Langmuir 2003, 19, 505-508 505

Optical and Photochemical Properties of Sodium

Dodecylbenzenesulfonate (DBS)-Capped TiO2
Nanoparticles Dispersed in Nonaqueous Solvents
G. Ramakrishna and Hirendra N. Ghosh*
Radiation Chemistry & Chemical Dynamics Division, Bhabha Atomic Research Center,
Trombay, Mumbai 400 085, India
Received July 17, 2002. In Final Form: December 13, 2002

TiO2 nanoparticles capped with sodium dodecylbenzenesulfonate (DBS) have been synthesized so that
they can be dispersed in many organic and nonaqueous solvents. It has been found that DBS-capped TiO2
nanoparticles have a significant red shift of the optical absorption band edge and clear photoluminescence
at room temperature in contrast to that of bare TiO2 nanoparticles. The results obtained indicate that the
surface structure, that is, the capping group and the defect states, plays an important role in the electronic
states of TiO2 nanoparticles. The recombination dynamics of the photoexcited charge carriers (electron and
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hole pairs) of DBS-capped TiO2 as studied by picosecond transient absorption spectroscopy is found to be
much slower as compared to that of bare TiO2 nanoparticles as reported earlier.
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Introduction Photoelectrochemical solar cells based on dye-sensitized

Semiconductor nanoparticles have attracted significant
interest in the past 15 years due to their potential
applications in solar energy conversion, nonlinear optics,
and heterogeneous photocatalysis.1 Surface modification
of semiconductor nanoparticles changes their optical,
chemical, and photocatalytic properties significantly.1c
Surface modification of nanoparticles lead to the following
effects: (i) it may enhance their excitonic and defect
emission by blocking nonradiative electron/hole (e-/h+)
recombination at the defect sites (traps) on the surface of
the semiconductor nanoparticles;2 (ii) it may enhance the
photostability of semiconductor nanoparticles;2 (iii) it may
create new traps on the surface of the nanoparticles,
leading to the appearance of new emission bands;3 (iv) it
may enhance the selectivity and efficiency of light-induced
reactions occurring on the surface of semiconductor
nanoparticles.1c,4
Excitation of TiO2 with light energy greater than its
band gap (3.2 eV) generates electron/hole (e-/h+) pairs
that can be exploited in various processes at the particle
interface. Photogenerated carriers migrate to the particle
surface and participate in reduction and oxidation pro-
cesses at the surface. The lifetime of charged pairs is very
short, and they very quickly go to the trapped state. Only
very fast reactions with adsorbed species lead to efficient
charge separation. Higher reaction efficiencies can be
obtained if the lifetime of charge carriers is more. Mod-
ifying the particle surface by adsorption of one or more
monolayers of adsorbate might block the surface states
and create new surface states, which can significantly
change the chemistry occurring at the particle surface. In
this process the separation distance of the trapped charges
can be increased and thus both redox and kinetic properties
of TiO2 can be enhanced.
* Corresponding author. E-mail: hnghosh@magnum.barc.ernet.in.
(1) (a) Oregan, B.; Gratzel, M. Nature 1991, 353, 737. (b) Henglein,
A. Chem. Rev. 1989, 89, 1861. (c) Bawendi, M. G.; Steigerwald, M. L.;
Brus, L. E. Annu. Rev. Phys. Chem. 1990, 41, 477. (c) Kamat, P. V.
Chem. Rev. 1993, 93, 267. (d) Alivisatos, A. P. J. Phys. Chem. 1996, 100,
13226. (e) Fox, M. A. Top. Curr. Chem. 1987, 72, 142.
(2) Spanhel, L.; Haase, M.; Weller, H.; Henglein, A. J. Am. Chem.
Soc. 1987, 109, 5649.
(3) Spanhel, L.; Weller, H.; Fojtik, A.; Henglein. Ber. Bunsen-Ges.
