Applied Surface Science 302 (2014) 198–204

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Applied Surface Science

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

Recent progress in the synthesis of magnetic titania/iron-based,

composite nanoparticles manufactured by laser pyrolysis
C.T. Fleaca a , M. Scarisoreanu a,∗ , I. Morjan a , R. Alexandrescu a,1 , F. Dumitrache a ,
C. Luculescu a , I.P. Morjan a , R. Birjega a , A.-M. Niculescu a , G. Filoti b , V. Kuncser b ,
E. Vasile c , V. Danciu d , M. Popa d
a
National Institute for Plasma, Laser and Radiation Physics (NILPRP) , Atomistilor 409, P.O. Box MG 36, R-077125, Magurele, Bucharest, Romania
b
National Institute for Materials Physics (NIMP), Atomistilor 105bis, P.O. Box MG7, R-077125, Magurele, Bucharest, Romania
c
METAV R&D, C.A. Rosetti 31 and Politehnica University of Bucharest, Independenei 313, 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: We report the continuous, single step synthesis of titania/iron-based magnetic nanocomposites in a sin-
Received 1 July 2013 gle step using gas-phase laser pyrolysis technique by separately and simultaneously introducing the
Received in revised form 20 October 2013 precursors (together with C2 H4 sensitizer) in the reaction zone: Fe(CO)5 on the central flow and, using
Accepted 21 October 2013
air as carrier, TiCl4 on the annular coflow. The laser power and, for the last experiment, the injection
Available online 30 October 2013
geometry were modified in order to change the Fe/Ti ratio in the resulted nanopowders. Due to the spe-
cific geometry, the reaction zone (visible as a flame) have a reductive inner central zone surrounded
Keywords:
by and oxidative environment, allowing the formation of the metallic–carbidic iron and/or iron-doped
Laser pyrolysis
Iron-based magnetic nanocomposites
titania and iron oxide nanophases. The raw Fe-containing nanopowders have a ferromagnetic behavior,
Titania those synthesized at higher laser power and gas velocities show significant saturation magnetization
Ms values (10–12 emu/g), whereas those obtained (with higher yield and carbon content) at lower laser
PACS: power and gas velocities (using wider central nozzle cross-section) have a very weak magnetization
81.16.Mk (Ms ∼ 0.05 emu/g) in spite of the higher ethylene carried Fe(CO)5 flow. The powders were annealed in air
75.75.Fk
at 400 ◦ C show lower carbon content and, for those highly Fe-doped, the hematite phase formation. Pre-
85.70.−w
liminary tests using UV light confirm the photocatalytic action of the annealed nanopowders in salicylic
81.07.Wx
61.46.Df acid degradation process in solution.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction [2]. In order to be applied for wastewater depollution, TiO2 must

Titania (titanium dioxide TiO2 ) have three main crystallographic
forms: anatase, rutile (both tetragonal) and brookite (orthorom-
bic). Their most spread application are as fillers in paints, varnishes,
plastics or for paper (∼80% of the world consumption). Other appli-
cations, which have a ∼8% market share, are as pigment for inks,
fibers, rubber, cosmetics or food products. The remaining ∼12%
are for producing metallic pure Ti, glass/electroinsulating ceram-
ics, electrical conductors, chemical intermediates and catalysts [1].
The last specified application of TiO2 (especially the anatase form)
is related to their photocatalytic properties, allowing the decom-
position of organic pollutant compounds or photogeneration of
hydrogen, enhanced for is nanosize form, which have a greater
specific surface and activity than bulk/micronic-size counterpart
∗ Corresponding author. Tel.: +40 21 4574489; fax: +40 21 4574243.
E-mail address: monica.scarisoreanu@inflpr.ro (M. Scarisoreanu).
1
The Senior Researcher Dr. Rodica Alexandrescu had deceased during the prepa-
ration of the manuscript.
have long-term stability, a high efficiency, low-cost and long-term
stability [3]. The slurry/suspension TiO2 reactor is usually employed
for this scope, due to the intrinsic high specific surface area, good
dispersion conditions and efficient light absorption [4]. After the
water purification, the separation of the employed TiO2 photocat-
alyst is required, especially from a large volume of water, which
is both cost-expensive and time-consuming even when various
solid support immobilization/impregnation techniques were used
which also decrease the effective surface photocatalytic area [5].
A convenient way to overcome these drawbacks is to coat a mag-
netic nanocore with TiO2 shell or to connect the TiO2 to magnetic
nano-particles, resulting nanocomposites which can be easily sep-
arated with the aid of a magnetic field and eventually recycled
[6]. Obviously, a simple mechanical mixture of magnetic and pho-
tocatalytic particles (even a very homogeneous one) can’t have
the behavior shown by these nanocomposite due to the lack of
connectivity between the two components which not allow the
high magnetic recovery of the photocatalyst. These new materials
belong indeed to the nanocomposites category, fulfilling de defini-
tion of being “a multiphase solid material where one of the phases

