Transition Met Chem (2009) 34:915923

DOI 10.1007/s11243-009-9281-1

UV-sensitized nanomaterial semiconductor catalytic reduction

of CoIII(NN)33+/nm-TiO2 and Co:TiO2 formation: SEM-EDX
and HRTEM analyses
Krishnamoorthy Anbalagan Lazor Devaraj Stephen

Received: 17 July 2009 / Accepted: 8 September 2009 / Published online: 25 September 2009
Springer Science+Business Media B.V. 2009

Abstract Interfacial electron transfer induced by 254 nm

light at nanomaterial (nm) titanium dioxide/CoIII(NN)33?
interface in binary mixed solvent media such as water/
methanol (or 1,4-dioxane) has been probed. The distinct
photo reduction of cobalt(III) complexes, CoIII(NN)33?;
(NN)=(NH3)2, en (1,2-diamino ethane), pn (1,2-diamino
propane), tn (1,3-diamino propane), and bn (1,4-diamino
butane), by excited nm-TiO2 particles: CoIII ? nm-TiO2 ?
hm ? TiO2 (h?;e-) ? CoIII ? nm-TiO2 (h) ? CoII is
solvent controlled. The electron transfer from the conduction band of TiO2 (e-, CB) onto the metal centre of the
complex consists of (i) electron transport from CB into
surface-adsorbed species A: CoIII(NN)33? (ii) solution
phase species B: CoIII(NN)33?(sol.), accumulated at the
surface of the nanoparticle. In addition, UV irradiation of
CoIII(NN)33? stimulates generation of CoIIaq ion, due to
charge transfer transition, in solution phase. After UV
irradiation, cobalt-implanted nm-TiO2 separated as gray
ultrafine particles, which were isolated. Photo efficiency of
the formation of CoII ion was estimated and the cobalt
implanted nanomaterial crystals isolated from the photolyte
solutions were subjected to SEM-EDX, X-ray mapping,
and HRTEM-SAED analyses. Solvent medium was found
to contribute in both the formation of CoII ion and interstitial insertion of cobalt into the lattice of nm-TiO2.

Introduction
Nanocrystalline semiconductor catalysts have become
widely useful for many technological applications, mainly
K. Anbalagan (&)
L. D. Stephen
Department of Chemistry, Pondicherry University,
Pondicherry 605 014, India
e-mail: kanuniv@gmail.com

due to their light transparency, charge separating properties, and electronic conductivity [1, 2]. Due to the high
chemical stability and favorable energy band structure,
titanium dioxide has drawn attention for its potential
applications in photo catalysis in different fields. Semiconductors, especially TiO2, ZnO, and SnO2 are very
promising components in the development of solar cells
[3], electrochromic devices [4, 5], sensors [6, 7], photoelectrocatalytic and photochromic cells [8, 9]. Recent
investigations have shown that Co(dbbip)22?/3? complexes
are promising candidates [10] for use as redox mediators in
dye-sensitized solar cells. Metal-doped semiconductors
find extensive applications in conjunction with the lattice
structures; for example, Chamber et al. [11, 12] reported
that the local structural environment for Co species in
anatase is similar to that of cobalt in CoTiO3 (highly
distorted octahedral coordination with oxygen ligands).
Nanosized metal-doped materials with novel morphologies
can have somewhat better performance than bulk materials.
From the point of view of kinetic investigations of electron transfer reactions of inorganic complexes in solution,
mixed solvents have a number of distinct advantages. These
include: (a) mixed solvents greatly influence the formation
and stability of transition states [13]/ion-pairs [14]/excited
states [15, 16], (b) they ensure definite rate of electron
transfer reactions even in dilute solutions through potential
matching, (c) the tuning of redox property is facile by the use
of mixed solvents of varying compositions. However,
despite these advantages, the potential of catalytic effect of
TiO2 as electron transfer mediator with cobalt(III) complexes in binary-mixed solvents remains relatively unexplored. In this article, we have designed a novel solution
chemical reaction route to study the interfacial ET processes
and also report formation of surface-modified nm-TiO2
particles due to cobalt implantation.