Phys. Chem. 1987, 91, 88.
(4) Fox, M. A.; Dulay, M. T. Chem. Rev. 1993, 93, 341.
TiO2 films have received much attention in recent years
because of their potential applications as a cost-effective
alternative to silicon-based cells.1a Since the report by
Gratzel’s group that solar cells based on Ru(dcbpy)2(NCS)2
[dcbpy ) (4,4′-dicarboxy-2,2′-bipyridine)] (or Ru N3)-
sensitized nanocrystalline TiO2 thin films can achieve a
solar to electric power conversion efficiency of about 10%,1a
electron injection and recombination properties of dye-
sensitized semiconductors have been studied by us5 and
many groups.6 It is necessary to establish conditions of
both fast electron injection and slow recombination for an
efficient solar energy conversion. However, the detailed
mechanisms, the nature and the rate of electron injection
into the semiconductor, and factors determining the rate
of back electron transfer are not well understood. Inter-
facial electron-transfer kinetics for TiO2 nanoparticles has
been monitored mostly in aqueous medium5,6a,d and in
thin films.6b,c,e Only a few examples of electron-transfer
processes in ethanol7 and acetonitrile7 medium for dye-
sensitized TiO2 nanoparticles are reported in the litera-
ture. The effect of solvents and solvent polarity on electron-
transfer dynamics in dye-sensitized TiO2 nanoparticles
has not been reported in the literature. To explore the
above said effects, there is a need to synthesize TiO2
nanoparticles, which can be dispersed in many organic
solvents.
In the present investigation we have synthesized and
studied the photophysical properties of TiO2 nanoparticles
capped with sodium dodecylbenzenesulfonate (DBS) (Chart
1) through a phase-transfer mechanism. DBS-capped TiO2
nanoparticles can be dissolved in many organic or non-
aqueous solvents such as dimethylformamide (DMF),
(5) (a) Ghosh, H. N. J. Phys. Chem. B 1999, 103, 10382. (b)
Ramakrishna, G.; Ghosh, H. N. J. Phys. Chem. B 2001, 105, 7000. (c)
Ramakrishna, G.; Ghosh, H. N.; Singh, A. K.; Palit, D. K.; Mittal, J. P.
J. Phys. Chem. B 2001, 105, 12786. (d) Ramakrishna, G.; Ghosh, H. N.
J. Phys. Chem. A 2002, 106, 2545.
(6) (a) Ghosh, H. N.; Asbury, J. B.; Lian, T. J. Phys. Chem. B 1998,
102, 6482. (b) Asbury, J. B.; Hao, E.; Wang, Y. Q.; Ghosh, H. N.; Lian,
T. J. Phys. Chem. B 2001, 105, 4545. (c) Benko, G.; Hilgendroff, M.;
Yartsev, A. P.; Sundstrom, V. J. Phys. Chem. B 2001, 105, 967. (d)
Dang, X.; Hupp, J. T. J. Am. Chem. Soc. 1999, 121, 8399. (e) Hannapel,
T.; Burfeindt, B.; Storck, W.; Willig, F. J. Phys. Chem. B 1997, 101,
6799.
(7) Kamat, P. V.; Fox, M. A. Chem. Phys. Lett. 1983, 102, 379.

