Journal of Sulfur Chemistry

ISSN: 1741-5993 (Print) 1741-6000 (Online) Journal homepage: https://www.tandfonline.com/loi/gsrp20

Synthesis of carbon nanotube/titanate nanotube

composites with photocatalytic activity for H2S
oxidation

Thu Ha Thi Vu, Hang Thi Au, Thu Trang Thi Nguyen, Manh Hung Do, Minh Tu
Pham, Duy Hung Bui, Thanh Son Phan & Dinh Lam Nguyen

To cite this article: Thu Ha Thi Vu, Hang Thi Au, Thu Trang Thi Nguyen, Manh Hung Do, Minh Tu
Pham, Duy Hung Bui, Thanh Son Phan & Dinh Lam Nguyen (2017) Synthesis of carbon nanotube/
titanate nanotube composites with photocatalytic activity for H2S oxidation, Journal of Sulfur
Chemistry, 38:3, 264-278, DOI: 10.1080/17415993.2016.1276182

To link to this article: https://doi.org/10.1080/17415993.2016.1276182

Published online: 09 Jan 2017.

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JOURNAL OF SULFUR CHEMISTRY, 2017
VOL. 38, NO. 3, 264–278
http://dx.doi.org/10.1080/17415993.2016.1276182

Synthesis of carbon nanotube/titanate nanotube composites

with photocatalytic activity for H2 S oxidation
Thu Ha Thi Vua , Hang Thi Aua , Thu Trang Thi Nguyena , Manh Hung Doa ,
Minh Tu Phama , Duy Hung Buia , Thanh Son Phanb and Dinh Lam Nguyenb
a National Key Laboratory for Petrochemical and Refinery Technologies, Hanoi, Vietnam; b The University of
Danang, University of Science and Technology, Danang, Vietnam

ABSTRACT ARTICLE HISTORY

Composites of carbon nanotubes – titanate nanotubes (MWNTs/ Received 27 May 2016
TNTs) – were successfully synthesized by the hydrothermal reac- Accepted 19 December 2016
tion process. The morphology of the MWNTs/TNTs composites was KEYWORDS
observed by transmission electron microscopy. Fourier transform Composite materials;
infrared spectroscopy was used to characterize the molecular inter- nanostructures; carbon
actions between TNTs and MWNTs in the composites. The X-ray nanotubes; titanate
diffraction of TNTs and MWNTs/TNTs composites exhibited the exis- nanotubes;
tence of titanate phase (100), (102), (020) and (422). The charge photoluminescence
recombination of MWNTs/TNTs composites was examined by pho- spectroscopy
toluminescence spectrum. The photocatalytic activity of TNTs and
MWNTs/TNTs composites was evaluated on the basis of the model
oxidation reaction of H2 S.

100
H2S Conversion (%)

90 (a)
1/10 MWNTs/TNTs
80 1/1 MWNTs/TNTs
2/1 MWNTs/TNTs
70

60

50

40
0 100 200 300 400 500 600 700 800 900 1000 1100
Time on Stream (minutes)

100
Sulfur Selectivity (%)

90 (b)
80

70

60
1/10 MWNTs/TNTs
50 1/1 MWNTs/TNTs
2/1 MWNTs/TNTs
40
0 100 200 300 400 500 600 700 800 900 1000 1100
Time on Stream (minutes)