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Experimental
A series of CoIII(NN)33?; (NN)=(NH3)2, en (1,2-diamino
ethane), pn (1,2-diamino propane), tn (1,3-diamino propane),
and bn (1,4-diamino butane) were prepared as in literature
[17] and reagents used were generally of AnalaR grade
(Sigma-Aldrich) samples. For the UV excitation studies,
nm-TiO2 suspension in neat water/binary solvent mixture
was prepared by adding definite amounts of nanoparticulates (surface area = 200220 m2/g, Sigma-Aldrich) and
pure crystals of CoIII(NN)33?. In a typical solution,
complex concentration was 3.88 9 10-35.60 9 10-3 M
CoIII(NN)33? (ionic strength: 0.1 M NaNO3) in neat water
or water/(methanol or 1,4-dioxane) binary mixtures:
(water:organic co-solvent = 95:5, 90:10, 85:15, 80:20,
75:25, 70:30), in which nm-TiO2 was introduced, stirred,
and ultrasonicated. Multiple photolysis experiments were
performed under identical conditions to confirm the
reproducibility. Light intensities were measured by ferrioxalate actinometry [18] and quantum yield, UCo(II), was
computed by estimating Co(II) by Kitsons method [19].
Solution absorption measurements were made using a
Shimadzu Model UV-2450 double beam UVVis spectrophotometer. Complexes were photolysed by irradiation of
254 nm light source using 6 Watt Low Pressure Mercury
Vapor Lamp (Germicidal G4T5, 3H) Model 3006, in a
small Quartz Immersion Well Model 3210, 80 mL cap.
(Photochemical Reactors Ltd, UK). Photo irradiation was
carried out at definite time intervals. Pure semiconductor
catalyst, nm-TiO2, powder (labeled as sample: a), and
ultrafine crystals isolated from the photolyte solutions
before irradiation at 0 s (labeled as sample: b) and after
definite time interval at 120 s, (sample: c) were subjected
to SEM and HRTEM analyses.
Scanning electron microscopy and X-ray microanalyses
(EDX) of the samples were performed on a Hitachi S3400N, magnification: 59 to 300,0009, SE image resolution: 3.0 nm, Accln. voltage 0.3 kV to 30 kV, working
distance: 560 mm, maximum specimen size: 200 mm.
Prior to analysis, pressed powder samples were coated with
a thin layer of evaporated carbon for conduction and
examined at 25 kV accelerating voltage using a standardless procedure on a Hitachi S-3400N instrument equipped
with a energy-dispersive X-ray microanalysis system.
Three measurements were recorded for each sample over a
sample area of 2 mm. High-resolution transition electron
microscopy (HRTEM) scans of the samples were performed on a JEOL 3010 instrument with a UHR polepiece.
This gave a lattice resolution of 0.14 nm and a point-topoint resolution of 0.12 nm with standard probe and a
variable temperature probe (100500 K). The instrument
has a Gatan digital camera. Droplets of aqueous suspensions of the samples were placed on carbon-covered copper

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Transition Met Chem (2009) 34:915923

grids for 30 s, supernatant fluid was blotted off and the

grids were left to air dry. Microscopy was carried out at
different primary nominal magnifications in the range of
M = 100 K up to 390 K.