0169-4332/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2013.10.138
 C.T. Fleaca et al. / Applied Surface Science 302 (2014) 198–204
has one, two or three dimensions of less than 100 nanometers (nm)”
[7], having a nanometric dispersed magnetic phase and a nano or
submicron titania as the dispersing/surrounding phase. In these
nano-composites, the titania high specific surface area in contact
with the external mediun is not altered by the magnetic compo-
nent, allowing thus a good photocatalytic action. As magnetic cores,
usually magnetite covered with thin silica [5,6], [8–10] or carbon
[11] layer or uncovered [12] were employed. Also, a spinel magnetic
core (zinc manganese ferrite) on activated carbon particles cov-
ered with TiO2 was reported to surpass the photocatalytic methyl
orange dye degradation efficiency of commercial TiO2 Degussa
P25 [13]. Better than Degussa P25 in solar light photodegrada-
tion of Reactive Brilliant Red X3B dye was also another activated
carbon supported/absorbed Fe3 O4 /␥Fe2 O3 NPs and coated with
N-doped TiO2 photocatalyst [14]. One original approach involves
the utilization as magnetic cores of the metallic Fe-filled graphitic
carbon nanocapsules (made by arc discharge) and coated with
nano-crystalline TiO2 , resulting a better than normal sol–gel
made TiO2 recyclable photocatalyst for NO photooxidation [15].
The second approach involved the same P25 NPs (nanoparticles)
covered with polycationic poly(dialyldimethylammonium chlo-
ride) which were electrostatically linked with polyanionic sodium
poly(styrenesulfonate) covered maghemite NPs [16].
It is known that the support materials greatly influence the
activity of catalyst. Titania was studied as support for Fe:Co
bimetallic catalyst in Fischer–Tropsch hydrogenations of CO to
obtain methane and various alkanes and olefins. In this case,
the Fe3+ and Co2+ incipient wetness TiO2 impregnated ions
were reduced to metallic phase by long-term hydrogenation at
250–400 ◦ C [17].
Laser oxidative pyrolysis using TiCl4 as volatile precursor (with
C2 H4 sensitizer) was reported by us to be a continuous technique
that allows the obtaining titania nanoparticles with high anatase
concentration [18]. Using premixed TiCl4 and Fe(CO)5 vapors and
air (or N2 O) as oxidant, we reported the synthesis of low and high
concentation Fe doped TiO2 nanopowders (Fe/Ti atomic ratio from
0.07 up to 0.51) with uniform and interstitial/substitutional doping
which was certified by the absence of any Fe-based phase XRD
peaks (only anatase and rutile are visible) [19], [20]. Here, based on
our previous experiences concerning the synthesis of Fe–Fex C@C
nanocomposites [21], we analyzed the nanopowders obtained
from a laser pyrolysis experimental set-up where the ethylene-
sensitized Fe and Ti precursors are separately and simultaneously
introduced, keeping a reductive environment in the center of reac-
tion zone (where the Fe(CO)5 vapors were injected) and a more
oxidative medium at towards periphery (where air and TiCl4 were
supplied). This specific configuration allows the one-step synthe-
sis of magnetic nanocomposites which contain metallic/carbidic Fe
toghether with titania phases. This kind of nanocomposites was
never been reported to be synthesized in a single step and in con-
tinous mode to our knowledge. We must emphasize that exist
also other reports in which Fe-doped TiO2 NPs/or coatings were
obtained by gas-phase techniques, such as those which employed
oxidative RF (Radio Frequency enhanced) thermal plasma [22] or
Metal Organic Chemical Vapor Deposition (MOCVD) [23,24] from
titanium tetrabutoxide and ferrocene as precursors which have as
a major desavantage their high boiling temperatures compared to
those of the volatile TiCl4 and Fe(CO)5.
2. Experimental
The laser pyrolysis experimental set-up used in to synthesize
the TiO2 -based nanopowders is similar with those reported in
[21]. Briefly, the continuous-wave CO2 laser beam ( = 10.6 ␮m)
orthogonally intersect the gas flows emerging from three tubular
