JOURNAL OF OPTOELECTRONICS AND ADVANCED MATERIALS Vol. 19, No. 3 - 4, March – April 2017, p.

272 - 277

Synthesis and characterisation of titanium dioxide

nanoparticles sensitised with natural chlorophyll dye
extracted from Mentha leaves
A. MOLEAa, V. POPESCUa*, G. L. POPESCUb, R. C. SUCIUc, A. DINESCUd, M. MOLDOVANe
a
Technical University of Cluj-Napoca, Faculty of Material and Environmental Engineering, Physics and Chemistry
Department, No.103-105 Muncii Avenue, 400641 Cluj-Napoca, Romania
b
Technical University of Cluj-Napoca, Faculty of Mechanical Engeneering, The Department of Automotive Engineering
and Transports, No.103-105 Muncii Avenue, 400641 Cluj-Napoca, Romania
c
National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103 Donat, PO 5 Box 700,
400293 Cluj-Napoca, Romania
d
National Institute for Research and Development in Microtechnologies, 126A Erou Iancu Nicolae Street, 077190
Bucharest, Romania
e
Babes Bolyai University - “Raluca Ripan” Institute of Chemistry, 30 Fântânele Street, 400294 Cluj-Napoca, Romania

For this study a facile ultrasounds assisted method was used for synthesis of chlorophyll-sensitised titanium dioxide
nanoparticles. The chlorophyll was extracted from Mintha leaves by a solvent extraction method and based on ultraviolet-
visible spectroscopy it was showed that was extracted chlorophyll (a+b) mixture with concentration of 87 mg/L. Based on X-
ray diffraction patterns analysis was demonstrated that chlorophyll does not change the structural matrix of titanium dioxide.
Field emission – scanning electron microscopy images revealed the formation of nanoparticles with dimensions between 3
nm and 36 nm. Ultraviolet-visible and photoluminescence spectra confirmed that all chlorophyll-sensitised titanium dioxide
nanoparticles absorb the radiation from the visible range. Also, we have proposed a sensitisation mechanism of titanium
dioxide particles with natural chlorophyll dye.

(Received September 20, 2016; accepted April 6, 2017)

Keywords: Natural dye, Chlorophyll, Sensitisation, Titanium dioxide, Nanostructure, Optical properties

1. Introduction natural dyes like: antocyanine [9,12], carmine and morin

[13] or curcumin [14], sensitised-systems utilised in
Titanium dioxide (TiO2) has attracted much attention fabrication of solar cell devices or used as photocatalyst in
due to its various possible applications in: water splitting environment remediation. Beside these dyes, chlorophyll
[1,2] heterogeneous photocatalysis processes used for can be an excellent sensitiser for semiconductors due to
degradation of organic pollutants [3-5] and solar cell the non-toxic nature, can be extracted from renewable bio-
devices [6,7]. However, TiO2 present limitations mostly by resources (mostly from all the green leaves), having a
the fact that it can absorb light only in the ultraviolet minimum impact on environment. Moreover, chlorophyll
region, neglecting the visible and infrared regions, thus, presents two strong absorption peaks in the visible range
neglecting near 95% from the available solar energy. In located at 430 and 660 nm wavelengths, which make it to
order to utilise more effective the sunlight as a renewable be a suitable sensitiser of semiconductors with photoactive
energy, natural dye sensitisation is a promising technique properties in the visible range [15-17]. Al-Alwani et al.
for extension of the excitation energy of TiO2 into visible [15] extracted different natural dyes, namely chlorophyll
region [8-11]. Sensitisation with organic dyes of the and betanin dyes, from Cordyline fruticosa, Pandannus
semiconductors process implies three steps: (1) adsorption amaryllifolius leaves and Hylocereus polyrhizus fruits.
of the sensitizer dye at the semiconductor surface; (2) With these dyes authors sensitised TiO2 commercial
absorption of the radiation from the visible range by dye powder and confirmed the absorption of the natural dyes at
molecules and electrons generation; (3) the electrons titanium dioxide powder surface by optical and infrared
generated by the dye molecules are injected into the spectroscopy analysis. Kathiravan et al. [16] sensitised
conduction band of the semiconducting material [8,9]. In colloidal titanium dioxide with chlorophyll extracted from
1991, O’Regan and Gratzel [8] has sensitised titanium green algae and described the interaction between
dioxide film with ruthenium complex dye in order to chlorophyll and colloidal TiO2 nanoparticle surface by
obtain photovoltaic cell with high efficiency in conversion absorption and fluorescent analysis which confirmed the
of solar energy into electrical current (nearly 11%), known electron transfer from excited state of chlorophyll to the
today as “Gratzel solar cell”. Since then, a series of conduction band of TiO2. Benjamin et al. [17] enhance the
researchers reports the sensitisation of semiconductor with photocatalytic activity of zinc oxide by coating of
 Synthesis and characterisation of titanium dioxide nanoparticles sensitised with natural chlorophyll dye … 273