CONTACT Thu Ha Thi Vu ptntd2004@yahoo.fr; Hang Thi Au auhang28@gmail.com

© 2017 Informa UK Limited, trading as Taylor & Francis Group

 JOURNAL OF SULFUR CHEMISTRY 265

1. Introduction
Titanate nanotubes (TNTs) are anticipated to have great potential on decomposing toxic
and hazardous organic pollutants in air and water due to their high photocatalytic activity,
chemical stability, physical properties, high specific surface area and uniformity. Since the
titanate nanotubes were found to be rather stable during thermal treatment, their appli-
cation as catalysts or as supports for catalytic metal particles dispersion seems to be quite
attractive [1,2]. However, TNTs have some drawbacks such as the relatively high band gap
and easy recombination of the electron–hole pair [3,4]. To overcome these shortcomings,
several works have been performed in the production of new functional materials by cou-
pling TNTs with other organic and inorganic materials [4]. One of the most commonly
used methods for improving the photocatalytic activity is the combination of MWNTs with
TNTs [5–8].
Carbon nanotubes (MWNTs) have been extensively studied because they have abun-
dant useful properties such as good electrical conductivity, nano size, absolute black,
excellent mechanical properties, large surface area and high absorption capacity [5,9,10].
In addition, MWNTs have large electricity-storage capacity; therefore, it could accept
photon-excited electrons in mixtures of composites with titania, thus retarding or hinder-
ing recombination [5,11–13]. Hence, the combination of MWNTs with TNTs can reduce
charge recombination, enhance reactivity and improve photocatalytic ability of TNTs
[4,14–16].
Composites of TNTs with MWNTs have recently attracted much attention due to inher-
iting properties associated with MWNTs, which contribute to the higher surface area, and
those associated with the TNTs, which result in lower space-charge recombination [17,18].
As a photocatalyst, the MWNTs/TNTs composite has been widely used in solving various
environmental problems such as degradation of contaminants in water and air cleaning.
MWNTs/TNTs composites not only retain the characteristics of each component, but also
exhibit high photo-chemical activity [16,19,20].
In this study, the obtained MWNTs/TNTs composite was synthesized by the hydrother-
mal reaction process. The morphology of the MWNTs/TNTs composites was observed by
transmission electron microscopy (TEM). Fourier transform infrared (FTIR) spectroscopy
was used to characterize the molecular interactions between TNTs and MWNTs in the
composites. The photoluminescense and UV–VIS DRS spectrum were used to demon-
strate that the TNTs photocatalytic activity was considerably enhanced by MWNTs in the
composite. In addition, the photocatalytic activity of TNTs and MWNTs/TNTs composites
driven by UV was investigated via the photo-oxidation of H2 S.

2. Result and discussion

The Brunauer–Emett–Teller (BET) surface areas of TNTs, MWNTs and MWNTs/TNTs
composites prepared from MWNTs and TNTs with different mass ratios are shown in
Table 1. The surface areas of TNTs and MWNTs are 311.44 and 152.48 m2 /g, respectively.
The BET surface areas of MWNTs/TNTs composites were 270.32, 242.21 and 188.25 m2 /g
for MWNTs/TNTs mass ratios of 1/10, 1/1 and 2/1, respectively. It is found that TNTs and
MWNTs are the tubular materials whose diameters are located in the same nano scale as
266 T. H. T. VU ET AL.

Figure 1. Photocatalytic reactor setup for oxidation reaction of H2 S.

Table 1. BET surface area (SBET ) of the

MWNTs/TNTs composites.
Samples SBET (m2 /g)
TNTs 311.44
1/10 MWNTs/TNTs 270.32
1/1 MWNTs/TNTs 242.31
2/1 MWNTs/TNTs 188.25
MWNTs 152.48

shown in Figure 2(a,b), so that the combination of MWNTs with TNTs can create new
nanocomposites with high surface area and good dispersion.
Figure 2 shows TEM micrographs of MWNTs/TNTs composites. Figure 2 (a,b) exhibits
that the length of TNTs is about 100–200 nm, much shorter than that of MWNTs. On the
 JOURNAL OF SULFUR CHEMISTRY 267

Figure 2. TEM micrographs and HRTEM micrographs of: (a) TNTs, (b) MWNTs, (c) 1/10 MWNTs/TNTs com-
posites, (d) 1/1 MWNTs/TNTs composites, (e) 2/1 MWNTs/TNTs composites, (f) and (g) HRTEM of 1/1
MWNTs/TNTs composites.

