Applied Surface Science 336 (2015) 226–233

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Laser oxidative pyrolysis synthesis and annealing of TiO2

nanoparticles embedded in carbon–silica shells/matrix
C.T. Fleaca a,b , M. Scarisoreanu a,∗ , I. Morjan a , C. Luculescu a , A.-M. Niculescu a , A. Badoi a ,
E. Vasile c , G. Kovacs d
a
National Institute for Plasma, Laser and Radiation Physics (NILPRP), Atomistilor 409, P.O. Box MG 36, R-077125 Magurele, Bucharest, Romania
b
“Politehnica” University of Bucharest, Physics Department, Independentei 313, Bucharest, Romania
c
“Politehnica” University of Bucharest, Faculty of Applied Chemistry and Materials Science, Department of Oxide Materials and Nanomaterials,
Gh. Polizu 1-7, Bucharest, Romania
d
“Babes-Boyai” University, Faculty of Chemistry and Chemical Engineering, Arany Janos 11, Cluj-Napoca, Romania

a r t i c l e i n f o a b s t r a c t

Article history: Titania nanoparticles containing a mixture of anatase and rutile phases (with mean crystalline sizes up
Received 27 June 2014 to 24 nm) covered with/embedded in carbon/silica thin layers or matrix were obtained in a single step
Received in revised form 23 October 2014 using laser oxidative pyrolysis. Titanium tetrachloride and hexamethyldisiloxane (HMDSO) vapors were
Accepted 19 November 2014
separately introduced into the reaction zone – both together with the laser-absorbing agent (sensitizer)
Available online 3 December 2014
ethylene – which acts also as carbon source – and the oxidant (air) – through the inner and the concentric
nozzle, respectively. By increasing the air flow through the annular nozzle, while keeping constant the
PACS:
TiC4 , inner air, HMDSO and C2 H4 flows, the atomic carbon concentration as well as the rutile to anatase
81.16 Mk
82.33 Vx
ratio in the resulted nanopowders decrease. A much brighter and extended flame was observed for the
81.07 Wx experiment involving the greatest air flow. The Ti/Si atomic ratio in the resulted nanocomposites was
61.46 Df higher than that from the introduced precursors (1.8), indicating a partial siloxane conversion to silica.
62.23 Kn The annealed powders (at 450 ◦ C to further carbon content reducing) exhibit a lower bandgap energy
81.16 Hc than those of the reference sample without silica (and also lower than the commercial Degussa P25
nano-TiO2 ).
Keywords:
Laser pyrolysis
© 2014 Elsevier B.V. All rights reserved.
Core–shell nanoparticles
Anatase/rutile mixture

1. Introduction with very different morphologies such as aerogels [1] or nanopat-

Titanium dioxide-based nanomaterials have found a very wide
range of applications, from pigments to water remediation espe-
cially due to the optical and catalytic properties of the two main
TiO2 phases, anatase and rutile, enhanced by the high surface
area and reactivity provided by the nanosize dimension. More-
over, controlled combination of titania with other substances can
further enhance their performances through a synergistic interac-
tion. Benefiting from the specific advantages of both components:
semiconductive behavior and crystallinity from TiO2 and porous,
protective characteristic associated with the hydrophilicity and
thermal resistance of SiO2 , the titania–silica (nano)composites are
a representative class of such materials. Sol–gel is the most used
technique for their fabrication, allowing the synthesis of materials
∗ Corresponding author. Tel.: +40 21 4574489; fax: +40 21 4574243.
E-mail address: monica.scarisoreanu@inflpr.ro (M. Scarisoreanu).
terned nanodots/nanowires [2], having as targeted application the
performant photocatalytic oxidation of various organic molecules.
Moreover, silica–titania material was found to able to photode-
compose the water (accelerated by RuS2 doping) with H2 and O2
generation under UV light [3]. The same sol–gel approach was
used to obtain materials with various other light-related applica-
tions: superhydrophilic [4] or antireflective self-cleaning films [5],
solar [6] and transparent UV-shielding poly(methyl methacrylate)
(PMMA)-based composites [7]. The gas-phase methods starting
from various Ti and Si containing vaporized/sprayed precursors
allow the synthesis of TiO2 /SiO2 films and powders in a contin-
uous mode and much faster than in the sol–gel methods. Flame
combustion is the most used gas-phase method and was employed
for the obtaining of TiO2 doped SiO2 films for waveguide applica-
tions (from titanium tetraisopropoxide (TTIP) and [(CH3 )2 SiO]4 in
a O2 /H2 flame) [8], TiO2 @SiO2 core–shell composite nanoparticles
(from TiCl4 and SiCl4 using N2 -shielded oxy-hydrogen flame and a
multitubular injector) [9], column-shaped TiO2 –SiO2 phocatalytic