Results and discussion

Photoproduction of cobalt-implanted nm-TiO2
The photo reduction of CoIII(NN)33? complexes has been
investigated in watermethanol (or 1,4-dioxane) solutions
using nm-TiO2 as photo catalyst, which was excited with
254 nm light source. The cobalt(III) complex is also a good
UV light absorber, exhibiting two ligand to metal charge
transfer (LMCT) bands, one centered at 302.3349.1 nm
and the second one at 466.9501.4 nm (in water). It was
observed that the CoIII(NN33? complexes are considerably stable in neat water on exposure to light over long
periods of time [14, 15, 20]. However, addition of nm-TiO2
provoked the complexes to degrade, and cobalt(II) was
generated in either pure water or binary solvent media.
Tables 1 and 2 illustrate the quantum yield of CoII formation, which is strongly dependent on the mole fraction
of the organic co-solvent present in the mixture. Figure 1
exhibits the growth in photo efficiency (%), which is
altered by the increase in organic co-solvent content.
Surface survey using SEM and EDX analyses
Titanium dioxide semiconductor finds extensive use in a
number of applications, such as photoactive layers, superhydrophilic films, bifunctional membranes sensors, etc.
[21]. Therefore, the nano material crystalline powder from
the photolyte solution was isolated and characterized, since
nm-TiO2 illustrates an enhanced photo activity and porous
selectivity due to the organized internal structure. Figure 2
shows the SEM images of surface morphology, thickness,
and structural characteristics of ultrafine crystals of pure
nano material powder TiO2 (abbreviated as a), samples
isolated from the photolyte solution before irradiation (at
0 s, abbreviated as sample b), and after definite time of
irradiation (at 120 s, sample c). A significant difference of
the surface morphology and structure of nm-TiO2 of the
samples b and c could be seen, that is, significant aggregation of particles is observed.
In a typical experiment, SEM micrographs of
CoIII(tn)33?/nm-TiO2 in water/methanol (90:10) at the
initial (at 0 s) and after 120 s irradiation using k = 254 nm
show the presence of disordered filaments leading to an
almost fluffy structure due to cobalt deposition. A lower
coverage in the sample b and somewhat higher coverage in
sample c are visible. The particle size in sample b is

Transition Met Chem (2009) 34:915923

917

Table 1 Photoreduction efficiency of cobalt(III)alkyl amine complexes in air equilibrated watermethanol mixtures (pH = 6.82)
Methanol

Temperature (K)

% (v/v)

x2

UCo(II)
[CoIII(NH3)6]3?

[CoIII(en)3]3?

[CoIII(pn)3]3?

[CoIII(tn)3]3?

[CoIII(bn)3]3?

293

0.345 0.002

0.351 0.004

0.361 0.008

0.336 0.001

0.291 0.008

300

0.382 0.003

0.361 0.003

0.376 0.002

0.342 0.007

0.317 0.003

Percentage increase in photoefficiency

5

0.0229

293

4.1

5.4

3.3

2.1

1.5

300

5.8

5.4

2.1

5.6

1.6

10

0.0471

293

8.6

6.4

1.9

1.7

3.9

15

0.0728

300
293

7.9
16.6

7.5
9.9

1.5
1.8

3.6
2.5

3.6
5.8

300

9.1

8.3

1.7

5.5

4.3

20

0.1001

293

18.2

12.2

4.3

4.8

14.5

300

12.1

11.9

4.7

5.7

7.2

25
30

0.1292
0.1602

293

20.7

13.0

6.4

7.2

14.0

300

14.2

13.2

7.8

3.7

8.5

293

21.9

17.5

11.9

8.1

12.1

300

17.1

17.2

9.4

7.2

10.4

The estimated values of UCo(II) for complexes in neat water and the increase in values in percentage
[Co(III) = 3.88 9 10-3 to 5.60 9 10-3 M, [NaNO3] = 0.1 M

Table 2 Photoreduction efficiency of cobalt(III)alkyl amine complexes in air equilibrated water-1,4-dioxane mixtures (pH = 6.82)
1,4-dioxane

Temperature (K)

% (v/v)

x2

UCo(II)
[CoIII(NH3)6]3?

[CoIII(en)3]3?

[CoIII(pn)3]3?

[CoIII(tn)3]3?

[CoIII(bn)3]3?