other side, the similarity of TNTs and MWNTs diameters could improve the good dis-
persion between these two nano-materials in the hydrothermal treatment condition. At
a higher content of MWNTs in the composites with the MWNTs/TNTs ratio of 1/1 and
2/1, the TNTs were uniformly dispersed on the surface of all the MWNTs (Figure 2 (d,e)).
Even at a lower MWNTs/TNTs ratio of 1/10, TNTs were observed well wrapped on the
surface of MWNTs in MWNTs/TNTs composites (as shown in Figure 2(c)). The inter-
faces of TNTs to surface of MWNTs in the MWNTs/TNTs composites were investigated
by HRTEM and illustrated in Figure 2 (f,g). HRTEM images indicated that the wall of TNTs
with a thickness of 2 nm was closely attached with the wall of MWNTs with a thickness of
5 nm. Thank to these HRTEM images, the internal diameters of TNTs and MWNTs were
also determined as 2 and 8 nm, respectively. From these results, the external diameters of
TNTs and MWNTs were calculated to be 6 and 18 nm, in accordance with the values of 7.4
268 T. H. T. VU ET AL.

Figure 3. FT-IR spectra of TNTs, MWNTs, and MWNTs/TNTs (1/10) composite.

and 16.3 nm measured on single materials and confirming that the diameters of TNTs and
MWNTs are in the same nano scale.
The FTIR spectra of TNTs alone, MWNTs alone and MWNTs/TNTs (1/10) nanocom-
posites are shown in Figure 3. In all three traces, the absorption peaks at 3421 cm−1 are
induced by stretching vibration of the surface –OH group and the absorption peaks of
1628 cm−1 can be ascribed to bending vibration of the adsorbed H2 O molecules [21]. The
FTIR spectrum of MWNTs, the peak at 1634 cm−1 , is assigned to the bending vibration of
absorbed H2 O, the peak at 1383 cm−1 belongs to the C–OH stretching band and peak at
1132 cm−1 belongs to C–O stretches, indicating the presence of oxygen-containing func-
tional groups which will aid in building a nanocomposite between the MWNTs and TNTs
[22]. In trace of TNTs alone, TNTs displayed adsorption bands at 400–700 cm−1 , which
are attributed to Ti–O stretching and Ti–O–Ti bridging [23]. In trace of MWNTs/TNTs
(1/10) nanocomposites, the peak at 463 cm−1 is more intense than the corresponding peak
in trace of TNTs. As reported previously, this absorption peak can be attributed to the
combination of Ti–O–Ti and Ti–O–C vibration, demonstrating that chemical bonds were
formed between MWNTs and TNTs after the hydrothermal process [24]. Thus, FTIR and
TEM results indicate that the MWNTs/TNTs composites are bonded together.
X-ray diffraction (XRD) patterns of the MWNTs, TNTs and the MWNTs/TNTs com-
posites after annealing at 400o C for 5 h are shown in Figure 4. The XRD peaks were
observed to be broadened caused by the size of the nanotubes. A characteristic peak of the
MWNTs corresponding to the peak appears at 2θ = 25° as shown in Figure 4(a) [25,26].
For the TNTs and MWNTs/TNTs composite samples, the major XRD peaks are found at
2θ = 10.8°, 24.8°, 48.1° and 62.6° indicating the existence of titanate phase (100), (102),
(020) and (422), respectively [27]. From the comparison of spectra between Figure 4 (b–d),
 JOURNAL OF SULFUR CHEMISTRY 269

Figure 4. XRD patterns of (a) MWNTs; (b) TNTs; (c) 1/10 MWNTs/TNTs and (d) 1/1 MWNTs/TNTs
composites.

the structure of TNTs in the MWNTs/TNTs catalyst is almost the same. This result indi-
cates that there is no difference in the crystallographic structure of the TNTs before and
after combination with MWNTs.
Photoluminescence (PL) spectra are often used to investigate surface structure and
excited states and to follow surface processes involving the electron–hole fate of TNTs
[4,28]. When electron–hole pair recombination occurs after the photocatalyst irradia-
tion (i.e. laser), photons are emitted, resulting in PL. This behavior is attributed to the
reverse irradiative deactivation from the excited-state of the Ti [4]. Figure 5 shows the
270 T. H. T. VU ET AL.