http://dx.doi.org/10.1016/j.apsusc.2014.11.106
0169-4332/© 2014 Elsevier B.V. All rights reserved.
 C.T. Fleaca et al. / Applied Surface Science 336 (2015) 226–233
nanoparticles/fibers deposed on glass (from TTIP, tetraethoxysilane
(TEOS) and a liquefied petroleum gas (LPG) – air/O2 /N2 combustible
mixture) [10] and also binary SiO2 /TiO2 mixed oxide and composite
nanoparticles from N2 -diluted TTIP [11] or TiCl4 [12] and HMDSO
(or also SiCl4 or SiBr4 [13]) in an O2 /N2 /CH4 flame at atmospheric
pressure.
Other material that can improve the properties of titania is the
carbon, which was reported to stabilize the anatase phase [14] and,
as a thin coating under porous form, to enhance the adsorption
of the organic molecules, without reducing too much the amount
of UV radiation that reaches the TiO2 photocatalytic surface [15].
Due to the formation of titania–graphite heterojunction which
enhanced the separation of photogenerated electrons and holes,
the TiO2 anatase/carbon nanowalls (CNWs) material presented a
higher UV light-induced photodegradation of phenol compared
with TiO2 nanotubes [16]. Similar deposition of TiO2 coatings by
metal organic chemical vapor deposition (MO CVD) on activated
carbon (using titanium tetrabutoxide (TBOT) precursor instead of
TTIP) yielded a recyclable photocatalyst, successfully tested for
methylorange dye degradation in aqueous suspension under UV
irradiation [17]. Moreover, the presence of carbon provides a strong
absorption in visible light (up to 750 nm) and also induces a visible-
light photodegradation activity [18] as compared with pure anatase
which requires the more energetic UV photons to perform the pho-
tocatalytic role. Thus, by a very thin (few graphene layers) coating
deposed on the TiO2 surface resulted a hybrid material better than
the pure TiO2 Degussa P25 reference under UV light irradiation,
presenting also a high activity under visible light due to the cou-
pling between the ␲ electrons of graphite-like carbon and those
from the conduction band of TiO2 [19]. Visible-light activity was
reported too for sol–gel synthesized carbon-doped TiO2 where the
dopant was provided by the butyl groups from the TBOT precursor
[20]. Other authors used the one-pot hydrothermal method to form
TiO2 @C (from TiCl4 and glucose) with greatly enhanced photocat-
alytic activity under visible light compared with noncarbon-TiO2
toward Acid Orange dye or 2,4-dichlorophenol [21]. They also
report the presence of C OH, C O C, C O and COOH groups in
the carbonaceous layer and point out the existence of two differ-
ent sensitization processes: one induced by carbon and other by
the organic dye. The coating of pre-formed TiO2 nanoparticles with
disordered carbon was also successfully achieved using C2 H2 in a
CVD process, resulting again an increasing visible-light photocat-
alytic activity against phenol [22]. One-step gas-phase synthesis
of TiO2 @C nanostructured particles was reported using low oxi-
dant concentration from TTIP and C2 H2 in flame aerosol reactor
[23] or from TiCl4 and C2 H4 with/without C2 H2 by laser pyrolysis
[24]. Recently, carbon-incorporated TiO2 microspheres prepared by
flame-assisted hydrolysis of TBOT proved enhanced H2 production
from water (when compared with TiO2 P25) during simulated solar
light irradiation [25].
More complex than the TiO2 –SiO2 and TiO2 –C materials, the
ternary TiO2 /SiO2 /C composites can also be obtained, potentially
benefiting from both specific properties of carbon and silica added
to those of titania and possible enhanced by synergistic effect.
One such material was the carbonized mesoporous silica gel/CVD-
titania composites with different C and TiO2 concentrations [26].
The mechanochemical intercalation technique was used to obtain
nanoporous graphite-derived carbon/TiO2 –SiO2 composites from
C16 H33 N(CH3 )3 Br (CTAB) pre-intercalated graphite oxide, TEOS and
TTIP which was successfully tested for phenol adsorption and
degradation under UV sterilizing light [27]. The TiO2 supported
by silica gel composite capacity to photodegrade the gray water
(rich in organic carbon) was increased through the addition of acti-
vated carbon which enhances the composite’s absorption capacity