199
concentric injectors (nozzles). The Fe(CO)5 vapors are introduced
together with the C2 H4 carrier/sensitizer through the inner central
nozzle, whereas TiCl4 is bubbled with an ethylene-air mixture and
the resulted vapors pass through the annular space of the second
nozzle. In the same time, a third argon external co-flow is employed
to shield the reactive mixture. The main experimental parameters
are summarized in Table 1, where the circular or annular cross-
sections active surface areas of the nozzles are also presented. The
pressure inside the reaction chamber is kept constant by balancing
the incoming flows and the extracted (with a vacuum pump) flow
with the aid of a throttle valve. Due to the laser absorption and to the
oxidation reactions, the injected gas/vapor are very rapidly heated
(up to 800 ◦ C) and the precursors decomposed/oxidized resulting
nano-sized particles which leave the laser irradiation zone (visi-
ble as a floating flame) and are carried by the non-reacting and
reaction-resulted gases as a smoke. The nanocomposites are finally
captured on the inner walls of the collecting chamber and on the
surface of a ceramic porous filter.
The samples were investigated with a Tecnai F30 G2 (300 kV)
Transmission Electron Microscope (TEM), a PANalytical X’Pert MPD
theta–theta X-ray diffraction (XRD) system using a Cu K␣ source
(0.15418 nm) and Cryogenic Limited Vibrating Sample Magne-
tometer (VSM).
The Mossbauer spectra were collected using a constant accel-
eration spectrometer with a symmetrical waveform, having a Co57
source in Rh matrix. The resulted isomer shifts are referred to bcc Fe.
A He-bath cryostat was used for low-temperature measurements.
EDS (Energy Dispersive Spectrometry) from liquid N2 cooled
EDAX Spectrometer mounted on a Scanning Electron Microscope
SEM FEI Quanta Inspect was employed to evaluate the atomic com-
position of the nanopowders.
For the photocatalytic activity measurements, a photore-
actor system with six Black Light Blue Linear Fluorescent
Tubes (F6T5, 6 W, Lumen) (irradiation distance = 3 cm, irradiation
time = 3.5 h) was used. The photocatalyst suspension containing
salicylic acid (c0 , substrate = 0.5 mM, csuspension = 1.0 g/l photocatalyst,
Vsuspension = 50 ml) was continuously purged by air in order to main-
tain the dissolved oxygen concentration constant during the whole
experiment. The reactor was thermostated at 25 ± 1 ◦ C and the sus-
pension pH was 5.3. Before UV irradiation the photoreactor with
the suspension was kept in dark for 30 min in order to achieve the
equilibrium of the adsorption/desorption process. The decrease of
the salicylic acid concentration was monitored by UV spectroscopy
( = 297 nm). Before the spectrophotometric measurement, the
samples were filtered by using hydrophylic Teknokroma syringe fil-
ters (M.E. Cellulose, 0.45 ␮m mean pore size, 25 mm diameter). The
assessed error of the photocatalytic tests (based on reproducibil-
ity experiments) was 5–9%. The average rate of the photocatalytic
degradation of the model compounds was considered to evaluate
the efficiency of the photocatalyst.
3. Results and discussions
Laser pyrolysis technique is based on the resonant absorption of
infrared laser photons by the specific molecules called sensitizers
which become vibrationally excited and transfer the excess energy
by collisions to other species from reactive mixture. In our specific
case, supplementary heat comes from oxidation reactions of both
metallic precursors and the ethylene sensitizer. Thus, the central
Fe(CO)5 molecules in an anoxic, reductive C2 H4 -rich environment
rapidly decompose to form hot Fe atoms, clusters and nanoparti-
cles which are saturated in carbon (from C2 H4 decomposition and
CO disproportionation). The resulting Fe and Fe3 C nanocrystals are
visible in the HR-TEM images of the IT1 sample from Figs. 2 and 3
inserts and in X-ray diffractograms of the IT1 and IT3 samples
200 C.T. Fleaca et al. / Applied Surface Science 302 (2014) 198–204