10.1021/la026252q CCC: $25.00 © 2003 American Chemical Society

Published on Web 01/08/2003
506 Langmuir, Vol. 19, No. 3, 2003
Chart 1. Schematic Diagram of Sodium
Dodecylbenzenesulfonate (DBS)-Capped TiO2
Nanoparticles
dimethyl sulfoxide (DMSO), cyclohexane, benzene, and
many other polar and nonpolar solvents. Band-edge and
trap state emissions are very common for direct band-gap
semiconductors8 like CdS, GaAs, and ZnO. But, for indirect
semiconductors8 like TiO2 and GaP, these types of emission
are very difficult to observe. Emission from specially
synthesized nanosized TiO2 particles (d ) ∼3 nm) has
been observed by Clause et al.9 Emission from widely used
anatase TiO2 nanoparticles in solution phase is not
reported in the literature except the one reported by us,10
where trap state emission from TiO2 nanoparticles in
microemulsion solutions has been observed. In the present
study we have observed trap state emission from DBS-
capped TiO2 nanoparticles on band-gap excitation in many
solvents. We have also carried out picosecond time-
resolved absorption studies for the capped semiconductor
particles to elucidate the charge carrier dynamics within
the particles. We have observed that charge carrier
recombination dynamics is much slower for DBS-capped
TiO2 nanoparticles compared to widely used uncapped
TiO2 nanoparticles, as reported earlier.11-14
Experimental Section
(a) Materials. Titanium(IV) tetraisopropoxide {Ti[OCH-
(CH3)2]4} (Aldrich, 97%) and isopropyl alcohol (Aldich) were
purified by distillation. Sodium dodecylbenzenesulfonate (DBS)
was obtained from Aldrich. Cyclohexane, methylcyclohexane
(MCX), chloroform (CHCl3), N,N′-dimethylformamide (DMF),
dimethyl sulfoxide (DMSO), and benzene were obtained from
Spectrochem India Ltd. and were used without further purifica-
tion.
(b) Nanoparticle Preparation. We have synthesized DBS-
capped TiO2 nanoparticles, which can be dissolved in many
nonaqueous organic solvents in the following way. To 500 mL of
freshly prepared TiO2 colloids in water synthesized as reported
earlier5,15 was added 250 mL of toluene in a round-bottom flask.
The resulting mixture was stirred slowly for 15-20 min. To the
(8) Pankove, J. I. Optical Processes in Semiconductors; Dover
Publications: New York, 1971.
(9) Liu, Y.; Claus, R. O. J. Am. Chem. Soc. 1997, 119, 5273.
(10) Ghosh, H. N.; Adhikari, S. Langmuir 2001, 17, 4129.
(11) Serpone, N.; Lawless, D.; Khairutdinov, R.; Pelizzetti, E. J. Phys.
Chem. 1995, 99, 16655.
(12) Rothenberger, G.; Moser, J.; Gratzel, M.; Serpone, N.; Sharma,
D. K. J. Am. Chem. Soc. 1987, 109, 5649.
(13) Rothenberger, G.; Moser, J.; Gratzel, M.; Serpone, N.; Sharma,
D. K. J. Am. Chem. Soc. 1985, 107, 8054.
(14) Furube, A.; Asahi, T.; Masuhara, H.; Yamashita, H.; Anpo, M.
J. Phys. Chem. B 1999, 103, 3120.
Letters
Figure 1. Particle size distribution histogram of TiO2 nano-
particles: (a) anatase TiO2 nanoparticles in water; (b) DBS-
capped TiO2 nanoparticles in DMF.
stirred solution was added 100 mL of 0.2 M DBS (C12H25C6H4-
SO3Na, sodium dodecylbenzenesulfonate), and the final mixture
was stirred slowly for 3 h. DBS can be dissolved only in water,
because of its ionic nature. As the surface of the TiO2 nanoparticles
is positively charged, DBS molecules can easily bind through the
sulfonic group (SO3-) with the nanoparticles. The newly capped
TiO2 nanoparticles look like reverse micelles (Chart 1) and can
be dissolved in organic solvent. In this situation TiO2 nanopar-
ticles migrate from water to organic phase (toluene). Now with
the help of a separating funnel the organic phase was separated
out. At this stage the organic phase looked a little cloudy. The
organic phase was dried in CaCl2 and transformed to an optically
clear solution. The organic phase was then refluxed for 2 h, and
the solvent was taken out with the help of a rotary evaporator
in an N2 atmosphere. Dry TiO2 particles capped by DBS, which
were left in the flask, can be dissolved in many nonaqueous
solvents to get a colloidal solution in that particular solvent.