[28]. Another recent paper reported an enhancing of the visi-
ble photocatalytic activity of TiO2 –SiO2 solvothermal-synthesized
227
photocatalyst by the synergetic effect of carbon and silver co-
doping [29]. Laser pyrolysis gas-phase technique was also used
to obtain in a single step oxygen-deficient blue Ti/Si/C/O compos-
ite nanopowders from TTIP aerosol mixed with SiH4 gas, without
external oxidative agent [30]. This approach (due to the fixed
atomic ratio between Ti and O atoms in the TTIP precursor) does not
allow the independent variation of the introduced oxygen. More-
over, it is known that the silane reacts explosively when encounters
the molecular oxygen, and consequently, a considerable amount of
inert gas it is necessary to control this reaction which dramatically
diminishes the resulted oxide powder productivity.
In this paper, we report the using the laser pyrolysis method to
study the influence of the supplementary outer air oxidant intro-
duction together with the HMDSO vapors (carried by the same C2 H4
flow after bubbling) when the TiCl4 inner flow and their accompa-
nied air and C2 H4 sensitizer flows are also kept constant on the
structure and optical properties of the resulted TiO2 @SiO2 /C nano-
composites.
2. Experimental
Titanium tetrachloride (>99%) and hexamethyldisiloxane (min.
99%) volatile liquids were purchased from Merck, whereas ethyl-
ene (99.95%) sensitizer, synthetic air (80% nitrogen, 20% oxygen)
and auxiliary argon (99.998%) were purchased from Linde Gas.
Our laser pyrolysis experimental set-up was described in [31,32],
when a similar three concentric nozzles injector was used for the
synthesis of titania-based nanoparticles. Briefly, the TiCl4 vapors
carried from a bubbler by an air–ethylene mixture were introduced
from the bottom of a vertical injector through the central noz-
zle, the ethylene-carried HMDSO vapors and various air flows
through the second annular nozzle, whereas an Ar confinement
flow pass through the third annular nozzle. These flows orthog-
onally encounter a focused continuous-wave infrared laser beam
( = 10.6 ␮m) centered at 7 mm above the injector. Due to the pres-
ence of the laser-absorbing ethylene molecules, the mixture is
rapidly heated, initiating the emergence of the oxidative pyrolysis
flames (presented in Fig. 1). The freshly resulted nanocompos-
ite powders, carried by the gas flow, were then captured on a
porous filter. The main experimental parameters are resumed in
Table 1, including those for the synthesis of the reference sample
without silica (TLOP 01). In order to decrease their surface-carbon
content, the as-synthesized nanopowders were annealed during
3 h in a furnace under synthetic air at 450 ◦ C. The raw powders
morphology was examined with a Tecnai F30 G2 (300 kV) Trans-
mission Electron Microscope (TEM) and the elemental composition
evaluation (for all (un)treated samples) was performed by energy-
dispersive X-ray spectroscopy (EDS) using a liquid nitrogen-cooled
SiLi detector from EDAX Inc. mounted inside a FEI Quanta Inspect
S Scanning Electron Microscope (SEM) working up to 30 kV accel-
eration voltage. Their crystalline phase composition was revealed
using a PANalytical X’Pert MPD theta-theta X-ray diffraction (XRD)
apparatus using a Cu K␣ source (0.15418 nm). The weight fractions
(expressed in percents) of anatase (YA ) and rutile (YB = 100 − YA )
phases in the raw and annealed nanopowders were calculated
from the relative intensity of (1 0 1) anatase at 2 = 25.3◦ (IA )
and (1 1 0) rutile at 2 = 27.5◦ (IB ) diffraction peaks according to
Spurr and Myers formula YA = {1/[1 + 1.26 (IR /IA )]} × 100 [33]. A
Shimadzu 8400S Fourier Transform Infrared (FT-IR) Spectroscope
was used for the analysis of the different chemical bonds of the
nanocomposites. UV–vis diffuse reflectance spectroscopy (DRS)
spectra of calcined samples were recorded with a JASCO V-530
UV–vis Spectrophotometer in the wavelength range 200–800 nm
for the determination of the absorption edge and bandgap energy
of the post-synthesis heat-treated powders using Kubelka–Munk
function or remission, F(R) and the Tauc plot.
228 C.T. Fleaca et al. / Applied Surface Science 336 (2015) 226–233