Table 1
Main experimental parameters for the laser pyrolysis synthesis of titania reference nanoparticles and iron-titania nanocomposites.

Sa mple ˚Ar windows /˚Ar 3 rd ˚air/TiCl4 2 nd ˚C2 H4 /TiCl4 2 nd ˚C2 H4 /Fe(CO)5 1 st 1st nozzle 2 nd nozzle 3
rd
nozzle Laser Pressure Productivity
nozzle [sccm] nozzle[sccm] [sccm]
nozzle nozzle [sccm] cross-section area cross-section area cross-section area power [W] [Pa] [g/h]
[mm2 ] [mm ] 2
[mm ] 2

IT-0 1700/2000 300 45 0 1.7 31.4 175.8 450 4 × 104 1.92

IT-1 1700/2000 300 45 30 1.7 31.4 175.8 600 4 × 104 1.41
IT-3 1700/2000 300 45 30 1.7 31.4 175.8 450 4 × 104 1.95
IT-4 1700/800 350 50 50 4.9 45.97 44.5 400 4 × 104 4.27

Table 2
Atomic composition of raw and air-annealed samples from EDS measurements.

Sample Fe [at.%] Ti [at.%] O [at.%] C [at.%] Fe/Ti atomic ratio

IT0 Raw powder 0 30.84 58.36 10.80 0

Treated in air at 400 ◦ C (2 h) 0 26.27 63.01 10.72

IT1 Raw powder 6.52 18.23 35.53 39.72 0.36

Treated in air at 400 ◦ C (2 h) 7.86 21.75 51.47 18.92

IT3 Raw powder 6.23 19.47 45.25 29.05 0.32

Treated in air at 400 ◦ C (2 h) 7.09 22.48 50.42 20.01

IT4 Raw powder 0.41 22.26 35.58 41.75 0.02

Treated in air at 400 ◦ C (2 h) 0.71 26.40 46.70 26.19

Table 3
Anatase/rutile compositions and their mean crystalline size from XRD.

Samples As prepared (raw) TiO2 Calcinated at 400 ◦ C TiO2

A (%) R (%) DA (nm) DR (nm) A (%) R (%) DA (nm) DR (nm)