semiconductor surface with chlorophyll and anthocyanin size and strain was calculated by the Williamson-Hall
dyes. It was observed the shifting of the optical response method [20].
from ultraviolet to the visible range, a decrease of the Morphological properties of chlorophyll-sensitised
energy band gap and a increase of the rate of TiO2 nanoparticles were emphasised using Scanning
photocatalytic degradation of rose bengal (used as electron microscopy. The samples were examined using a
pollutant model) of the dye coated semiconductor. field emission scanning electron microscope (FE-SEM) –
In this paper we described a facile method for Raith e_Line with in-lens electron detection capabilities.
sensitisation of titanium dioxide nanoparticles with UV-Vis spectroscopy studies were carried out in order
chlorophyll extract, using an ultrasound-assisted method. to determine the optical properties of the chlorophyll-
The structural, morphological, optical and fluorescent sensitised TiO2 nanoparticles. The total transmittance of
properties of the chlorophyll-sensitised TiO2 nanoparticles the materials was recorded using a Lambda 35 Perkin-
have been evaluated. Elmer spectrometer equipped with an integrated sphere,
using a spectralon as a reference. Based on the spectra, the
energy band gap of the materials was determined using the
2. Materials and method Tauc’s relation [21]:

2.1. Synthesis of chlorophyll-sensitised titanium h  Ah  Eg 

m
(1)
dioxide nanoparticles
where: α is absorption coefficient, hν is photon energy, E g
In the first stage of the studies, the chlorophyll dye
is the energy band gap, A is an energy dependent constant
was extracted from Mentha leaves, using solvent
and m is an integer depending on the nature of electronic
extraction method. Thus, 3 g of leaves were washed,
transitions. For the direct allowed transitions, m has a
steamed in order to enhance the extraction process and
value of 1/2 while for indirect allowed transitions, n=2.
added 50 ml ethanol heated at 60 0C, for 7 minutes. The
Also, the Urbach energy was determined based on the
extract was kept in a 50 ml volumetric flask.
absorption tail, which can be correlated with the structural
Titanium dioxide nanoparticles were synthesised by a
disorder and strain caused by the synthesis method of the
hydrolysis method, using as precursor titanium III-
chlorophyll-sensitised TiO2 nanoparticles [22]:
chloride, followed by heating at different temperatures i.e.
200 0C, 400 0C, 600 0C and 8000C, respectively. The
synthesis process and characterisation of TiO2 un-  h 
ln    0 exp  (2)
sensitised nanoparticles, annealed at different
 EU 
temperatures, are presented, in details, in our previous
published article [18]. Sensitisation with chlorophyll
where: α0 is a constant and the Eu is the Urbach energy. Eu
extract of TiO2 nanoparticles annealed at different
was determined from the slope of lnα versus (hν).
temperatures was made by an ultrasound-assisted method.
Thus, a volume of 5 ml chlorophyll extract was mixed Photoluminescence measurements were carried out
with 0.5 g TiO2 nanoparticles. The mixtures were using an Able & Jasco FP 6500 spectrofluorometer with a
subjected to ultrasounds for 30 min, followed by a slow xenon lamp of 150 W as the excitation source and a
drying at 40 0C, for 24 h in order to remove the solvent. photomultiplier tube (PMT) as detector. For comparison,
The obtained samples were aged for 48 h, at 40 0C, in all emission spectra were measured at room temperature
order to stabilise the natural dye at TiO2 nanoparticles with the same instrumental parameters using an excitation