Fig. 1. Photographies of the reactive flames from TLOP 6 (left), TLOP 7 (center) and TLOP 8 (right) experiments.

Table 1
Main experimental parameters for the raw titania-based nanopowders laser pyrolysis syntheses.

Experiment Gas flows through nozzles [sccm] having each a specific cross-section area ˚

Inner (cylindrical) ˚1 = 4.9 mm2 Middle (annular) ˚2 = 46 mm2 Outer (annular) ˚3 = 44.5 mm2

Air > TiCl4 C2 H4 > TiCl4 Air C2 H4 > [(CH3 )3 Si]2 O Ar Ar

TLOP 01 200 60 – – 1700 –

TLOP 6 200 60 200 20 – 1700
TLOP 7 200 60 300 20 – 1700
TLOP 8 200 60 400 20 – 1700

The inner air flow (noted Air > TiCl4 ) was mixed with the inner ethylene flow (C2 H4 > TiCl4 ) and then bubbled through the liquid TiCl4 . The middle ethylene flow
(C2 H4 > [(CH3 )3 Si]2 O) was bubbled through HMDSO liquid and then mixed with supplementary air flow (Air). Flushing ZnSe windows flows: 2 × 850 sccm Ar; resulted TiCl4
vapor flow carried by air–ethylene mixture: 7.2 sccm; resulted [(CH3 )3 Si]2 O vapor flow carried by ethylene: 2 sccm; laser power density above the injector: 1780 W/cm2 ;
working pressure: 550 mbar.

3. Results and discussions
As can be seen in the TEM an HR-TEM images (Figs. 2–5), all
the resulted raw crystalline nanoparticles (including those from
the TLOP 01 reference sample without silica) are surrounded by
a more or less thick disordered shell/coating. In order to explain
their formation, one must take into account the composition of
the reaction mixture and the particularities of the laser pyrolysis
technique. After absorbing the infrared laser photons, the vibra-
tionally excited ethylene molecules undergo collisions with the
surrounded species, transforming thus the laser energy into a
thermal one of the mixture molecules/radicals. In the same time,

Fig. 2. TEM and inserted HR-TEM images from TLOP 01 nanopowder. Fig. 3. TEM and inserted HR-TEM images from TLOP 6 nanopowder.
 C.T. Fleaca et al. / Applied Surface Science 336 (2015) 226–233
Fig. 4. TEM, HR-TEM (right inset) and the electron diffraction pattern including the
Miller indices and the measured interplanar distances (in nm) for anatase (A) and
rutile (R) phases (left inset) images from TLOP 7 nanopowder.
due to the presence of oxygen, competing exothermal oxidative
reactions occurs in the pyrolysis flame. Thus, TiCl4 , HMDSO and
C2 H4 species compete for the available amount of oxidant, result-
ing the corresponding solid (TiO2 , SiO2 ) and gaseous (CO2 ) oxides.
In our experiments, the reactive mixtures were oxygen-deficient,
as can be calculated from the amount of precursors. The total
oxidation of one C2 H4 mole (to form CO2 and H2 O) requires three
moles of O2 , thus each sccm of C2 H4 needs 15 sccm of air. The total
C2 H4 introduced flow was 60 sccm (for TLOP 01 experiment) or
80 sccm (for TLOP 6, 7, and 8), which requires 900 or 1200 sccm of
Fig. 5. TEM and inserted HR-TEM images from TLOP 8 nanopowder.
229
air, respectively, for their complete oxidation (600 or 800 sccm for
incomplete oxidation to CO and H2 O). The employed air flows were
lower than those required for a stoichiometric ethylene oxidation
to CO2 and even to CO: 200 sccm (for TLOP 01), 400 sccm (for TLOP
6), 500 sccm (for TLOP 7) and 600 sccm (for TLOP 8) as can be
extracted from Table 1. It seems that the oxygen affinity of TiCl4
is higher than those of C2 H4 , as proved by the presence of TiO2
phases and the absence of metallic Ti, TiC or Ti suboxides in our raw
nanopowders – as can be observed in the X-ray diffractograms from
Fig. 6, where the phase identification was based on the reference
X-ray diffractograms edited by International Centre for Diffraction
Data (former Joint Committee on Powder Diffraction Standards):
JCPDS card 21-1272 for anatase and JCPDS card 21-1276 for rutile.
The elemental composition (extracted for the mediated EDX
analyses) presented in Table 2 proves the presence of carbon in
all samples and points out the ethylene as their main source. The
formation of carbonaceous material as a result of a partial ethylene
decomposition is an indicator for the oxygen deficiency in the
reactive mixtures used in our laser pyrolysis experiments and was
reported by us in [24,34] for nanotitania-based particle synthesis
using the same method, Ti precursor and sensitizer. Following all
these considerations, the titania-based core–shell nanostuctures
genesis can be explained starting from the hot freshly formed
titania nanoparticles in the flame central zone which act as cat-
alytic surfaces for the deposition of carbonaceous layer provided
by ethylene decomposition, combined (for the TLOP 6,7 and 8
experiments) with the amorphous silica from HMDSO (introduced
through the annular nozzle) oxidation. As expected, with the
increasing amount of oxidant (O2 from air) the atomic carbon
percent in the resulted silica-containing titania powders decreases
from ∼25% to ∼15% due to the conversion to CO2 (and/or CO) of
a larger percent of C2 H4 molecules. Moreover, when comparing
the flame photographies from these three experiments (Fig. 1), a
clear change in their morphology for the experiment involving the
highest air flow (TLOP 8) can be observed. The flame was brighter
and extended not only upwards but also downwards to the injector
edge, whereas a light-green conical component appears in the
annular zone. Apparently, it seems that in this case the burning
process starts before the intersection with the infrared laser beam,
Fig. 6. Superposed X-ray diffractograms for the raw and post-synthesis annealed
nanopowders.
230 C.T. Fleaca et al. / Applied Surface Science 336 (2015) 226–233

