attributed to both
the resonance Raman effect and SERS-CT (charge-transfer)
enhancement. A SERS chemical enhancement is due to electron
charge transfer between an amide group and the metal surface
atoms, as well as involvement of metallic electrons in the
MrOdC bond. This gives rise to polarizability that is associ-
ated with the CdO bond. However, in the case of PVP adsorbed
on Al foil with a native-insulating layer of Al2O3 (which acts
as a barrier for participation of metallic electrons), only the
normal resonance Raman effect was observed. Figure 14A
schematically depicts three studied systems with monodentate
structure: (I) PVP/Pt with a monolayer of PtO, which may be
easy reduced; (II) PVP/Rh with a thicker RhOx layer that may
also be reduced; and (III) PVP/Al with nonreducible oxide,
which completely screens interactions between adsorbed amide
groups of PVP and conductive electrons of aluminum. The UV-
Raman spectrum of PVP adsorbed on Pt and Rh nanoparticles
extended the number of SERS systems in which the contribu-
tions of electromagnetic enhancement is negligible.20 Figure 14,
panel B (reproduced from a scheme by Campion and Kamb-
hampati)21 emphasizes the role of conductive electrons in
chemically enhanced Raman lines attributed to the chromophoric
group adsorbed on a metallic surface. For PVP/Pt and PVP/
Figure 14. Illustrated effect of the dielectric barrier on CT-SERS
spectra of PVP adsorbed on Pt, Rh, and Al surfaces. (A) Schematic
picture of PVP/Pt, PVP/Rh, and PVP/Al interface structures with oxide
layers. (B) Energy-level diagram for a molecule adsorbed on metal
surface and possible charge-transfer excitation, showing involvement
of conductive electrons in resonance Raman.21
Interaction of Poly(vinylpyrrolidone)
Rh, excitation at a wavelength of 244 nm induces intermolecular
processes, since both channels a, b, and c are involved in UV
excitation from the electronic background state to the exited
state. In the case of the PVP/Al system, the b, c channel is
blocked by the insulating nonreducible layer of alumina.
Consequently, resonance excitation is exclusively intramolecular.
Conclusion
We have shown that UV-Raman (244 nm) spectroscopy is
useful for monitoring the interaction between the first layer of
the PVP capping agent and Pt and Rh nanoparticle surfaces
because of a chemically enhanced SERS effect. The in-situ study
of PVP/Pt with consecutive heating in H2 and O2 showed
reversible changes in the intensities of carbonyl-stretching lines,
indicating reversible changes to the strength of the charge-
transfer interaction due to the >CdO-Pt mode. In effect, the
PVP polymer breathes around the metal nanoparticle, as a
function of the oxidation state of surface metal atoms. In
comparison, the PVP-Rh interaction appears to be stronger than
observed for Pt; redox treatment of PVP/Pt and PVP/Rh samples
was found to induce not only a change in the surface electronic
state but also to promote thermal cross-linking and degradation
of PVP, catalyzed by the metal nanoparticles. This results in
release of pyrrolidone rings from the aliphatic polymer back-
bone. Pyrrolidone fragments can then strongly adsorb on the
metal surface as bridging ligands. This polymer degradation
pathway may have direct consequences on the relative catalytic
ability of PVP/M materials, as surface sites are potentially
blocked from reaction. This work demonstrates that deep UV-
Raman spectroscopy is a highly sensitive tool to study the
influence of surface oxide layers on chemically enhanced SERS.
Acknowledgment. This work was supported by the Director,
Office of Science, Office of Basic Energy Sciences, Division
of Chemical Sciences, Geological and Biosciences of the U.S.
Department of Energy under Contract No. DE-AC02-05CH11231.
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