Figure 5. PL spectra of TNTs, MWNTs/TNTs composites and MWNTs.

PL spectra of the MWNTs/TNTs composites with various MWNTs/TNTs mass ratios.

When the excitation wavelength is fixed at 266 nm, the pure TNTs show a high and broad
peak at around 500 nm, whereas no luminescence of MWNTs is observed in the range
of 450–700 nm. The PL intensities of the MWNTs/TNTs composites decreased with an
increase in MWNTs content indicating reduced charge recombination of MWNTs/TNTs
composites in comparison with pure TNTs. In other words, the combination of MWNTs
and TNTs contributes to improve photocatalytic activity of TNTs [29,30].
The mechanism has been proposed to explain the enhancement of photocatalytic activ-
ity of the MWNTs/TNTs composite. With high dispersion, in addition to the excellent
electrical conductivity of MWNTs in the MWNTs/TNTs, the nanocomposite decreased
charge recombination of photon-generated electrons and holes, and increased the efficient
electron transport in the composite. Under UV illumination, electrons (e− ) are excited
from the valence band (VB) to the conduction band (CB) of the TiO2 anatase phase, creat-
ing a charge vacancy, or hole (h+ ) in the VB. In the absence of the MWNTs, most of these
charges recombine quickly without undergoing any chemical transformation [31]. Typi-
cally, only a small number of electro ns and holes are trapped and these trapped electrons
and holes participate in photocatalytic reactions, resulting in low reactivity. Hence, when
a high-energy photon is absorbed by titanium oxide, it will stimulate an electron of the
photocatalyst to transfer from the valence band to the CB. These electrons are absorbed
and transported elsewhere by the MWNTs, whilst the holes remain always in TNTs. This
phenomenon tends to separate the photon-generated electrons and holes in the different
sites where they participate in redox reactions [32]. A diagram of the mechanism is shown
in Figure 6 [10,31].
 JOURNAL OF SULFUR CHEMISTRY 271

Figure 6. Schematic representation of the photogenerated electron–hole separation mechanism.

Table 2. Band-gap values of the synthesized pho-

tocatalysts.
Samples Band gap (eV)
TNTs 3.26
1/10 MWNTs/TNTs 3.21
1/1 MWNTs/TNTs 3.08
2/1 MWNTs/TNTs 3.05
MWNTs –

UV–VIS –DRS spectra of all samples are presented in Figure 7. The precise band gap
of all samples was calculated using the mathematical method from the Kubelka–Munk
model (Table 2). From Figure 7 it can be observed that all samples exhibit a broad intense
absorption at around 400 nm, corresponding to the characteristic absorption of TiO2 . The
incorporation of MWNTs into TNTs causes an extension of the absorption toward the red
shift in the spectrum. The results of Table 2 indicate that band gap values of the composites
decrease with an increase in the amount of MWNTs in the composite. It can be explained
that a close contact between TNTs and MWNTs may affect the electron–hole formation by
inducing charge transfer, leading to effective separation of charge carries, and enhancing
the photocatalytic activity of TNTs.
Based on the result from the PL analysis, 1/1 MWNTs/TNTs composite and TNTs were
selected to evaluate the photocatalytic activity in oxidation of H2 S. The process may be
based on the MODOP process as follows: H2 S is mainly converted to elemental sulfur by
reaction (1) and partly to SO2 by reaction (3). The SO2 formed by reactions (2) and (3)
can be converted into elemental sulfur by the Claus reaction (4), which may increase the
selectivity for elemental sulfur [24].