somewhat similar with the case presented in [35], where a N2

YR %rutile/[%anatase + %rutile]
shielded and air coflow assisted H2 /O2 diffusion flame was used
also for titania nanoparticles synthesis from TiCl4 . However, in
that experiment, the CO2 laser beam irradiated a pre-existing
flame and, because of the absence the laser-absorbing molecules,

Mediated elemental composition extracted from EDX measurements, mean XRD anatase/rutile crystallite sizes and XRD derived anatase/rutile weight fractions from raw and annealed TiO2 -based nanopowders.
the only absorbing species were the freshly formed nanoparticles

Raw/calcined
which undergoes advanced coalescence, melting and even partial

46.45/45.74
17.70/16.99
60.64/60.35

22.00/21.80
evaporation. In our case, without the laser beam, the flame cannot
be ignited, requiring a certain laser power density threshold in
order to be enough to heat the ethylene-containing mixture and
to ignite the flame. In the TLOP 8 case, where the largest amount
%anatase/[%anatase + %rutile]

of available oxidant was used, it seems that the flame not only
propagates upstream, but also expanded downstream, thus part
of ethylene molecules from both inner and intermediate flow
(including also the TiCl4 and HMDSO vapors) undergo a similar
oxidation with those encountered in a normal combustion flame.
Raw/calcined

39.36/39.65
53.55/54.26
83.30/83.01

78.00/78.20

In the typical laser-induced suspended flame experiments, the

reaction zone could not propagate downstream due to the lower
amount of oxygen available and as consequence, even if the total
YA

gas velocity was lower than in the last experiment, the advancing
of the reaction front was possible only in the direction of the
crystalline size [nm]

reactive flows (one can observe from Fig. 1 that all the presented
Rutile XRD mean

flames expand upwards, inside the cylindrical collector, well above

Raw/calcined

the laser beam). In the last experiment, in spite of the higher

central flow velocity, the presence of supplementary oxygen
(even nitrogen-diluted) induces a more advanced oxidation of
17/15
15/14

24/23
19/20

combustible species with the releasing of more heat, which is

translated in the faster expansion of the reaction front in all direc-
tions, including also downstream (countercurrent propagation
crystalline size [nm]
Anatase XRD mean

flame). Here is possible that the system had passed a threshold

when the reaction front propagation velocity surpasses those of
Raw/calcined

the reactive mixture (which depends on the gas/vapors fixed mass

flows and on the nozzles cross-sections). The reaction front stops
22/21
17/17
18/19
18/18

near the end of the injector, where the gas confined in the tubular
and annular spaces suddenly expands in the reaction chamber, sig-
24.7 ± 1.7/12.4 ± 1.5
19.4 ± 1.7/10.2 ± 1.4

15.1 ± 0.7/12.3 ± 1.2

nificantly losing their laminarity (especially the annular flow which

19.9 ± 0.7/11 ± 0.4

clearly expands toward the inert argon external flow) and partially
Raw/calcined

mixing. The flames could not propagate further downstream due

to the higher gas velocities inside the confined concentric channels
C [at.%]

of the glass injector. Moreover, this change can be related not

only with the higher oxygen concentration but also with a higher
gas velocity through the intermediate annular nozzle from the
54.9 ± 0.3/63.4 ± 2.6
59.1 ± 2.6/9.6 ± 0.9

TLOP 8 experiment toward those from TLOP 6 and TLOP 7 runs.

54.1 ± 0.5/61.9 ± 2
55.5 ± 1.7/59 ± 1

Another observation come when comparing the 1.8 value of the

Raw/calcined

Ti/Si atomic ratio in the introduced volatile precursors (TiCl4 and

HMDSO) flows with those in the resulted powders extracted from
O [at.%]

the same Table 2 (∼2.4 for TLOP 6, ∼1.9 for TLOP 7 and ∼2 for TLOP
8). Thus, one can conclude that a part of siloxane precursor was not
converted to solid form and therefore the resulted powders have a
higher titanium (and a lower silicon) content than the precursors
9.8 ± 0.8/10.1 ± 0.9

mixture. This observation can be explained if we compare the rates

8.9 ± 0.8/9.3 ± 1
6 ± 0.4/7.7 ± 0.8
Raw/calcined

of our titania and silica precursors oxidative reactions at flame

temperatures around 1000 K (or less) presented in Fig. 9 from the
Si [at.%]