293

0.345 0.002

0.351 0.004

0.361 0.008

0.336 0.001

0.291 0.008

300

0.382 0.003

0.361 0.003

0.376 0.002

0.342 0.007

0.317 0.003

Percentage increase in photoefficiency

5
10

0.0109

293

1.8

1.4

4.1

1.3

3.2

300

2.7

1.7

3.6

1.7

3.7

0.0229

293

4.8

4.8

5.1

2.5

5.8

15

0.0359

300
293

4.2
7.8

4.7
6.4

5.7
7.0

4.1
6.9

4.9
10.2

300

6.1

7.9

7.4

5.1

9.0

20

0.0502

293

9.6

9.7

10.2

8.4

12.1

300

8.4

9.5

10.1

8.6

10.8

293

6.72

12.4

13.4

11.4

16.2

300

10.3

13.2

14.5

10.8

15.3

293

15.1

13.3

15.4

12.5

18.4

300

14.6

15.6

17.1

13.6

17.1

25

0.0659

30

0.0831

The estimated values of UCo(II) for complexes in neat water and the increase in values in percentage
[Co(III) = 3.88 9 10-3 to 5.60 9 10-3 M, [NaNO3] = 0.1 M

510 nm but the size becomes 2560 nm in sample c.

Figures 3 and 4 present the EDX profiles and X-ray mapping of the samples, in which Ti:Co = 33.33:0 (before
irradiation) and Ti:Co = 33.19:0.21 (%) (after irradiation

for 120 s). It indicates the implantation and homogeneous

distribution of cobalt on the lattice of titania. This is very
well confirmed by X-ray mapping, in which a minimum
percent of cobalt on the nm-surface is evident for all other

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Transition Met Chem (2009) 34:915923

3

Quantum Efficiency (%)

20

CoIII NN3 3 S ! CoII NN3 S ! CoII LMCT

3

16
12
8
4
0
0

0.05

0.1

0.1

0.2

x2
Fig. 1 Dependence of quantum efficiency (in %) versus mole
fraction of organic co-solvent (x2) in watermethanol. Filled circle
CoIII(NH3)63?, filled triangle CoIII(en)33?, open triangle CoIII(pn)33?,
open square CoIII(tn)33?, filled square CoIII(bn)33? at 300 K

complexes. The metal centre reduction could be due to

(i) CoIII(NN)33? ? nm-TiO2 (h?;e-) ? hm ? Co(II) or
(ii) charge transfer to metal transition (LMCT) leading to
the generation of Co(II); CoIII(NN)33? ? hm (LMCT) ?
Co(II). Tables 1 and 2 illustrate that the photo efficiency
of Co(II) production which is dependent on the organic
co-solvent content of the medium. Therefore, reduction of
cobalt(III) centre of the complex was competitively initiated by both nm-TiO2 (e-, CB) and solvent-influenced
LMCT transition of the complex as given in Eqs. 13.
TiO2 h ; e VB hm ! e CB

CoIII NN3 3 e CB ! CoII NN3 2 ! CoII

2

Fig. 2 SEM images of pure and

isolated samples; a pure nmTiO2, b nm-TiO2/CoIII(tn)33?
(before irradiation, at 0 s), size:
10 lm (inset: 5 lm) and
(c) nm-TiO2/CoIII(tn)33? (after
irradiation, at 120 s) size:
10 lm (inset: 5 lm) in
water:methanol = 90:10

123

These reactions are taking place in competition with the

undesirable back electron transfer; however, the photo
efficiency is gradually enhanced as given in Tables 1 and 2.
We would now like to address the question of photo
reduction of CoIII by the nm-TiO2 surface (Eqs. 1, 2). The
differences observed in the quantum yields in the presence
of nm-TiO2 suspensions of CoIII complexes in binary
solvents could also be due to differences in the surface
chemistries, such as the mechanisms of adsorption,
desorption or the specific reactions of surface concentrated
species.
Surface morphology and cobalt implantation
According to HRTEM results, the cobalt-implanted nm-TiO2
isolated from the photolyte solutions are mainly nanosized
crystallites and contain relatively wide distributions. Figure 5 presents the HRTEM images of the samples a and b
for a typical complex, CoIII(tn)33?, which illustrate segregated but hexagonal patterns of the crystal lattice. The
weak fast Fourier transform (FFT) signals of Co for the
samples (iii) and (iv) indicate the presence of some Co in
the TiO2 matrix in the form of substituted particles. This
suggests the possibility of a small quantity of Co occupying
the substitutional sites of Ti of titania leading to solid
solution of anatase nm-TiO2. The lattice fringes due to
cobalt insertion are about 5 nm indicating the modified
anatase product. The selected area electron diffraction
(SAED) pattern further confirms the formation of cobalt