1 1
H2 S + O2 → Sn + H2 O, (1)
2 n
1
Sn + O2 → SO2 , (2)
n
272 T. H. T. VU ET AL.

Figure 7. UV–VIS DRS spectra of TNTs, MWNTs/TNTs composites and MWNTs.

3
H2 S + O2 → SO2 + H2 O, (3)
2
3
2H2 S + SO2 ↔ Sn + 2H2 O. (4)
n
H2 S conversion and sulfur selectivity were measured over the 1/1 MWNTs/TNTs cat-
alyst in comparison with those over pure TNTs (Figure 8). The high photoactivity of the
MWNTs/TNTs catalyst reveals a total conversion of H2 S during reaction time of more than
1000 min, whereas the selectivity to sulfur, the desired product, takes a value of 100% for
more than 200 min before a continuous decrease in the reaction time. In the same reaction
conditions, the H2 S conversion and sulfur selectivity of pure TNTs catalyst decreased sig-
nificantly with the reaction time. The total H2 S conversion on the pure TNTs catalyst began
to drop after 340 min of streaming, while the sulfur selectivity on this catalyst tumbled
down dramatically just after only 30 min of reaction. This phenomenon may be explained
by the capacity of sulfur storage on catalyst surfaces. For the MWNTs/TNTs composite
catalyst, the obtained sulfur with high hydrophobicity had covered preferentially on the
MWNTs surface, while for the pure TNTs catalyst, the sulfur was deposited directly on the
TNTs’ active sites of the catalyst leading to total oxidation of the H2 S reaction and SO2
formation (3).
When using the MWNTs/TNTs composite as the catalyst for H2 S conversion to sulfur,
the presence of MWNTs had the following two functions: (i) preventing the recombination
of photogenerated electrons and holes, that is enhancing the photoactivity of the catalyst;
(ii) capturing and storing sulfur for avoiding the total oxidation to SO2 and thus improving
 JOURNAL OF SULFUR CHEMISTRY 273

100

90 (a)

H2S Conversion (%)

1/1 MWNTs/TNTs
TNTs
80

70

60

50

40
0 100 200 300 400 500 600 700 800 900 1000 1100
Time on Stream (minutes)

100
(b)
Sulfur Selectivity (%)

90
1/1 MWNTs/TNTs
TNTs
80

70

60

50

40
0 100 200 300 400 500 600 700 800 900 1000 1100
Time on Stream (minutes)
Figure 8. (a) H2 S conversion of photo-oxidation over1/1 MWNTs/TNTs composite and TNTs. (b) Sulfur
selectivity of photo-oxidation over1/1 MWNTs/TNTs composite and TNTs.

the selectivity to sulfur. However, the high black nature of MWNTs may be a negative fac-
tor to the photocatalytic performance because it absorbs solely radiations hence the TNTs
could not be photoactivated enough. The effect of MWNTs contents in the nanocomposite
was investigated by comparing conversion and selectivity in sulfur of the MWNTs/TNTs
nanocomposite with increasing MWNTs/TNTs ratios of 1/10, 1/1 and 2/1 in the identi-
cal catalytic test conditions. The conversion values were collected in Figure 9(a), whereas
the sulfur selectivity assessments were regrouped in Figure 9(a). The catalytic test results
evidenced clearly the high effect of MWNTs content to the photoactivity performance of
MWNTs/TNTs catalysts. At the highest MWNTs/TNTs ratio of 2/1, the S conversion and
also the sulfur selectivity were especially stable. The SO2 trace just only appeared in the
product fluid after 800 min on stream. This stability of sulfur selectivity was established,
274 T. H. T. VU ET AL.