reference [13]. In these conditions the TiCl4 reacts much faster than
0/0

HMDSO, thus part of the Si-based precursor was not converted to

silica due to the insufficient residence time in the reactive flame.
Concerning the TLOP 01 reference sample (without silica) mor-
14.2 ± 1.7/16.5 ± 3.3
16.9 ± 1/17.7 ± 1.4
21 ± 4.2/30.1 ± 0.4

phology, the TEM image from Fig. 2 reveals the presence of round
19.2 ± 2/18.7 ± 1

particles, having sizes between 20 and 40 nm and surrounded with

Raw/calcined

a conformal few nm thick shell. The HR-TEM inset image from

Ti [at.%]

the same figure shows a group of crystalline nanoparticles sur-

rounded by turbostratic/disordered graphitic sheets. The 3.52 Å
interplanar distance measured on the top particle can be attributed
TLOP 01
Sample

to (1 0 1) anatase phase, found also in the corresponding X-ray

TLOP 6
TLOP 7
TLOP 8
Table 2

diffractgram (Fig. 6). In Fig. 3 TEM image from the raw TLOP 6
sample, the round (and few facetted) nanoparticles are embedded
 C.T. Fleaca et al. / Applied Surface Science 336 (2015) 226–233
in/surrounded by a thicker layer formed due the supplementary
introduction of HMDSO silica precursor in the reaction zone. In
this image, a bimodal particle distribution can be observed with
small nanoparticles having sizes around 10–12 nm, whereas for
the bigger ones diameters between 15 and 45 nm can be mea-
sured. The inset from the same image shows a well-crystallized
particle (25 nm in size) coated with rather disordered carbona-
ceous/amorphous silica layer, where the 2.18 Å interplanar distance
specific to (1 1 1) planes of the rutile phase can be identified. This
phase is also the majority one in this sample (60.64%) according to
Table 2 data extracted from XRD. For the next TLOP 7 sample, the
TEM image from Fig. 4 reveals the presence of aggregates composed
from round, ellipsoidal or partially facetted nanoparticles (with
sizes from 8 up to 54 nm, typical around 25–30 nm) also coated
with the more diffuse layer. A more detailed structure can be visu-
alized in the right down corner HR-TEM inset from the same image,
where the (1 0 1) anatase planes can be identified, delimited by tur-
bostratic graphite units composed from short packed graphenes
(spaced at ∼3.6–4 Å) mixed with more disordered zones (possibly
containing amorphous silica). The presence of turbostratic carbon
on the surface of laser-assisted synthesis of titania nanocrystals was
also reported by us in [24,32]. In the same Fig. 4, the left SAED image
on the inset (presenting rings and spots due to the diffraction of the
electrons on multiple nanocrystals) attests the simultaneous pres-
ence of anatase and rutile titania phases in this sample, confirming
thus the X-rays diffraction analysis (see Fig. 6 and Table 2). The
nanoparticles resulted from the last experiment (TLOP 8) – where
the greatest amount of air (and oxygen) was used – have sizes
between 8 and 25 nm and a more facetted, polyhedral morphol-
ogy, being covered with a very thin disordered layer and as can be
seen in the TEM and HR-TEM images from Fig. 5. In this case, due to
the different flame morphology (discussed above), associated with
the separate introducing of the two precursors we suspect that a
part of siloxane precursor was oxidated independently from the
titania particles surfaces, and a mixture of titania-rich and silica-
rich particles was obtained. Thus, the particles from Fig. 5 seem
to below to the titania-rich category. In the same time, having the
lowest carbon loading from all experiments, it is expected that the
TLOP 8 nanoparticles to have the thinnest carbonaceous shell. The
facetted nanocrystal form the HR-TEM inserted image (see Fig. 5)
can be attributed to the rutile phase due to the 3.21 Å identified
interplanar distance value of their (1 1 0) planes (a value close to
3.247 Å from XRD standard), which in this case is the minority phase
(22%) as resulted from Table 2. Generally, the mean crystallite size
values of each phase extracted with the aid of Scherrer equation
from the anatase (1 0 1) and rutile (1 1 0) XRD peaks (Table 2) can
be correlated with those from the presented TEM images, where
much smaller nanoparticle populations were considered. A clear
tendency of the rutile to anatase ratio (as well as the carbon con-
tent) to decrease with the increasing amount of injected air through
the second annular nozzle can be observed and was also reported
by us in [24]. This effect can be related to the role of carbon in
the enhancing the transformation of anatase to rutile through the
formation of oxygen vacancies [36], correlated with the high tem-
peratures in the flame environment. The mean crystallite size and
anatase to rutile ratios of the 450 ◦ C annealed powders (with lower
carbon content) are close to those of the raw powders as resulted