Transition Met Chem (2009) 34:915923

919

Fig. 3 EDX spectrum of

Co:nm-TiO2 material isolated
from the photolyte solution of
nm-TiO2/CoIII(tn)33? complex
in water:methanol = 90:10.
(before irradiation, at 0 s,
sample b). X-ray mapping
of (i) Ti and (ii) O

(i)

(ii)

5m

Element

O
Ti
Total

Net
Counts

1259
41503

Weight %

Atom %

Formula

40.05S
59.95
100.00

66.67
33.33
100.00

TiO2

Fig. 4 EDX spectrum of

Co:nm-TiO2 material isolated
from the photolyte solution of
nm-TiO2/CoIII(tn)33? complex
in water:methanol = 90:10.
(after irradiation, at 120 s,
sample c). X-ray mapping
of (i) Ti and (ii) O

(i)

(ii)

(iii)

5m

Element

O
Ti
Co
Total

Net
Counts

1615
38516
159

insertion on the surface of nm-TiO2 (Co:nm-TiO2),

obtained from the photolyte solution after high dose (at
120 s) of 254 nm light. Moreover, there might not be
amorphous products on the surface as the image shows
regular lattice spacing. The cobalt phase is quite homogeneous with a diameter of about 5 nm with inter-cluster
distance generally greater than 5 nm.

Weight %

Atom %

Formula

39.94S
59.59
0.47
100.00

66.60
33.19
0.21
100.00

TiO2
CoO

Tuning of photoreduction
The photoredox processes of nm-TiO2:CoIII(NN)33? can be
tuned in watermethanol/1,4-dioxane solutions, which also
ensures an efficient injection of electrons from the conduction band of titania to the metal centre of the complex ion
leading to the formation of Co(II) species; simultaneously,

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Transition Met Chem (2009) 34:915923

Fig. 5 High-resolution TEM image of a CoII:TiO2 (before irradiation, at 0 s, sample b) and b CoII:TiO2 (after irradiation, at 120 s,
sample c). c Lattice image taken from CoII:TiO2 away from
segregated area (before irradiation) (inset selected area diffraction

patterns (SADPs) taken from CoII:TiO2 and fast Fourier transform for
CoII:TiO2 complex). d Lattice image taken from CoII:TiO2 away
from segregated area (after irradiation) (inset selected area diffraction
patterns (SADPs) taken from CoII:TiO2 and FFT for CoII:TiO2

surface modified semiconductor species was generated at the

end of high dose of 254 nm irradiation. Evidently, addition
of methanol (or 1,4-dioxane, C4H8O2) in the medium
increases the photo efficiency of reduction of metal ion of the
complex mainly due to MLCT. On the other hand, it is
suggested that the density of CoIII(NN)33? ion at the surface
of semiconductor is enhanced by the hydrophobic nature of
the CH3OH/C4H8O2 organic co-solvent molecules. The
condition provides prominent forward ET compared to back
ET and the net effect is an enhanced-electron transfer rate.
Introduction of excess concentration of methanol/1,4-dioxane ensures uniform distribution of the complex ion on the
oxide surface and promotes electronic coupling of the
donoracceptor levels. Moreover, the choice of the methanol
or 1,4-dioxane controls water content in the pores during the
loading of the metal complex due to surface adherence [22].
EDX analysis of cobalt-deposited TiO2 samples as illustrated in Figs. 3 and 4 indicate that enhancement of Co(II) on
the surface is more probable in solvent medium with higher
organic co-solvent content (methanol; when x2 = 0.1602/
1,4-dioxane; x2 = 0.0831), which results in efficient accumulation of CoIII(NN)33? near the active sites of nm-particles, thereby CoIII centers could capture the photo-excited
electrons; simultaneously, improved surface active sites of
TiO2 would increase the mobility of electrons resulting in
enhanced photo efficiency [23].
The EDX spot probe analysis shows that Co loading is
enhanced in all the samples after definite time (120 s) of