Figure 9. (a) H2 S conversion of photo-oxidation over 1/10, 1/1 and 2/1 MWNTs/TNTs composites.
(b) Sulfur selectivity of photo-oxidation over 1/10, 1/1 and 2/1 MWNTs/TNTs composites.

thank to sulfur storage capacity of MWNTs surface that is as highly hydrophobic as sulfur.
Nevertheless, the strong radiation absorption of MWNTs due to high MWNTs concen-
tration hindered the photon accessing to TNTs surface of nanocomposite, only the TNTs
on the extreme outer surface can be photoactivated and lead to the reaction. This phe-
nomenon decreased significantly the efficiency of used TNTs amount and consequently
the H2 S conversion fell to a value of 65%. At lower concentrations of MWNTs in the case
of MWNTs/TNTs ratios of 1/1 and 1/10, the H2 S conversions were total at least during
the first 600 min on the catalyst with MWNTs/TNTs ratios of 1/10, notably no deviation
to the 100% conversion was observed on the catalyst with equivalent weight contents of
MWNT and TNTs (ratio of 1/1). This catalyst convinced also the excellent selectivity of
 JOURNAL OF SULFUR CHEMISTRY 275

sulfur, almost 100%, during 200 min, more stable than one of MWNTs/TNTs ratios of 1/10
and of bulk TNT catalyst.

3. Conclusions
MWNTs/TNTs composites were successfully prepared by the hydrothermal reaction pro-
cess. MWNTs/TNTs composites have a uniform microstructure with the crystallographic
structure of titanium dioxide. TNTs were well wrapped on the surface of MWNTs in
MWNTs/TNTs composites. There is no difference in the crystallographic structure of the
TNTs before and after combination with MWNTs. The addition of MWNTs improved
the TNTs photocatalytic performance, thanks to the prevention of electron–hole recom-
bination and to the sulfur storage capacity of MWNTs. The high concentration of
MWNTs in the composite could prohibit the photoactivity for the H2 S conversion on
account of its absorption toward the light radiation. Considering the weight ratio of
between MWNTs and TNTs, the photocatalytic activity of 1/1 MWNTs/TNTs compos-
ite for H2 S oxidation to sulfur was evaluated with the best performance among three
ratios of 1/10, 1/1 and 2/1 in this current project. The H2 S conversion remains con-
stant at 100% during a reaction time of more than 1000 min with sulfur selectivity
of 100% for more than 200 min. Nevertheless, complementary studies need to be per-
formed to optimize the MWNTs/TNTs ratio of composite for the H2 S selective oxidation
to sulfur.

4. Experimental
4.1. Materials
Commercial titanium oxide (99.4% about 130 nm, ROHA Dyechem Vietnam Co., Ltd,
Vietnam) was used without further treatment. Carbon source, NaOH, HCl and other
chemicals were purchased from Sigma Aldrich (USA).

4.2. Preparation of MWNTs and MWNTs/TNTs

MWNTs were prepared by the chemical vapor deposition method using Fe/γ -Al2 O3 as
the catalyst and liquefied petroleum gas (LPG) as the carbon precursor at 690–710°C [33].
In the center of a tubular quartz reactor, 0.2 g of Fe/γ -Al2 O3 was placed, and an LPG and
hydrogen mixture were added into the reactor. The reaction temperature and reaction time
were around 690–710°C and 2 h, respectively.
To prepare TNTs, 0.6 g of TiO2 was added into 10 M NaOH solution with a molar ratio
of TiO2 /NaOH at 1/25 in a Teflon-line stainless steel autoclave. The autoclave was sealed
and kept inside an oven at 150°C in 24 h. The solid products were recovered by filtration
and carefully washed by deionized water until pH = 7 before being treated with 0.1 M HCl
solution for 1 h to obtain the TNTs. The TNTs product was dried and calcined at 400°C in
air for 5 h.
Prior to MWNTs/TNTs composites synthesis, the MWNTs were functionalized by acid
treatment. MWNTs were suspended in concentrated HNO3 , sonicated, and refluxed for 5 h
276 T. H. T. VU ET AL.