from Fig. 6 and summarized in Table 2. These results are expected
since for the pure titania nanopowders (synthesized by laser pyrol-
ysis from alkoxides) the anatase to rutile transformation becomes
significant only over 550 ◦ C [37]. It is worth nothing that no other
peaks than anatase and rutile were found in our raw or annealed
powders X-ray diffractograms, indicating thus the disordered or
amorphous state of the carbon and/silica components.
The superposed infrared spectra of the raw powders (Fig. 7)
show significant changes after the HMDSO introduction due to the
231
Fig. 7. Superposed FT-IR spectra of the raw titania-based nanopowders.
supplementary silica formation. There are also many peaks that
are common to all samples. The large peak at 3390–3420 cm−1 and
the small peak at 1632 cm−1 can be also found in [4,38,39]. They
were attributed to the stretching modes of O H bonds from the sur-
face adsorbed water and to the bending vibrations of physisorbed
and/or chemosorbed water, respectively. The weak band around
1410–1420 cm−1 found also in all samples was identified at
1400 cm−1 in a TiO2 hydrosol and attributed to Ti O Ti vibra-
tions [5]. The intense peak centered at 1095 cm−1 with his shoulder
at 1227 cm−1 , found only for silica-containing powders was also
reported at 1065 and 1200 cm−1 in [1] and attributed to Si O Si
vibrations. The small peak visible in the same powders spectra
centered around 940 cm−1 was considered an indication of the
chemical connection between titania and silica, being reported and
ascribed to Ti O Si vibrations [2,4,38]. Also, at 955 cm−1 the pres-
ence of Si OH stretching vibrations corresponding band was also
reported in [1], whereas the same Si OH attributed peak was found
at 921 cm−1 from SiOx films prepared by plasma CVD [40]. The
(Si C) stretching vibration infrared peak observed at 846 cm−1 for
Si/C/H materials obtained by CO2 laser decomposition of Si(C2 H3 )4
[41] or the peak at 802 cm−1 attributed to (Si C) + (CH3 Si)
vibrations (seen in a film obtained from [(CH3 )2 HSi]2 O laser decom-
position) [42] are missing from our silicon-containing samples
spectra, indicating the oxidation of HMDSO molecules in the pres-
ence of oxygen from the injected air in our experiments. The large
peak around 690–700 cm−1 was fond also in flame-made titania
FTIR spectrum and attributed to Ti O Ti bonding [9]. Another
intense peak, found also for all samples around 460–510 cm−1 and
may be a signature from Ti O bonds, reported also for titania thin
films [43] at 430 cm−1 or nanotubes [44] at 496 cm−1 . In the same
article [44], for titania–carbon nanocomposite, a strong IR line at
488 cm−1 was attributed to Ti C bond. Finally, for TLOP 8 sample,
another peak at 460 cm−1 can be identified, close to the Si O Si
bending mode peak at 470 cm−1 observed in the laser-synthesized
oxygen-deficient titania–silica powders [30].
The UV–vis absorbance superposed spectra of the annealed
powders (with lower carbon content) obtained from diffuse
reflectance spectroscopy (DRS) are presented in Fig. 8a. Their ultra-
violet absorption peaks are positioned around 330 nm, a value close
to those measured for TiO2 @C laser-synthesized nanocomposites
[24]. A clear enhanced visible light absorption can be observed for
the annealed silica-containing nanopowders (especially for TLOP
6(H) and TLOP 7(H) particles), when compared with the calcined
232 C.T. Fleaca et al. / Applied Surface Science 336 (2015) 226–233
Fig. 8. UV–vis absorbance spectra of annealed samples (a) and the corresponding Tauc plot data (b) for indirect electronic transition [F(R)h]1/2 vs. E (eV) for the same
annealed powders.
reference sample TLOP 01(H), even if their atomic carbon concen-
tration are quite similar (between 10.2% and 12.3% as can be seen
in Table 2). Moreover, unlike the carbon-modified TiO2 (n-TiO2 )
prepared from Ti sheet in furnace or in flame whose absorbance
goes to zero at 430 and 570 nm, respectively [45], our annealed
titania–carbon–silica samples do not show an absorbance satura-
tion even at 800 nm. The optical bandgap values of the annealed
powders were extracted from the Tauc plot of the Kubelka–Munk
functions [F(R)h]1/2 versus energy (h) measured in electron-
volts, according to Tandom and Gupta’s method [46] and presented
in Fig. 8b. Due to the fact that pure SiO2 phases do not exhibit
absorption in the 200–500 nm domain [38], the absorption prop-
erties observed for our annealed powders are only due to titania
phases and carbon. Yet, the amorphous silica on/near the titania
surface interacting with carbonaceous layer can influence the pho-
tocatalytic properties for example by enhancing the hydrophylicity
and the organic species adsorption. The pure (non-doped) anatase
and rutile phases exhibit an indirect bandgap of 3.2–3.3 eV and
3.0–3.1 eV, respectively [47]. Our annealed samples with the high-
