DOI 10.1007/s11243-009-9281-1
Received: 17 July 2009 / Accepted: 8 September 2009 / Published online: 25 September 2009
Springer Science+Business Media B.V. 2009
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.
123
916
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
123
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
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
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
123
918
20
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
123
919
(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
(i)
(ii)
(iii)
5m
Element
O
Ti
Co
Total
Net
Counts
1615
38516
159
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,
123
920
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
123
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
TiO2(h+,e-) +
III
Co
II
Co
more effecient
TiO2(h+,e-) +
III
Co
II
Co
5
II
II
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
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)
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
123
922
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
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