Applied Surface Science 355 (2015) 891901

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Applied Surface Science

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

Effectively CO2 photoreduction to CH4 by the synergistic effects of Ca

and Ti on Ca-loaded TiSiMCM-41 mesoporous photocatalytic systems
Seung Won Jo a , Byeong Sub Kwak a , Kang Min Kim a , Jeong Yeon Do a , No-Kuk Park b ,
Si Ok Ryu b , Ho-Jung Ryu c , Jeom-In Baek d , Misook Kang a,
a

Department of Chemistry, College of Science, Yeungnam University, Gyeongsan, Gyeongbuk, Republic of Korea
School of Chemical Engineering, College of Engineering, Yeungnam University, Gyeongsan 712-749, Gyeongbuk, Republic of Korea
c
Korea Institute of Energy Research, 152, Gajeong-ro, Yuseong-gu, Daejeon 305-343, Republic of Korea
d
Korea Electric Power Corporation (KEPCO) Research Institute, 105 Munji-ro, Yuseong-gu, Daejeon 305-760, Republic of Korea
b

a r t i c l e

i n f o

Article history:
Received 2 April 2015
Received in revised form 26 June 2015
Accepted 24 July 2015
Available online 28 July 2015
Keywords:
CO2 photoreduction
CH4
Ca-loaded TiSiMCM-41
Recombination of electronhole pairs

a b s t r a c t
Tix SiMCM-41 is a mesoporous photocatalyst with a tetragonal framework and high structural regularity. In this study, Ca was introduced to the Tix SiMCM-41 surfaces to improve CO2 absorption. The
catalytic performance of mesoporous Ca/Tix SiMCM-41 was superior to that of the reported Ca/Tix SiO2
nano-sized composite catalyst. The photoreduction of CO2 to CH4 improved remarkably over the
Ca(10.0 wt.%)/Ti35 Si65 MCM-41 catalyst, producing 82.0 mol g1 cat L1 after an 8 h reaction. A model for
the enhanced photoactivity over Ca/Tix SiMCM-41 was suggested, and the results were attributed to the
effective charge separation and inhibited recombination of the photogenerated electronhole pairs over
Ca/Tix SiMCM-41.
2015 Elsevier B.V. All rights reserved.

1. Introduction
The increasing CO2 emissions and the shortage of the fossil
resources have stimulated research into the utilization of CO2 . Currently, the conversion of CO2 into useful materials, mainly CH4 ,
a high density energy source, or other inorganic and organic substances, such as CO, HCOOH, HCHO, and CH3 OH, is important to the
development of alternative fuel sources or various raw materials
for industry. In particular, CH4 production from the photocatalytic
reduction of CO2 and H2 O has become one of the leading methods
[1,2]. This method is also environmentally friendly: CO2 reduction
with H2 O through photocatalysis is vital for the development of
the solar energy-based carbon neutral cycle. In addition, the solar
spectrum is an abundant, permanent and reliable source of energy.
TiO2 -based nanomaterials, which are generally obtained by
solgel, hydrothermal, and solvothermal methods, have a large
BET surface area and strong adsorption ability, and are one
of the most intensively studied and widely used [36]. These
materials also have several advantages including higher oxidation potential, relatively inexpensive, abundance, non-toxicity,
and chemically/thermally stable. On the other hand, lower CO2

Corresponding author. Tel.: +82 53 810 2363; fax: +82 53 815 5412.
E-mail address: mskang@ynu.ac.kr (M. Kang).
http://dx.doi.org/10.1016/j.apsusc.2015.07.176
0169-4332/ 2015 Elsevier B.V. All rights reserved.

reduction efciency and selectivity over TiO2 has been also

reported because of the immediate recombination of photogenerated charges (e /h+ ) [7]. To prevent the recombination of
electron and hole pairs, metal doped titanates, including rareearth metals, such as Ag, Cu, Pt, Rh, Pb, Ce, Cd, and La, [816] and
bimetallic titanates [1719], have been researched most widely.
These catalysts, however, exhibit CH4 conversions of less than
2.5 mol gcatal h1 ; thus, a variety of approaches are necessary to
develop new catalysts to improve methane production.
Recently, mesoporous network structures such as Ti incorporated MCM or the SBA series, were reported to enhance the
adsorption of the reactive species and utilization of the incident
light, and thereby increase the photocatalytic activity [2022].
Ye et al. reported [23] the photoreduction of CO2 over the wellcrystallized ordered mesoporous TiO2 via the conned space effect.
They found that the ordered mesoporous TiO2 not only shows a
higher production efciency of CH4 , which is 71 and 53 times higher
than that of commercial TiO2 and disordered mesoporous TiO2 ,
respectively, but also exhibits better stability for CO2 photoreduction. In addition, they suggested that the remarkable performance
of ordered mesoporous titanium dioxide for CO2 photoreduction
probably benets from the conned space effect of the ordered
mesoporous structure. Still many researches on the nanoparticles are progressing, but the studies on the porous photocatalytic
particles are seldom, in particular the cases using the alkaline