irradiation. These observations strongly illustrate that

adsorption/accumulation is a main factor responsible for the
photo activity enhancement. This suggests two features; (i)
the adsorbed molecules can efficiently reach light-activated
sites and (ii) electron transfer is efficient due to mobility of
the molecules near the surface at the interface. Photo catalysis of nm-TiO2 in mixed solvents is more efficient; however, the surface structure collapses readily leading to cobalt
insertion with some agglomeration of nm-particles from size
510 to 2560 nm. An interesting observation is the unique
behavior of nm-photo catalysts in (i) enhanced activity, (ii)
agglomeration of particle size, and (iii) insertion of the
photo-generated Co(II) ion substitutionally into the lattice of
titanium dioxide retaining the crystalline phase. This implies
that a favourable interface exists in the electron transfer
process in TiO2/CoIII(NN)33?/watermethanol (1,4-dioxane)
system. Moreover, complex cation-binding ability on nmTiO2 is established as the solvent environment is varied,
which could affect (i) attachment of complex ion and (ii)
detachment of the metal centre after reduction (EDX shows a
small increase in Co on nm-surface). As shown in Fig. 5,
aggregates are visible both for TiO2 as well as CoII:nm-TiO2
in dried samples. A closer look at high-resolution images
shows that the aggregates appear with the same crystallographic orientation. Therefore, the shape and aggregation of
particles might be different in binary solvent mixtures.
Accordingly, the target molecules [24] are adhered on photo
catalyst particle surface. Thus, excited nm-TiO2 transfers the

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Transition Met Chem (2009) 34:915923

921

photo electron to surface as well as solution locations; ultimately, it could be possible to apply some solvent designing
for photo catalytic systems to enhance their activity.

eTiO 2
III
Co

Surface Species, A

Sensitization by nm-TiO2
Direct band-gap excitation of the semiconductor is achieved
at k = 254 nm excitation (band gap & 3.2 ev) [25]; however, the electron-hole recombination rate retards the
product yield. Solvent environment could modify the
surface-solution species interaction due to hydrophobic/
hydrophilic contributions, for instance, Kusumoto et al. [26]
reported the photo catalytic activity of TiO2 in hydrogen
production from methanol/water solution. In this investigation, photo reaction was carried out in watermetanol/1,4dioxane solutions, in which the efficiency of the photo
catalyst and the medium to pass the photon energy to the
reaction system is anticipated to be high. Mechanism
of solvent assisted [27] reduction of CoIII(NN)33? on
nm-TiO2 is as presented in the following Eqs. 46.


 hm 

CoIII NN3 3 ;nm-TiO2 ! CoIII NN3 3 ; nm-TiO2




III

Co NN3 ; nm-TiO2

4
 II

! Co NN3 2 ; nm-TiO2

e-

III
Co

Solution Species, B

Surface Species (A)

TiO2(h+,e-) +

III
Co

II
Co

more effecient

Solution Species (B)

TiO2(h+,e-) +

III
Co

II
Co

5


II

II

Co NN3 ; nm-TiO2 ! Co NN3

nm-TiO2
6

Based on the observations, it can be concluded that photoinduced reduction takes place (i) at the surface of
semiconductor particle and (ii) at the solution phase of
the surface, where accumulation of the species is more
predominant. Scheme 1 represents the achieving of photoinduced electron transfer at the surface (surface complex
ion; species A: CoIII(NN)33?(sol.S)) and at the solution
phase where the complex species accumulation is more
(solution phase complex ion; species B: CoIII(NN)33?(sol.)).
Light absorption by the semiconductor particles leads to the
generation of e-(CB), which is efficiently injected to the
metal center as given in Eqs. 79. However, efficiency of
reduction of CoIII(NN)33?(sol.) and CoIII(NN)33?(sol.S)
species ions is more in binary solvent mixture containing
higher concentration of organic co-solvent than that of
solvent mixture containing less or in neat water.
nm-TiO2 hm ! e CB

