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Article history: Mesoporous WO3 was synthesized by replicating technique using ordered mesoporous silica KIT-6 as
Received 3 June 2014 the template. The obtained material exhibits high surface area (151 m2 g−1 ) and porous structure. The
Received in revised form 21 July 2014 photocatalytic conversion of methane into methanol from an aqueous suspension containing mesoporous
Accepted 25 July 2014
WO3 was studied, as well as the effect of the addition of electron scavengers (Fe3+ , Cu2+ , Ag+ ) and H2 O2
Available online 12 August 2014
species. In the presence of Fe3+ ions the production of methanol was about two and a half times higher than
that of pure mesoporous WO3 , which was principally attributed to the largely improved electron-hole
Keywords:
separation in this system. However, the CO2 generation rates were also increased, mainly in the presence
Mesoporous WO3
Photocatalysis
of Ag+ ions. It was also corroborated that extra hydroxyl radicals in the aqueous medium do not improve
CH4 conversion the generation of methanol but a noticeable increase in the formation of ethane was evidenced. This
Methanol suggests that only a higher availability of HO• s adsorbed on the catalyst can enhance the performance
of methanol generation in the photocatalytic process.
© 2014 Elsevier B.V. All rights reserved.
1. Introduction to TiO2 and NiO, the WO3 showed the largest conversion of methane
to methanol [5]. On the other hand, the addition of chemical addi-
Methane is a highly stable hydrocarbon with a wide distribution tives to improve the performance of WO3 in this photocatalytic
in nature. Moreover, it is the principal component of natural gas reaction has also been reported. Taylor and Noceti showed that
(about 75–90%). Due to its abundance, this gas could provide a new the addition of H2 O2 improved the generation of methanol, as this
alternative in the field of fuels and chemicals [1]. For instance, the species can be a source of hydroxyl radicals, which are an impor-
methane conversion into methanol is a good alternative to obtain a tant intermediate that contributes to the CH3 OH formation [6]. In
liquid compound that can be used as starting material to synthesize contrast, Gondal et al. evidenced that hydrogen peroxide has no
a variety of chemicals such as formaldehyde, acetic acid, methyl t- influence in enhancing the production yield of methanol but the
butyl ether, etc. Also, methanol is considered a much more efficient addition of Fe3+ can help to maintain the production of methanol
fuel than petroleum-based ones [2,3]. over the reaction (batch type) [7].
Photocatalysis is one of the processes that allow this methane Recently, there has been a growing interest in ordered
conversion under mild conditions, by using an appropriate catalyst mesostructures of metal oxides due to their properties and wide
and light. In this sense, this technique can be considered a green potential applications. This kind of materials exhibit a large surface
alternative for performing selective oxidations in a wide range of area that improves the adsorption of reactant molecules [8] and
applications [4]. Among the candidate materials that have been the ordered mesopore channels facilitate fast intraparticle molec-
examined as possible photocatalysts, tungsten oxide (WO3 ) is one ular transfer, resulting in a decrease of charge recombination and
of the most promising, due to its high chemical stability in aqueous thus, a higher photoactivity. Ordered mesoporous WO3 has been
solution under acidic conditions, non-toxicity, and moderate oxi- widely studied for sensor applications [9,10,11], but limited stud-
dizing power. For example, Gondal et al. found that, in comparison ies have been performed for photocatalytic reactions [12,13,14].
To the best of our knowledge, there is no report on the appli-
cation of ordered mesoporous WO3 toward methane conversion
by photocatalysis. Hence, in this work we investigated the par-
∗ Corresponding authors. Tel.: +34 933 562 615.
tial photocatalytic oxidation of methane into methanol using an
E-mail addresses: kvilla@irec.cat (K. Villa), tandreu@irec.cat (T. Andreu).
1
Tel.: +34 933 562 615. ordered mesoporous WO3 that exhibits high crystallinity. Although
http://dx.doi.org/10.1016/j.apcatb.2014.07.055
0926-3373/© 2014 Elsevier B.V. All rights reserved.
K. Villa et al. / Applied Catalysis B: Environmental 163 (2015) 150–155 151
prior works have reported the effect of the addition of Fe3+ and spectrometer supplied with a diffuse reflectance attachment and
H2 O2 on the reaction yield, a more comprehensive study of the with a MCT detector. The catalyst powder weighing approximately
efficacy of such systems has been lacking. Thus, the influence of 10 mg was then pressed mechanically to obtain a disk. This disk was
the addition of several chemical additives as Fe3+ , Cu2+ , Ag+ and placed into the diffuse reflectance infrared cell with CaF2 windows.
H2 O2 in the photoactivity and the role of free hydroxyl radicals in The sample was firstly cleaned under flow of helium at 150 ◦ C for
the reaction mechanism to produce methanol or ethane was also 24 h. The spectrum was referenced to that of the catalyst at 55 ◦ C