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S.W. Jo et al. / Applied Surface Science 355 (2015) 891901

earth metals to increase the absorption of carbon dioxide are even

rare.
Therefore, this study is focused on a synergistic effect of
mesoporous titanate material and the alkaline earth metal. The
Tix SiMCM-41 (x = 0, 15, 35, and 50 mol.%) mesoporous materials,
which partially replace Ti ions in the Si sites in the SiMCM-41 framework, were synthesized by a conventional hydrothermal treatment,
and introduced in this study. Among the potential CO2 sorbents,
CaO is the most promising for CO2 capture because of its low cost,
easy production from natural minerals (limestone or dolomite) and
high CO2 absorption capacity [24,25]. The cyclic absorption of CO2
by CaO is based on the reaction of CaO with CO2 to yield CaCO3 , as
shown in the following equation:
CaO + CO2 CaCO3

(1)

Therefore, in this study, Ca was loaded on the surface of

Tix SiMCM-41 mesoporous materials (Ca-loaded Tix SiMCM-41) to
capture CO2 . These materials were the applied to CO2 photoreduction to obtain CH4 . The experiments were conducted to
identify the most appropriate Si/Ti ratios and the appropriate
amount of Ca for efcient methane production. The Ca-loaded
Tix SiMCM-41 materials were characterized by X-ray diffraction
(XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), (BrunauerEmmettTeller (BET) surface
area, ultravioletvisible (UVvis) spectroscopy, photoluminescence (PL) spectroscopy, and photocurrent density.
2. Experimental
2.1. Synthesis and characterization of the Ca-loaded
Tix SiMCM-41 (Ca/Tix SiMCM-41)
The hydrothermal method for MCM-41 synthesis has been
reported in many papers [2628], and was also considered in
this study. Cetylmethylammonium bromide (CTABr, Aldrich co.)
as a template was dropped slowly into a mixed solvent of
water and ethanol to produce the mesopores. NH4 OH and TEOS
(tetraethylorthosilicate, Aldrich co.) were dropped step by step
into the solution. The composition of the nal sol solution was
6.0SiO2 :1.0CTABr:0.15(NH4 )2 O:350H2 O. The pH was xed to 11.
The nal solution was stirred until it was homogeneous, and crystallization was performed at 100 C for 24 h in an autoclave. After
synthesis, the resulting powder was washed, ltered and then calcined at 550 C for 5 h in air (named SiMCM-41). On the other hand,
titanium ions (TTIP, Titanium tetraisopropoxide, Junsei Co.) substituted for silicon sites in the mesoporous framework, and the
Si:Ti molar ratios were 0, 15, 35, and 50% (named Tix SiMCM-41).
Ca doping was conducted in the nal step using an impregnation
method. CaO (CaCl2 , Aldrich Co.) at 1.0, 5.0 (standard sample), 10.0,
and 15.0 wt.% were added to 25.0 mL of an ethanol solution containing the Tix SiMCM-41 powders. The slurries were stirred at 40 C
for 3 h, evaporated at 80 C for 3 h, and dried at 50 C for 24 h in an
oven. The nal samples were treated thermally at 500 C for 2 h in
air (named Ca/Tix SiMCM-41).
The synthesized Ca(5.0 wt.%)/Tix SiMCM-41 (x = 0, 15, 35, and
50) powders were examined by XRD (MPD, PANalytical) using
nickel-ltered CuK radiation (30 kV, 30 mA). The morphology of
the particles were studied by TEM (JEOL 2000EX) and the atomic
compositions of the lm was measured by energy dispersive Xray spectroscopy (EDAX, EX-250, Horiba) operated at 120 kV. XPS
(Axis-Nova, Kratos Inc.) of Ti 2p, Ca 2p, Si 2p, and O1s in the samples was performed using a non-monochromatic AlK (1486.6 eV)
X-ray source. The reectance UVvis spectra were obtained using
a Cary 500 spectrometer with a reectance sphere in the range,
200800 nm. The recombination tendency of the photogenerated

electronhole pairs (e /h+ ) was estimated by PL (Perkin Elmer)