surfaces. at 285 nm for chlorophyll and 405 nm for chlorophyll-
sensitised TiO2 nanoparticles, emission originated from
2.2. Characterization of chlorophyll-sensitised the luminescent centres. All spectra were registered
titanium dioxide nanoparticles exactly in the same conditions: excitation/reflection into 5
mg of powder samples with identical incidence intensity,
The chlorophyll extract was analysed using UV-Vis the excitation slit (5 mm) and emission slit (5 mm).
spectroscopy in order to determine the chlorophyll types
and the concentration of the extract [19].
For the determination of the structural properties of 3. Results and discussion
chlorophyll-sensitised TiO2 nanoparticles a Bruker D8
Advance X-ray diffractometer working with CuKα The UV-Vis absorption spectrum of the chlorophyll
radiation was used. The patterns were evaluated using a extract from Mentha leaves is presented in Figure 1. Based
standard X-ray powder diffraction data file, JCPDS 12- on the spectrum it was observed that chlorophyll a and b
1272 (space group I41/amd, a0=3.78(5) [Å], c0=9.51(3) types, with chlorophyll a:b ratio 3:1 were extracted from
[Å]) for anatase crystalline phase and JCPDS 21-1276 the leaves, having the total concentration of chlorophyll
(space group P42/mnm), a0=4.59(3) [Å], c0=2.95(9) [Å]) (a+b) of 87 mg/L.
for rutile crystalline phase. Using the Powder Cell
software, the structural parameters were calculated using
the Pseudo-Voigt refinement and the average of crystallite
274 A. Molea, V. Popescu, G. L. Popescu, R. C. Suciu, A. Dinescu, M. Moldovan

Based on the obtained data, we can affirm that the

sensitisation assisted by ultrasounds process, does not
change the structural phases of chlorophyll-sensitised TiO2
materials (Table 1) compared with un-sensitised materials
[18], so the chlorophyll do not interacted with titanium
dioxide structural matrix. Shang et al. [23] obtained
Benzimidazolone Yellow-sensitised TiO2 photocatalyst
thought solvothermal method and observed that the
sensitizer do not changed the crystalline structure of
original TiO2.

Fig. 1. UV-Vis absorption spectra of chlorophyll extract

X-ray patterns of chlorophyll-sensitised TiO2

nanoparticles are presented in Fig. 2 and in Table 1 are
summarised the results following the calculations of the
average crystallite size, strain and cell parameters. It has
been remarked the amorphous state of the sample treated
at 200 0C and the formation of the anatase crystalline
phase with increasing of the temperature to 600 0C. At 800
0
C a large part of anatase it’s transformed into rutile. This
behaviour is also observed for the un-sensitised TiO2
nanoparticles [18]. However, a small decrease of strain can
be observed compared with the un-sensitised materials. It Fig. 2. XRD patterns of chlorophyll-sensitised TiO2 particles
was not detected any diffraction peaks characteristic for
chlorophyll.

Table 1. Structural parameters of chlorophyll-sensitised TiO2 nanoparticles

Sample name Crystalline Phases Average Strain Structural parameters Cell

phase ratio crystallite size [%] volume
[%] [nm] a [Å] c [Å] [Å3]
Chlorophyll-sensitised Amorphous 100 - - - - -
TiO2 200 0C
Chlorophyll-sensitised Anatase 100 15 0.5 3.78(5) 9.51(3) 135.88
TiO2 400 0C
Chlorophyll-sensitised Anatase 100 19 0.1 3.78(7) 9.50(3) 135.73
TiO2 600 0C
Chlorophyll-sensitised Anatase 46 70 0.3 3.78(9) 9.52(1) 136.02
TiO2 800 0C Rutile 54 21 0.2 4.61(7) 2.97(7) 63.11
TiO2 anatase Anatase - - 3.78(5) 9.51(3) 135.88
JCPDS 12-1272
TiO2 rutile Rutile - - 4.59(3) 2.95(9) 62.15
JCPDS 21-1276