IT-0 91 9 29 43 91 9 29 43
IT-1 81 19 22 33 79 21 19 27
IT-3 81 19 25 33 81 19 21 27
IT-4 96 4 23 28 95 5 23 27

(around 2 = 45◦ , Fig. 5). Due to the higher gas velocity on the The same sample contains the lowest percentage of Fe, in spite of
central flow, some Fe(CO)5 molecules and Fe clusters are mixed introduction the highest ethylene-containing Fe(CO)5 flow. On the
with the TiCl4 - and C2 H4 -containig oxidative medium from the other hand, the powder productivity in this experiment was more
annular co-flow, resulting Fe-doped TiO2 nanoparticles and/or than double that from any other three experiments, pointing the
titanomagnetite nanocrystals (visible as small peaks in the IT1 XRD role of Fe(CO)5 in the catalytic thermal decomposition of ethylene
from Fig. 5) and perhaps other “amorphous to XRD” oxidic iron (also the carbon atomic percent in this sample was the highest),
phases (phases that are too disordered to have distinctive peaks similar with those found in [21] for acetylene. The IT0 reference
in the X-Ray diffractograms and who can’t be distinguished from sample contains a high percent of the photocatalytic active,
the background noise). The second nozzle flow contains 61.5 (or
71.75) sccm O2 , 238.5 (or 278.25) sccm N2 (total 300 (or 350) sccm
as synthetic air – see Table 1), 45 (or 50) sccm C2 H4 and 14.79 (or
16.49) sccm of carried TiCl4 vapors. Each mole of ethylene requires
three or two moles of O2 for a total or partial oxidation (to CO2 or
to CO). In our experiments, the available oxygen is less than those
required even for the partial oxidation of the C2 H4 from the second
annular flow and thus a part of ethylene decomposes in the laser
beam with the formation of disordered carbon (and hydrogen).
Also, it seems that the reactivity towards O2 of TiCl4 is greater than
those of the C2 H4 , as proved by the titania formation in our exper-
iments. The resulted carbon can be seen in all the TEM images as a
more or less thin coating layer or matrix covering/embedding the
titania nanoparticles (Figs. 1–4). The carbon presence is attested
also through the EDS atomic evaluation (see Table 2). The TiCl4
conversion to TiO2 can be considered almost quantitative for IT1,
IT2 and IT3 experiments since no XRD peaks of metallic Ti, TiC
or lower-valence Ti oxides were observed at XRD and the Ti/O
atomic ratio (from EDS) is near 2. For the IT4 sample, obtained with
different injection geometry (larger inner and annular nozzles
cross-section areas) and with lowest laser power, there is a clear
oxygen deficiency, with Ti/O atomic ratio of 0.62, pointing for the
possible additional formation of TiO2−x or/and TiC phases which
seems to be too disordered to be visualized by X-ray diffraction. Fig. 1. TEM and inserted HR-TEM images form IT0 sample.
 C.T. Fleaca et al. / Applied Surface Science 302 (2014) 198–204
Fig. 2. TEM and inserted HR-TEM images form IT1 nanocomposite.
Fig. 3. TEM and inserted HR-TEM images form IT3 nanocomposite.
yet metastable phase – anatase (see Table 4). The preferential
formation of anatase in far-from-equilibrium conditions from the
laser oxidative flame can be explained from the kinetic point of
view on the basis of nucleation rate [22]. The TEM image from
Fig. 1 shows majoritary polyhedral equiaxed or elongated anatase
nanoparticles alongside with others having a spherical shape with
diameters between 15 and 50 nm, while the XRD calculated mean
crystallite diameter (Table 3) is 29 nm for anatase and 43 nm for
rutile. For the higher Fe-content samples IT1 and IT3, the presence
of iron seems to enhance the rutile percentage (see Table 4) and
Table 4
Salicylic acid UV photodegradation rates in the presence of the annealed titania-
based nanopowders or Degussa P25 Aeroxide reference.
Salicylic acid (0.5 mM) photodegradation rate [mM/min]
P25-Aeroxide IT0 annealed IT3 annealed IT4 annealed
2.23 × 10−6 1.59 × 10−6 0.47 × 10−6 0.77 × 10−6
201
Fig. 4. TEM and inserted HR-TEM images form IT4 nanocomposite.
in the same time decreased the XRD crystalline size. The main
difference between IT3 and IT1 experiments is the laser power
input (450 W versus 600 W) and implicit, the flame temperature
which increases with the laser irradiation intensity and thus
converting more ethylene to carbon. One can observe in the
higher temperature synthesized IT1 powder TEM image (Fig. 2) a
conformal thick carbon coating, whereas in the lower temperature
obtained IT3 sample TEM image (Fig. 3), the carbon coating have a
matrix porous appearance, containing, beside the big (20–50 nm)
anatase/rutile polyhedral nanoparticles a large number of few
nm “nodules”. Some of these small nanoobjects can be clusters of
metallic/carbidic iron protected from oxidation by the carbona-
ceous matrix, as can be seen in Fig. 3 insert. The last sample, IT4
presents also a high carbon content, visible in Fig. 4 TEM image
as a homogeneous diffuse coating which embeds the aggregated
rounded/facetted anatase nanoparticles with diameters around
30–40 nm. Also here are clearly visible the small 2–4 nm discrete
nanoparticles spreaded in great number in the carbon-based
matrix. All the raw samples were treated in air during 2 h at
400 ◦ C in order to oxidize the disordered carbon. As a result, the
carbon percent was significantly diminished in the Fe-containing
samples (see Table 2). Also, the post-synthesis annealed higher
iron content nanocomposites IT1 and IT3 diffractograms show
Fig. 5. X-ray diffractograms of raw nanopowders.
202 C.T. Fleaca et al. / Applied Surface Science 302 (2014) 198–204
Fig. 6. X-ray diffractograms of the 400 ◦ C air annealed samples.
hematite peaks (Fig. 6) instead those of metallic/carbidic iron,