(c) Particle Size Measurement. Dynamic light scattering
experiments were performed on a DynaPro-MS800 instrument
(Protein Solutions Inc., VA) which monitors the scattered light
at 90°. At least 20 measurements, each of 10 s duration, were
collected. Experimental solutions were filtered through 0.02 mM
filters (Whatman Anodisc 13, Cat. No. 6809-7003). Extreme care
was taken to reduce the contamination of samples by dust.
“Regularization” software provided by the manufacturer was used
in analyzing the results for obtaining the distribution of the
hydrodynamic radius of the particles in the solution.
(d) Picosecond Visible Spectrometer. Picosecond laser
flash photolysis experiments were carried out using a pump-
probe spectrometer, described elsewhere.16 Briefly, the third
harmonic output (532 nm, 5 mJ, 35 ps) of an active-passive
mode locked Nd:YAG laser (Continuum, USA, model 501-C-10)
was used for the excitation of the samples.
Results and Discussion
Figure 1 shows the particle size distribution histogram
for naked and DBS-capped TiO2 nanoparticles. It is seen
from the histogram that the radius of the bare TiO2 is ∼3
nm and that of DBS-capped TiO2 is ∼5.5 nm. So the particle
diameters are calculated to be ∼6 nm for the bare TiO2
and ∼11 nm for DBS-capped TiO2. For the measurements
in a DLS instrument, aqueous solution was used for bare
TiO2 nanoparticles and DMF was used for DBS-capped
TiO2 nanoparticles. It was observed that on capping the
particles, the size became double but still the capped
particles could be dispersed clearly in many organic or
nonaqueous solvents to carry out photophysical and
photochemical experiments.
DBS-capped TiO2 nanoparticles would be readily dis-
persed into many organic solvents due their surface
(15) Bahnemann, D.; Henglein, A.; Lilie, J.; Spanhel, L. J. Phys.
Chem. 1984, 88, 709.
(16) Ghosh, H. N.; Pal, H.; Sapre, A. V.; Mittal, J. P. J. Am. Chem.
Soc. 1993, 115, 11722.
Letters
Figure 2. Excitation (curve c) and emission (curve d) spectra
of DBS-capped TiO2 nanoparticles in DMF (φf ) 0.002). [Inset:
optical absorption spectra of anatase TiO2 nanoparticles in water
(a) and specially synthesized TiO2 nanoparticles in DMF (b);
[TiO2] ) 0.10 gm/L.]
modification. UV-vis spectroscopy (model: Shimadzu
160A spectrophotometer) is used to characterize the optical
absorption spectra of DBS-capped TiO2 nanoparticles in
DMF, as shown in Figure 2b (inset). UV-vis spectra of
uncapped TiO2 nanoparticles in water are also shown in
Figure 2a (inset). It has been observed from Figure 2 (inset)
that the optical absorption spectra of DBS-capped particles
are red shifted. Absorption at longer wavelengths, which
is called the absorption red shift, was also observed by
Zou et al.17 with ultrafine particles (UFPs) coated with a
surface dipole layer. The authors attributed the absorption
red shift to a dipole layer that induced an attractive
potential to electrons inside the UFP and led to reduction
of the band gap of the UFP. According to the results
obtained from the steady-state absorption, FTIR, and
particle size measurements in the present investigation,
the long wavelength can be attributed to the change in
the surface structure of the nanoparticles. Once a DBS
molecule is capped on TiO2 nanoparticles (Chart 1), an
important physicochemical process can occur. The negative
hydrophilic radical of DBS (sulfonate) binds chemically
to the surface of TiO2. These chemically bound molecules
on the TiO2 surface can form intraband surface states,18
which can also lead to the long wavelength absorption in
TiO2 nanoparticles. Recently Rajh et al.19,20 also have
reported a new route for surface modification of nano-
crystalline TiO2 particles which improves the optical
response in the visible region. The approach involves direct
electron transfer from the modifiers into the conduction
band of the TiO2 nanoparticles. Chelation of surface Ti
atoms with the electron donating bidentate ligands in
these systems changes the electronic properties of nano-
particles. They have observed that binding of surface
modifiers was exclusively characteristic of small particle
colloids and was stabilized by ligand induced surface
restructuring of the nanoparticle surface.