at 70°C. After 5 h, the reaction mixture was centrifuged, continuously washed with distilled
water until neutrality, and oven-dried at 90°C for 3 h for complete drying. The modified
MWNTs were labeled as MWNTs-f.
The MWNTs/TNTs composites were prepared as follows: MWNTs-f and TiO2 were dis-
persed in 10 M NaOH solution with different MWNTs/TiO2 mass ratios of 1/10, 1/1 and
2/1 in a Teflon-line stainless steel autoclave. The mixture solution was ultrasonically dis-
persed at 210 W during 5 min. Teflon-lined autoclave was sealed and kept inside an oven
at 150°C during 24 h. The products were recovered by filtration and underwent the same
treatment steps as those for the TNTs.

4.3. Characterization
TEM micrographs were recorded on a Leica LEO 906E instrument operating at 120 kV.
The molecular interactions between TNTs and MWNTs in the composites were deter-
mined by FTIR (Nicolet 670, USA). The PL spectra of MWNTs/TNTs composites were
obtained using a fluorescence spectrophotometer iHR550 (Jobin-Yvon, French). XRD pat-
terns were measured over the 2θ range 10–80° (D8 ADVANCE, Bruker, Germany) using
copper radiation Cu-Kα 1 (λ = 0,15418 Å) as the X-ray source. The BET surface area of
the samples was evaluated from the N2 adsorption isotherm at 77 K using a BET Sorp-
tometer. (Automated Sorptometer BET 201-A, USA). UV–VIS–DRS of MWNTs/TNTs
composites were recorded over the wavelength range of 300–700 nm using Varian Cary
5000 (USA). The UV–VIS–DRS were utilized for estimating the band-gap values of the
composites using the mathematical method from the Kubelka–Munk model as reported
elsewhere.

4.4. H2 S oxidation
The photocatalytic reactor used in this test is a coaxial cylindrical Pyrex tubes reactor
(length 270 mm, internal diameter 28 mm, external 30 mm). The reactant mixture flows
in the space between the internal and the external tubes. The UV light source is a commer-
cial 8-W black-light tube with a spectral peak at around 350 nm, placed inside the internal
tube of the reactor. The photocatalytic reactor is shown in Figure 1.
For each test, 100 mg of the catalyst was dispersed in 20 ml of distilled water and then
this aqueous suspension was covered on the internal surface of the external tube followed
by evaporation to dryness. Finally, the deposited catalyst layer was immobilized on the
surface by drying at 100°C for 1 h.
The reaction feed, mixture of H2 S 15 ppm in gaseous mixture of 97%vol air, and 3%vol
He was introduced with a flow of 200 ml/min regulated by a mass-flow controller, equiva-
lent to the speed of 3.65 cm/s and residence time of 7.4 s. Before the photocatalytic reaction,
the catalyst was exposed to the feed stream without lighting until the H2 S adsorption equi-
librium was established. This phenomenon was reached when the H2 S concentration of
the feed analyzed by GC did not change and was at 15 ppm. Subsequently, the UV lamp
was switched on and the reaction started. H2 S and SO2 , undesired reaction products were
analyzed online every 3 min by gas chromatograph equipped with a CP-Sil 5 CB column
linked to a pulsed flame photometric detector.
 JOURNAL OF SULFUR CHEMISTRY 277

The performance of the photocatalytic reaction was evaluated by values obtained from
H2 S conversion (ConvH 2 S ) and selectivity to sulfur (SelecS ) over reaction time as follows:

[H2 S]in − [H2 S]out

ConvH2 S (%) = × 100,
[H2 S]in
[H2 S]in − [H2 S[out − [SO2 ]out
SelecS (%) = × 100.
[H2 S]in − [H2 S]out

Disclosure statement
No potential conflict of interest was reported by the authors.

Funding
The authors would like to thank the National Foundation for Science and Technology Develop-
ment – NAFOSTED that funded the basic research oriented application project, code [DT.NCCB-
DHUD.2012-G/11] and this article is part of the research results.

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