which is an indication of the limited protective role of the carbon
coating/matrix against oxidation at relative high temperatures.
The hysteresis magnetic curves at different temperatures (Fig. 7)
points out the weak ferromagnetic behavior of all Fe-containing
samples. Due to their similar atomic Fe content the room tem-
perature saturation magnetization of IT1 and IT3 nanocomposites
are very near, around 10 emu/g, whereas the low Fe-containing
titania sample IT4 has also a very weak saturation magnetiza-
tion (around 0.05 emu/g). Their coercive fields values (400–600 Oe)
increases with decreasing the temperature. This magnetization
behavior can be a result of superposed magnetism of oxidic and
carbidic iron phases. The field cooled hysteresis curves (Fig. 8e–
g) do not shift with the temperature variation, which is a proof of
non-interacting magnetic phases (the oxidic phased do not inter-
act with metallic/carbidic ones), may be due to the protective role
of the carbonaceous coating/matrix. The Zero Field Cooling–Field
Cooling (ZFC–FC) curves of the IT1 sample (insert in Fig. 8c) suggest
the presence of relative big magnetic Fe-containing nanoparticles
with blocking temperatures much higher than 350 K. Magnetiza-
tion curve at 20,000 Oe shows the low temperature activation of a
new magnetic phase. Similar magnetization curves recorded from
4 to 273 K at 20 kOe were found from amorphous iron sulfide rich
(90 wt.%, having 11.4 wt.% atomic Fe concentration) solid extracted
from Western U.S. Paraho Shale Oil and their shape was explained
as resulting from the mixture of a weak ferromagnetic phase and
a paramagnetic one. The authors pointed that “the paramagnetic
phase seems to reflect the behavior characteristic of a Curie-Weiss
type material and appears to be more pronounced than the fer-
romagnetic phase” [25]. A similar shape curve, yet at much lower
magnetic fields (20 Oe) and with considerably lower magnetization
values (up to 0.002 emu/g) was also found for FC measurements
of maghemite nanowires inside double-walled carbon nanotubes
[26]. In this particular case, the missing of FC saturation “points
Fig. 7. Hysteresis magnetization curves at low and (inserted) high applied magnetic field at 5, 10, 20, 100, 200 300 K for IT1 (left), IT3 (middle) and IT4 (right) samples.
out to the existence of a (quasi) independent relaxation” related
to a superparamagnetic behavior [26]. The blocking temperature
of the low Fe content/TiO2 IT4 sample can be estimated from their
ZFC curve (insert Fig. 8 d) at ∼130 K. Similar activation of a new
magnetic phase (only much weaker than in IT1 or IT3) near 0 K
can also be observed in this sample magnetization curve at 20 kOe.
The shape of the inserted ZFC-FC curves of the IT4 sample is simi-
lar with those resulted from amorphous Fe2 O3 dispersed in a SiO2
matrix – also a nanoparticle system without interparticle inter-
actions (which has a lower blocking temperature: 25 K) [27]. By
analogy, it can be supposed that the role of the SiO2 matrix in the
separation of the magnetic nanoparticles is played by the carbona-
ceous matrix and TiO2 nanoparticles in our case, fact confirmed by
the TEM image from Fig. 4
Mossbauer spectroscopy spectra for the IT1 sample at different
temperatures (Fig. 8a) present a superposition of doublets and sex-
tets, suggesting the presence of the following phases: iron oxide
(mixture of maghemite and magnetite) about 22%, metallic iron
∼16%, iron carbide ∼18%, superparamagnetic iron oxide ∼18% and
superparamag-netic iron carbide ∼17%. Iron oxide nanoparticles
seems to be smaller than those of carbide. The Mossbauer spec-
tra for IT3 sample (Fig. 8 b) is very similar with those of IT1 (with
similar percentages of the four magnetic phases). The IT4 sample
Mossbauer spectrum at very low temperature (5 K) (lower part of
Fig. 8 b) is more difficult to be deconvoluted due to the very low Fe
content, yet also the four phases can be extracted.
The iron-containing raw powders show very weak photocat-
alytic activities in salycilic acid degradation from solution due to the
high carbon content (∼30–40 at.% – as shown in Table 2). This excess
carbon is a very good UV and visible light absorber and block the
active surfaces of anatase nanocrystals, thus drastically decreasing
the photocatalytic efficiency of these nanopowders. In order to
increase their photoactivity, the raw powders were annealed in air
at temperatures around 400 ◦ C during 2 h, when part of the car-
bon is burned. As consequence, the carbon content decreases to
∼19–26 at.% for the magnetic samples. It should be noted that the
IT0 raw powder have a smaller carbon content (10.8 at.%) which
almost not decrease upon air annealing. As pointed already, the
presence of Fe seems to catalyze the excess ethylene decomposition
in pyrolysis flame and consequently the formation of high carbon
content nanoparticles. Even upon oxidation, there is a part of carbon
resistant to burning and this seems to negatively influence the pho-
tocatalytic performance of the annealed powders when compared
with Degussa (Evonik) P25 Aeroxide® nanoparticles (the standard
TiO2 photocatalyst). Being obtained by the hydrolysis of TiCl4 vapor
in an oxy-hydrogen flame [28], the P25 nanoparticles do not con-
tain carbon and have a high anatase percent. The photodegradation
curves of the salicylic acid in presence of the annealed powders or
P25 are presented in Fig. 9 and the corresponding oxidative degra-
dation rate of the organic acid in Table 4. The annealed samples IT1
and IT3 behave very similar and only the data for IT3 are presented.
The annealed IT0 sample has the higher activity (yet smaller than
 C.T. Fleaca et al. / Applied Surface Science 302 (2014) 198–204 203