Emission from indirect band-gap semiconductors8 like
TiO2 and GaP is difficult to observe. Except for a few
examples such as photo- and electroluminescence spectra
were detected by Nakato et al.21 from n-TiO2 and transition
metal-doped n-TiO2 on the electrode surface. In situ
(17) Zou, B.; Xiao, L.; Li, T.; Zhao, J.; Lai, Z.; Gu, S. Appl. Phys. Lett.
1991, 59 (15), 1826.
(18) Salvador, P.; Gutierrez, C. J. Phys. Chem. 1984, 88, 3696.
(19) Rajh, T.; Nedeljkovic, J. M.; Chen, L. X.; Poluektov, O.;
Thurnauer, M. C. J. Phys. Chem. B 1999, 103, 3515.
(20) Rajh, T.; Poluektov, O.; Dubinski, A. A.; Wiederrecht, G.;
Thurnauer, M. C.; Trifunac, A. D. Chem. Phys. Lett. 2001, 344, 31.
(21) Nakato, Y.; Tsumura, A.; Tsubomura, H. Chem. Phys. Lett. 1982,
85, 387.
Langmuir, Vol. 19, No. 3, 2003 507
photoluminescence of commercially available TiO2 par-
ticles at 77 K was reported by Anpo et al.22 Emission from
bare colloidal anatase TiO2 nanoparticles was also ob-
served by Serpone et al.23 in the visible region. In the
present investigation the luminescence spectra of DBS-
capped TiO2 nanoparticles are shown in Figure 2. The
excitation spectrum of the emission at 460 nm presented
in Figure 2c exhibits a peak at 390 nm at room temper-
ature. This peak coincides well with the absorption band
edge at 390 nm in the steady-state absorption spectra of
TiO2 nanoparticles in Figure 2 (inset). We have recorded
excitation spectra with changing concentration of the TiO2,
and every time we have observed the similar spectra. Even
at very low concentration of TiO2 nanoparticles, we have
observed the excitation spectrum centered around 390
nm. The excitation spectra also matched well with that
reported by Zhu et al.24 for TiO2 ultrafine particles. It is
interesting to see that the excitation spectrum does not
match with the optical absorption spectrum of TiO2
nanoparticles. In molecular systems the excitation and
absorption spectra generally match well. In the present
investigation we have observed a peak in the excitation
spectra at the band edge of the optical absorption spectra
of the nanoparticles. In semiconductor nanoparticles, when
the excitation energy is larger than the band gap, the
photoexcited electron goes to the higher energy states in
the conduction band and then very quickly relaxes to the
conduction band edge and at the same time the recom-
bination reaction for the hot charge carriers will also take
place through radiative and nonradiative pathways.8 So
the probability of the electrons going to the trap states
will be less, as the excitation energy is more. The intensity
of the trap state emission will be less, as the excited photon
energy is high. As we are monitoring the trap state
emission, the peak of the excitation spectrum comes at
the band edge in the absorption spectrum. This kind of
shape of excitation spectrum for TiO2 nanoparticles is also
reported in the literature.24,25 Figure 2d shows the trap-
state emission DBS-capped TiO2 nanoparticles in DMF
solvent with a peak at 464 nm. The trap-state emission
peak at 444 nm for anatase TiO2 nanoparticles in
microemulsion had been observed by us10 earlier. The red
shift in emission spectra for a capped particle compared
to the naked one may be due the to formation of new trap
states.