est anatase content: TLOP 01(H) – 83.3% and TLOP 8(H) – 78%
show a lower bandgap (3.04 eV and 3.03 eV, respectively) than
pure anatase. Lower bandgap values were obtained for the sam-
ples with lower anatase content TLOP 6(H) – 39.65% and TLOP 7(H)
– 54.26% (2.94 eV and 2.79 eV, respectively). For these samples, the
corresponding absorption edge is 408, 409, 422 and 444 nm, respec-
tively, which is an indication of possible photocatalytic activity in
the visible region. These results confirm our precedent studies on
laser-synthesized TiO2 @C doped [32] or undoped [24] with sul-
fur, when also lower bangap values were reported. There are even
lower bandgap values reported for some interstitial and superficial
carbon doped/covered anatase obtained by sol–gel from TBOT [48]
which showed visible-light activity in methylorange degradation.
Recently, using a solvothermal method, other authors also obtained
carbon-doped TiO2 with low bandgap from TBOT (2.84 eV) – con-
taining only anatase – or from TiCl3 (2.39 eV) – where anatase, rutile
and brookite phases coexist –, both presenting in the same time
intense photoactivity under visible light [49]. It must be noted that
the reference commercial photocatalyst Degussa P25 pure nano-
metric titania contains a significant rutile percent (∼25%) [50] and
have a higher bandgap energy (3.2 eV) [32]. Moreover, another
nanometric titania photocatalyst having rutile as majority phase
(∼53%) was able to efficiently photodegrade chlorinated phenol
[51].
In contrast to our oxidative laser pyrolysis method, the carbon
incorporation control is more difficult to be achieved in the alter-
native classic atmospheric pressure open flame synthesis of such
materials due to the uncontrolled involvement of the surrounding
oxygen from air which acts as a supplementary oxidant besides
the fixed introduced O2 flow together with the fuel and the oxidic
precursor. Moreover, the laser power density in the flame can be
varied with the possibility to control the size, morphology, agglom-
eration degree and crystalline phase as was presented for the case
of pure TiO2 or SiO2 nanoparticles in [35]. A better degree of the
control of carbon percent and their morphology in these nanocom-
posites – without the need of the final air annealing step – can
also be achieved with our method by using higher oxygen to nitro-
gen (or argon) ratio in the reactive flow, independent introduction
of TiCl4 vapors and ethylene sensitizer/carbon donor flows and/or
by tuning the gas velocities through the injector nozzles. Besides
the fast continuous production of nanopowders, another advantage
of the laser oxidative pyrolysis method is the avoiding the large
amount of solvents usually needed by the sol–gel methods. The
scalability of the laser pyrolysis method to pilot plant production
of TiO2 was demonstrated [52], being thus an important advantage
of this technique.
4. Conclusions
Carbon and silica disordered/amorphous layers coated TiO2
nanopowders containing a mixture of anatase and rutile crystalline
phases were successfully synthesized using a continuous oxidative
laser pyrolysis method. We employed TiCl4 and HMDSO vapors as
precursors and C2 H4 as sensitizer/carbon precursor in the presence
of substoechiometric (relative to the ethylene oxidation) amount
of air. Infrared spectra of nanopowders confirm the presence of
Ti O, Si O and Ti O Si bonds, whereas EDX estimations show a
Ti to Si atomic ratio between 1.9 and 2.4. Their carbon content was
controlled using different air flows and subsequent furnace calcina-
tion down to ∼11–12 at.%. For the raw powders, a carbon content
decreasing accompanied by the anatase to rutile ratio increasing
with the increasing air flow was observed. Using the highest air
flow, the reaction zone change their morphology by extending
both upward and downward and the apparition of a second conical
flame, possibly due to exceeding of a threshold when the burning
velocity becomes higher than those of the central reactive flow.
UV–vis spectra of the annealing samples reflect the influence of
the anatase/rutile mixture and carbon content, whereas their lower
bandgap (when compared with those of Degussa P25 commercial
nanopowder) values suggest their possible photocatalytic activity
under visible light against organic substances, a direction that will
be explored in the future experiments.
Acknowledgements
The financial support is gratefully acknowledged to Roma-
nian Ministry of Education and Research under the Project
 C.T. Fleaca et al. / Applied Surface Science 336 (2015) 226–233
PNCD2 IDEI no. 80/2011 and to Romanian Ministry of European
Funds and Sectoral Operational Program for Human Resources
Development 2007–2013 through the Financial Agreement POS-
DRU/159/1.5/S/132395 (INNO Research).
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