Fig. 3 shows the FE-SEM images of chlorophyll- amorphous to anatase to rutile with the increase of the
sensitized TiO2 nanoparticles. It can be observed that at temperature. For the chlorophyll-sensitised TiO2 200 0C
low calcinations temperature (i.e. 200 0C) the particles are sample particles dimensions were near 3 nm and increased
spherical and uniform in size, while at 800 0C particles to 36 nm for the chlorophyll-sensitised TiO2 800 0C
appear irregular. The change in morphology can be sample.
attributed to the crystals grow during the calcinations and
to the transformation of the crystalline phases from
 Synthesis and characterisation of titanium dioxide nanoparticles sensitised with natural chlorophyll dye … 275

a b

c d

Fig. 3. SEM images of: (a) chlorophyll-sensitised TiO2 2000C; (b) chlorophyll-sensitised TiO2 4000C;
(c) chlorophyll-sensitised TiO2 6000C and (d) chlorophyll-sensitised TiO2 8000C

UV-Vis absorption spectra of chlorophyll-sensitised

TiO2 materials are presented in Fig. 4. It is well known
that pure TiO2 exhibits an absorption maximum in the UV
region (near 360 nm) [18] and from Fig. 4 is obvious that
all the chlorophyll-sensitised TiO2 materials shows
absorption bands in the visible region, between 400 and
800 nm, besides the characteristic UV absorption of TiO2,
indicating the extension of the absorption spectra of TiO2
into visible region by sensitisation with chlorophyll. Also,
visually, it was seen that all the samples, after sensitisation
with chlorophyll, change their colours from white to green.
Similarly, in the literature, a series of studies highlighted
the fact that the dye-sensitised or metal doped materials
presents absorption bands in the visible spectrum,
attributed to the dyes, which indicates that the sensitised-
material can absorb the radiation from the visible range Fig. 4. UV-Vis absorption spectra of chlorophyll-sensitised
[13,24,25]. TiO2 particles
The energy band gaps of the chlorophyll-sensitised
TiO2 materials are between 3.04 eV for the sample treated Urbach energy results showed that (Figure 5(b) and
at 200 0C and decrease to 2.71 eV for the sample treated at Table 2) all the chlorophyll-sensitised TiO2 nanoparticles
800 0C (Fig. 5(a)). Comparing the obtained values of the exhibits lower values (near 1 eV) than the un-sensitised
energy band gap with the one for un-sensitised materials TiO2 materials (between 1 and 2.6 eV) [18]. In this case,
[18] (with energy band gap between 3.47 eV and 2.87 eV), we suppose that by sensitisation process, i.e. treatment
it was observed that the chlorophyll-sensitised material with ultrasounds, a relaxation of crystalline matrix of TiO2
presents smaller values (Table 2). Ananth et al. [26] acquired, which implies a decrease of the strain.
sensitised titanium dioxide powders with Henna dye and Chlorophyll fluorescence analysis allows non-
observed that in the UV-Vis absorption spectra appear an invasive, near instantaneous measurement of key aspects
absorption broad band between 350 and 570 nm, and the of photosynthetic light capture and electron transport. In
energy gap decrease from 3.48 eV for pure TiO 2 to 3.01 the case of chlorophyll (a+b) characterised by UV-Vis
eV for the sensitised sample. absorption spectroscopy it’s still not known if the various
forms are identical in peak position and remained obscure
because is difficult separating of the chlorophyll types
without destruction [27,28]. The noticeable degradation
[29] of the intensity with time can be observed under
276 A. Molea, V. Popescu, G. L. Popescu, R. C. Suciu, A. Dinescu, M. Moldovan

excitation of the chlorophyll photoluminescence in plants. during the measurements and the researchers are faced
As a result, this phenomenon can affect the data obtained with a problem of reliability [30].