Figure 3 shows the results obtained from the picosecond
laser photolysis of DBS-capped TiO2 nanoparticles in DMF
solution. The temporal evolution of the transient spectrum
in the picosecond time domain is illustrated in Figure 3.
Each time delay consists of a broad spectrum in the entire
visible region (450-900 nm). This is practically identical
to the electron absorption in the conduction band as
observed by Serpone et al.11 and Rothenberger et al.12,13
on excitation of TiO2 sols. Figure 3 (inset) shows the
recombination dynamics of photoexcited electrons and
holes. The recombination dynamics of the charge carriers
for DBS-capped TiO2 nanoparticles is found to be 1.6 and
>3 ns (Figure 3 (inset)), which is much slower than that
observed by Serpone et al.11 and Rothenberger et al.12 for
bare TiO2 nanoparticles. The density of defect states for
uncapped particles is much higher than that of capped
particles. As a result, the rate of nonradiative transitions
of photoexcited charge carriers for uncapped particles is
(22) Anpo, M.; Tomonari, M.; Fox, M. A. J. Phys. Chem. 1989, 93,
7300.
(23) Serpone, N.; Lawless, D.; Khairutdinov, R. J. Phys. Chem. 1995,
99, 16646.
(24) Zhu, Y. C.; Ding, C. X. J. Solid State Chem. 1999, 145, 711.
(25) Zhu, Y. C.; Ding, C. X. J. Solid State Chem. 1998, 139, 124.
508 Langmuir, Vol. 19, No. 3, 2003
Figure 3. Transient absorption spectra at various time
intervals after picosecond laser excitation (35 ps) at a 355 nm
wavelength of specially synthesized TiO2 nanoparticles in
dimethylformamide (DMF) solvent at (a) 0 ps, (b) 132 ps, (c)
660 ps, (d) 1.32 ns, and (e) 2.97 ns; [TiO2] ) 5 gm/L. The broad
positive absorption feature in the whole spectral region (450-
900 nm) corresponds to electron absorption in semiconductor
nanoparticles. [Inset: recombination dynamics of electrons and
holes monitored at 720 nm.]
much higher than that of capped particles. The major
finding of this investigation is that the charge carriers
generated out of the excitation of these capped TiO2
nanoparticles recombine more slowly than those of widely
used bare anatase particles. Serpone and co-workers11
state that it is the electron/hole recombination that
determines the overall quantum yield of photocatalysis.
Letters
The present studies clearly indicate that a capping agent
can retard the electron/hole recombination process, which
in turn can increase the efficiency the photocatalytic
activity of the TiO2 nanoparticles. We have also observed
that the interfacial electron-transfer dynamics on TiO2
nanoparticle surfaces has been studied mostly in aqueous
medium and on thin films. Currently we are carrying out
experiments to see the effect of solvent and solvent polarity
on electron-transfer dynamics of dye-sensitized TiO2
nanoparticle systems dispersing the DBS-capped TiO2
nanoparticles in many organic and nonaqueous solvents.
Conclusion
In conclusion, the optical properties of DBS-capped TiO2
nanoparticles are different from those of bare TiO2
nanoparticles. Capped TiO2 nanoparticles have a signifi-
cant red shift of the optical absorption band edge and
clear photoluminescence at room temperature in contrast
with that of bare TiO2 nanoparticles. It can be concluded
that a capping agent plays a major role in modification
of the surface structure and defect states, which in turn
affects the electronic states of TiO2 nanoparticles. It has
been observed that the recombination dynamics of charge
carriers (electrons and holes pairs) of capped TiO2 nano-
particles is much slower as compared to that of the bare
ones.
Acknowledgment. We thank Mr. Ram Reddy of Tata
Institute of Fundamental Research, Mumbai, for his
assistance in particle size measurements. We are also
thankful to Dr. A. V. Sapre, Dr. T. Mukherjee, and Dr. J.
P. Mittal for their constant encouragement.
LA026252Q