Fig. 8. Mossbauer spectra at low temperatures for (a) IT1, (b) IT3 and IT4 nanocomposites. Magnetization curve at 20,000 Oe and inserted ZFC–FC curves for (c) IT1 or IT3
and (d) IT4 samples. Field cooled hysteresis curves at low temperatures for (e) IT1, (f) IT3 and (g) IT4 nanopowders.

pure titania Degussa P25 powder) and the lowest carbon content
from all our heated powders. The weaker photocatalytic activity is
provided by the annealed IT3 sample, in spite of their lower carbon
content (20 atomic %) than those of the corresponding IT4 sample
(26 at.%). This behavior can be explained by the higher anatase (the
most photoactive phase) content of annealed IT4 (95%) towards
those of annealed IT3 (81%) as shown in Table 3. Further experi-
ments using higher oxygen percent in the mixture with the inert
gas in the laser pyrolysis should allow the obtaining of lower carbon
content nanopowders with photocatalytic properties approaching
those of Degussa P25 which responds in the same time to external
magnetic fields.

4. Conclusions

Using a special configuration laser oxidative pyrolysis tech-

Fig. 9. UV photodegradation curves of salicylic acid in the presence of the annealed
nanopowders or Degussa P25 Aeroxide reference.
nique with the separately introduction of Ti and Fe precursors, we
succeeded to obtain in continuous mode and single step nanocom-
posite powders containing both metallic/carbidic iron and titania
phases. More experiments are needed to elucidate the mechanisms
and the phase segregation in this far-for-equilibrium gas-phase sys-
tem in order to obtain an advanced magnetic photocatalyst, which
204 C.T. Fleaca et al. / Applied Surface Science 302 (2014) 198–204

must to have a lower carbon content, a high anatase percent and
also to keep a significant percent of a magnetic phase
Acknowledgements
Financial support from is gratefully acknowledged to Romanian
Ministry of Education and Research under the Project PNCD2 IDEI
Nos. 80/2011 and C1-07 IFA-CEA.
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