e CB CoIII NN3 3 sol:S ! CoII NN3

2
sol:S

more efficient
8

less effecient
Scheme 1 Reduction of target cobalt(III) complex ion as (i) surface
adsorbed complex ion (Species A): Co(NN)33?(sol.S) and (ii) solution
phase complex ion (Species B): Co(NN)33?(sol.) accumulated near
the solution phase of nm-TiO2 surface (open circle water molecule,
filled circle organic co-solvent molecule)

e CB CoIII NN3 3 sol: ! CoII NN3

2
sol:

less efficient
9
That is, concerted geometrical and chemical environment
of solvent cage of binary mixed solvents, along with the
influence of the hydrophobic effect of CH3 of CH3OH and
C4H8 skeleton of 1,4-dioxane shows an enhancement in
photo efficiency as the organic co-solvent content in the
medium increases. It means the efficiency of electron
transport is a function of densities of cationic complex and
the influence of solvent [28]. That is, heterogeneous solvation-induced interfacial electron transfer dynamics can
be different between molecular donor and acceptors [28].
All the FranckCondon factors of the electron transfer
reaction are available in parallel, and thus electron transfer
is controlled by the electronic coupling strength between

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922

electron donation wave functions in TiO2 and the acceptor

orbitals of the metal complex [29].
It is clear, however, that only the very close contact
between the donor state of semiconductor and acceptor
orbital of the complex ion together with a strong chemical
bond, facilitated by solvation, can eliminate most of the
undesired slowing down effect. Binding in this way to the
surface of TiO2 in a selected binary solvent medium, that
can accommodate the complex ion at the pores but without
slowing down the electron transport, can modify the rate of
reduction. Three important features can be discerned in this
investigation; first, efficient reduction of metal center,
second, charge recombination can be controlled and third,
insertion of cobalt ion in the lattice of the nm-titanium
dioxide due to reduction of CoIII(NN)32?. The interfacial
electron-transfer processes are presumably associated with
the spatial heterogeneities of the nanoscale local environments and the inhomogeneous vibronic coupling between
the adsorbed molecules and the rough surfaces of the
semiconductors [30].

Conclusion
UV irradiation of nm-TiO2/CoIII(NN)33? complexes in
watermethanol/1,4-dioxane solutions stimulates generation of CoIIaq ion in solution phase and cobalt-implanted
anatase titanium dioxide as ultrafine particles. Photo efficiency of formation of CoII ion was estimated and the
nanomaterial crystals isolated from the photolyte solutions
were subjected to SEM-EDX, X-ray mapping, and HRTEMSAED analyses. It can be concluded that CoIII(NN)33?
complexes show an improved photo efficiency of metal
centre reduction catalysed by nm-TiO2 particles in binary
solvent media, which is due to accumulation of CoIII(N
N)33? at the pores due to solvation contributions. That is, the
attachment of complex ion is facilitated before photo
reduction and detachment after reduction [31, 32]. More
interestingly, after high dose of UV irradiation (k =
254 nm), cobalt implanted nm-TiO2 separated as gray
ultrafine particles. It indicates that Co(II) ion is inserted into
the lattice of the nm-particle leading to the formation of
CoII:nm-TiO2 with high order of crystallinity. The important
observations are the unique behavior of nm-photo catalysts
in enhanced activity, agglomeration of particle size, and
insertion of the photo-generated Co(II) ion substitutionally
into the lattice of titanium dioxide retaining the crystalline
phase. This implies that a favorable interface exists in the
electron transfer process in TiO2/CoIII(NN)33?/water
methanol (1,4-dioxane) system. Solvent medium was found
to contribute in both the formation of CoII ion and interstitial
insertion of cobalt in the lattice of nm-TiO2.

123

Transition Met Chem (2009) 34:915923

Acknowledgments Prof. K.A, Principal Investigator, records his
sincere gratitude to the Department of Science & Technology, New
Delhi and Council of Scientific and Industrial Research, New Delhi
for financial support through major research projects. The authors are
thankful to the Central Instrumentation Facility, Pondicherry
University for providing SEM instrumental facility.

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