Fig. 5 (a) Determination of energy band gap; (b) Determination of Urbach energy

Table 2 . Energy band gap and Urbach energy values of chlorophyll-sensitised TiO2 nanoparticles

Sample name Eg [eV] EU [eV]

Chlorophyll-sensitised TiO2 200 0C 3.04 0.99
Chlorophyll-sensitised TiO2 400 0C 2.93 0.94
Chlorophyll-sensitised TiO2 600 0C 2.88 1.00
Chlorophyll-sensitised TiO2 800 0C 2.71 1.08

chlorophyll complements leading to a high photon

absorbance in the visible range.

Fig. 6. PL spectra of chlorophyll

One band with peak position at 643 nm is observed

at room temperature in the PL spectra which is
characteristic to chlorophyll stabilised at TiO2 Fig. 7. PL spectra of chlorophyll-sensitised TiO2
nanoparticles surface (Fig. 6). Fluorescence emission of particles. Insert: Excitation and emission spectra of
chlorophyll presents one dominant peak at 684 nm, which chlorophyll-sensitised TiO2 particles
is attributed, principally, to the fluorescence emission by
the PSII-core complex and, further, a shoulder between
710-740 nm corresponding to several fluorescence Fig. 7 shows the PL spectra recorded at room
emission sources – particularly PSI-LHCI (Light temperature of chlorophyll-sensitised TiO2 nanoparticles,
harvesting complex II) and several minor PSII bands (PSII excited at 404 nm, emission originated from the
- Photosystem II) [30] and chlorophyll a absorbs at 430 luminescent centres (insert). Temperature was found to
nm and 662, whereas chlorophyll b absorbs at 453 nm and reduce the fluorescence intensity and shift emission band
642 nm [31], fact confirmed by our UV-Vis absorption to a smaller wavelength compared with the chlorophyll
spectra of chlorophyll-sensitised TiO2 nanoparticles (Fig. photoluminescence spectra.
1). The fluorescence emission of different types of
 Synthesis and characterisation of titanium dioxide nanoparticles sensitised with natural chlorophyll dye … 277