studied. before the introduction of feed gases. After this, CH4 bubbled in
water was dosed into cell for one hour. Finally, the sample was
irradiated for 2 h. In situ absorbance spectra were obtained each
2. Experimental minute by collecting 16 scans at 4 cm−1 resolution.
2.1. Reagents
2.4. Photocatalytic setup
Tetraethyl orthosilicate (TEOS, ≥99.0%), poly(alkylene oxide)-
based triblock copolymer Pluronic P-123 (EO20 PO70 EO20 , The photocatalytic partial oxidation of methane was carried out
MW = 5.800), AgNO3 , FeCl3 , Cu2 SO4 and H2 O2 , were purchased in a photochemical reactor (Ace Glass) of 500 mL volume equipped
from Sigma–Aldrich. Other chemicals as 1-butanol (99.0%) and with gas inlet and outlet. A medium pressure quartz mercury-
phosphotungstic acid hydrate were obtained from Alfa Aesar. vapor lamp (immersion-type Ace Glass) inside the reactor was used
Commercial gas mixtures of 500 ppmv of CH3 OH in He, 1% of CO2 to provide UVC-visible light irradiation. The reaction temperature
in air and a mixture of hydrocarbons with 250 ppmv of C2 H6 , was maintained at 55 ◦ C by recirculation of cold water in the outer
100 ppmv of CH3 CH2 OH and 250 ppmv of C2 H4 were used for GC jacket of the lamp. A mixture of methane (4.5 mL min−1 ) and helium
calibration. (17.9 mL min−1 ) was sparged continuously through the photocat-
alytic reactor. In order to avoid methanol condensation during the
path, a heating tape was wrapped around the tube outlet from the
2.2. Sample preparation
reactor up to the port valve of the gas chromatograph (GC). A six
port valve with a 0.5 mL loop was connected to the circuit to allow
KIT-6 mesoporous silica template with cubic Ia3d structure was
gas sample injection into GC. In a typical experiment 300 mL of
synthesized in acidic conditions using a mixture of Pluronic P-123
water (milli-Q) containing 0.3 g of WO3 were placed in the reac-
and 1-butanol, as reported in literature [15]. Ordered mesoporous
tor. Prior to illumination, the suspension was magnetically stirred
WO3 was prepared as follows: a solution of 5 mmol of phospho-
in the dark for 30 min to reach adsorption-desorption equilibrium.
tungstic acid hydrate in ethanol was incorporated into 0.75 g of
After that, the lamp was turned on and gas samples were period-
as-prepared KIT-6 silica under stirring. The sample was dried and
ically taken for analysis. Aqueous solutions of Fe3+ (2 mM), Cu2+
then calcined for 4 h at 350 ◦ C to decompose the precursors, and
(0.1 mM), Ag+ (2 mM) and H2 O2 (2 mM) were used as redox medi-
then further at 550 ◦ C for 6 h to obtain WO3 inside the hosting sil-
ators to improve the photocatalytic activity of WO3 . In the case
ica. Later, the obtained material was suspended under stirring in
of copper, a lower concentration was used because it has been
a 10 wt% HF solution to remove the KIT-6 silica template. Finally,
reported that larger amounts to 0.1 mM might negatively affect the
the mesoporous WO3 catalyst was separated by centrifugation,
performance [16]. The initial pH of the suspension was adjusted to
washed sequentially with water and ethanol and dried at room
∼3 with 1 M H2 SO4 .
temperature.
The crystal structure and the optical absorption of the cata- Detection and quantification of CH3 OH were carried out by using
lyst were characterized by XRD and UV–Vis diffuse reflectance a Shimadzu GC-2010 chromatograph equipped with a capillary col-
spectroscopy, respectively. The detailed procedures are described umn (HP-PLOT Q), a thermal conductivity detector (TCD) and a
in the Supporting Information. A Zeiss Auriga FESEM microscope flame ionization detector (FID). Pure He (99.99999%) was used as
was used to perform scanning microscopy of the sample and TEM carrier gas. A chromatographic ramp reported in literature was cho-
images were taken on a Zeiss LIBRA 120 instrument. BET sur- sen [5]. Under these conditions a good separation of the peaks of
face area was obtained with a Micromeritics TriStar II apparatus. products can be achieved and water can be effectively removed
In situ DRIFT spectra were collected on a Bruker Vertex 70 FTIR from the column.
Fig. 1. (a) TEM image of mesoporous WO3 , (b) SEM image of mesoporous WO3 and (c) magnification of the area marked by the dotted line square in (b).
152 K. Villa et al. / Applied Catalysis B: Environmental 163 (2015) 150–155
hydroxyl radicals (Eqs. (3) and (4)), which would react with CH4 to
produce methanol as shown in Eqs. (5) and (6).
hv
WO3 −→e−
CB
+h+VB (2)
h+VB +HO−
ads
→ HO·ads (4)
Fig. 3. In situ DRIFTS spectra recorded at 55 ◦ C under CH4 and H2 O flow for (a) WO3 hv
Mn+ + e−
CB
−→M(n−1) (10)
before irradiation and (b) WO3 after 2 h of irradiation UV–visible light.
H2 O2 +e−
CB
→ OH− +HO· (11)
hv
Fe3+ + H2 O−→Fe2+ + HO. + H+ (12)
Fig. 6. Yields of CO2 in the photocatalytic oxidation of CH4 in systems of WO3 /Fe3+
(2 mM), WO3 /Cu2+ (0.1 mM), WO3 /Ag+ (2 mM), WO3 /H2 O2 (2 mM) and WO3 at ∼
55 ◦ C under UVC–visible light irradiation. WO3 dosage is 1 g L−1 . Data corresponding
to 2 h of irradiation in continuous methane flow of 4.5 mL min−1 .
Table 1
Iron concentration, yield of CH3 OH, C2 H6 and CO2 . WO3 dosage is 1 g L−1 . Data corresponding to 2 h of irradiation in continuous methane flow of 4.5 mL min−1 .
System Concentration Yield of CH3 OH (mol h−1 g−1 ) Yield of C2 H6 (mol h−1 g−1 ) Yield of CO2 (mol h−1 g−1 )
References