4. Conclusion [14] S. Buddee, S. Wongnawa, P. Sriprang, C. Sriwong,

J. Nanopart. Res. 16, 2336 (2014).
The chlorophyll-sensitised titanium dioxide [15] M. A. M. Al-Alwani, A. B. Mohamad, Abd. A. H.
nanoparticles were successfully synthesised by a facile Kadhum, N.A. Ludin, Spectrochim. Acta A
ultrasounds assisted method. XRD analysis showed that 138, 130 (2015).
chlorophyll do not change the structural matrix of TiO2, [16] A. Kathiravan, M. Chandramohan, R. Renganathan,
although, a small decrease of strain has been observed S. Sekar, Spectrochimica Acta Part A
comparing with un-sensitized materials. In this case we 71, 1783 (2009).
suppose that the treatment with ultrasounds can reduce the [17] S. Benjamin, D. Vaya, P. B. Punjabi, S. C. Ameta,
strain by relaxation of the matrix. FE-SEM images reveal Arabian J. Chem. 4, 205 (2011).
the formation of nanoparticles with dimensions between 3 [18] A. Molea, V. Popescu, N. A. Rowson, Optoelectron.
nm and 36 nm. UV-Vis and photoluminescence spectra Adv. Mat. 9(3-4), 431 (2015).
confirmed that all chlorophyll-sensitised titanium dioxide [19] T. Ignat, Z. Schmilovitch, J. Fefoldi, N. Bernstein,
nanoparticles absorb the radiation from the visible range, B. Steiner, H. Egozi, A. Hoffman, Biosystems Eng.
so these materials can be used in various applications such 114(4), 414 (2013).
as optoelectronics devices or visible light-catalysts. [20] W. Kraus, G. Nolze, J. Appl. Crystallogr.
29, 301 (1996).
[21] J. Tauc, R. Grigorovici, A. Vancu, Phys. Status Solidi
Acknowledgment B 15, 627 (1966).
[22] S. H. Kang, J. W. Lim, H. S. Kim, J. Y. Kim,
This paper was supported by the Post‐Doctoral Y. H. Chung, Y. E. Sung, Chem. Mater.
Programme POSDRU/159/1.5/S/137516, project 21, 2777 (2009).
co‐funded from European Social Fund through the [23] X. Shang, B. Li, C. Li, X. Wang, T. Zhang, S. Jiang,
Human Resources Sectorial Operational Program Dyes Pigments 98, 358 (2013).
2007‐2013. [24] L. Li, W. Li, A. Ji, Z. Wang, C. Zhu, L. Zhang,
J. Yang, L-F Mao, J. Optoelectron. Adv. M.
18(7-8), 661 (2016).
References [25] H. Ding, H. Sun, Y. Shan, J. Photoch. Photobio.
A 169, 101 (2005).
[1] A. Fujishima, K. Honda, Nature 238, 37 (1972). [26] S. Ananth, T. Arumanayagam, P. Vivek,
[2] S. U. M. Khan, M. Al-Shahry, W. B. Jr. Ingler, P. Murugakoothan, Optik 125, 495 (2014).
Science 27, 2243 (2002). [27] J. S. Brown, Biophy. J. 9(12), 1542 (1969).
[3] A. Fujishima, X. Zhang, D. A. Tryk, Surf. Sci. Rep. [28] V. Pale, Improving the optical properties of
63, 515 (2008). chlorophyll aggregates with supramolecular design-
[4] A. Molea, V. Popescu, N. A. Rowson, A. M. Dinescu, Dissertation, Aalto University (2011).
Powder Technol. 253, 22 (2014). [29] O. O. Vakulenko, O. O. Grygorieva, O. I. Dacenko,
[5] A. C. Nechifor, A. A. K. K. Rikabi, D. D. Clej, Ukr. J. Phys. 57, 256 (2012).
S. K. Tanczos, C. Trisca-Rusu, C. Orbeci, Rev. Rom. [30] H. M. Kalaji, G. Schansker, R. J. Ladle, V. Goltsev,
Mater. 45, 80 (2015). K. Bosa, S. I. Allakhverdiev, M. Brestic, F. Bussotti,
[6] C. Kang, B. Du, Z. Yang, Optoelectron. Adv. Mat. A. Calatayud, P. Dabrowski, N. I. Elsheery,
10(9-10), 676 (2016). L. Ferroni, L. Guidi, S.W. Hogewoning, A. Jajoo,
[7] I. Robel, V. Subramanian, M. Kuno, P.V. Kamat, A. N. Misra, S. G. Nebauer, S. Pancaldi, C. Penella,
J. Am. Chem. Soc. 128(7), 2385 (2006). D. B. Poli, M. Pollastrini, Z.B. Romanowska-Duda,
[8] B. O’Regan, M. Gratzel, Nature 353, 737 (1991). B. Rutkowska, J. Serodio, K. Suresh, W. Szulc,
[9] M. K. Nazeeruddin, P. Pechy, T. Renouard, E. Tambussi, M. Yanniccari, M. Zivcak, Photosynth.
S. M. Zakeeruddin, R. Humphry-Baker, P. Comte, Res. 122, 121 (2014).
P. Liska, L. Cevey, E. Costa, V. Shklover, L. Spiccia, [31] M. Trytek, E. Janik, W. Maksymiec, J. Fiedurek,
G. B. Deacon, C. A. Bignozzi, M. Gratzel, J. Am. A. Lipke, M. Majdan, J Photochem. Photobiol.
Chem. Soc. 123, 1613 (2001). A Chem. 223, 14 (2011).
[10] Y. Cai, L. Tang, Y. Wang, N. Xu, Y. Li, G. Ji,
Optoelectron. Adv. Mat. 9(7-8), 1014 (2015).
[11] S. Hao, J. Wu, Y. Huang, J. Lin, Solar Energy
________________________________
80, 209 (2006). *
Corresponding author: [email protected]
[12] A. Zyoud, N. Zaatar, I. Saadeddin, M.H. Helal,
G. Campet, M. Hakim, D. H. Park, H. S. Hilal, Solid
State Sci. 13, 1268 (2011).
[13] M.-C. Rosu, R. C. Suciu, M. Mihet, I. Bratu, Mat.
Sci. Semicon. Proc. 16, 1551 (2013).