using a He-Cd laser source at a wavelength of 325 nm. The BET
surface areas of the catalysts were measured using a Belsorp II
instrument. All the catalysts were degassed under vacuum at 150 C
for 30 min before measuring the BET surface area, and were measured by nitrogen gas adsorption using a continuous ow method
with a mixture of nitrogen and helium as the carrier gas. A tube
was lled with 0.2 g of the samples under a N2 atmosphere and
then out-gassed for 2 h at 150 C before the measurements. After a
pre-treatment, the samples were exposed to liquid nitrogen for 2 h.
Finally, the samples were heated to 350 C at a programmed heating
rate of 10 C min1 . In the -plot method, the adsorption volume
(Vads , p/p0 ), which was normalized to Vads for the reference material, and (p/p0 ), which is used as a new x-axis to plot the adsorption
isotherms for the samples of interest, were employed. Photocurrent
densities were measured with an electrochemical station (CompactStat, IVIUM STAT tech.) using three-electrode mode in 1.0 M
NaOH aqueous solution, and an AM 1.5 Solar simulator (ABE tech.)
as the light sources. Platinum wire and Ag/AgCl electrode were
used as the counter electrode and reference electrode, respectively.
10 mg of sample was dispersed to the 1.0 mL of ethanol to form
a homogeneous turbid liquid. The turbid liquid was deposited on
FTO conductive glass with an area of 0.4 cm2 to form the working
electrode. The adsorption ability of the catalysts for CO2 gas was
measured from the CO2 -TPD (temperature programmed desorption) experiments in the same manner using BELCAT (Bel Japan
Inc., Japan). Each catalyst (0.05 g) was charged in the quartz reactor
of the TPD apparatus. The catalysts were pretreated at 300 C for 1 h
under a He ow (30 mL min1 ) to remove the physically absorbed
water and impurities. CO2 (5 vol.% CO2 /He) gas was injected into
the reactor for 1 h at a rate of 50 mL min1 at 50 C. The physically absorbed CO2 gases were removed by evacuating the catalyst
samples at 50 C for 30 min. The furnace temperature was then
increased from 50 to 900 C at a rate of 10 C min1 under He ow.
The desorbed CO2 gases were detected using a TCD detector.
2.2. Photocatalytic activity test for Ca/Tix SiMCM-41s
Fig. 1 presents a schematic diagram of the batch type photoreactor designed in the laboratory. The reactor consisted of
a rectangular quartz cell with a total volume of 15.0 mL. The
photocatalytic activity was examined using 0.20 g of powdered
Ca/Tix SiMCM-41 catalyst distributed uniformly at the bottom of
the reaction chamber. A 1.0 mm thick quartz glass window cover
was placed on the top of the reactor to enable the effective transfer of irradiation from a 6.0-W cm2 mercury lamp with a 365 nm
wavelength. The reactor chamber and lamp were covered with aluminum foil to ensure that all the irradiation that participated in the
reaction had passed through the quartz window only. The reactor,
which had been checked for leakage at atmospheric pressure for
several hours, was purged with helium carrier gas. The CO2 concentration was controlled using helium (99.99%) as the diluent gas. The
reaction temperature and pressure were maintained at 303 K and
1.0 atm. Before starting the experiment, the reactor was purged for
1 h with a mixture of CO2 and helium. The CO2 :H2 O ratio introduced
was xed to 1:2. During the photocatalysis process, the product
mixture was sampled off-line using a gas tight syringe (Agilent,
250 m) with the same volume, and analyzed by gas chromatography (GC, iGC7200, Donam Co., Korea) equipped with a thermal
conductivity detector (TCD) and a ame-ionized detector (FID).
First, the gaseous products produced by the in-situ system were
owed into the TCD detector, which was connected to a Carboxen
1000 (Young Lin Instrumentals Co., Korea) column, to analyze the
light gases (H2 , O2 , and CO), and the extracted gases were then
inserted into the FID detector to separate the C1 (methane)C3
light hydrocarbons, and oxygenated compounds, such as methanol,

S.W. Jo et al. / Applied Surface Science 355 (2015) 891901

893

Fig. 1. Schematic diagram of the batch type reactor for CO2 photoreduction that designed in our laboratory.

acetaldehyde and formic acid. The selectivity of the product was

calculated using the following equation: Ci (%) = Ci moles in product/total moles of C produced 100.
3. Results and discussion
3.1. Physical properties of the synthesized
Ca(5.0 wt.%)/Tix SiMCM-41 powders
Fig. 2(a) and (b) shows XRD patterns of the prepared
Ca(5.0 wt.%)/Tix SiMCM-41 (x = 0, 15, 35, and 50) powders. In
Fig. 1(a), a shape reection peak corresponding to the (100) plane
was observed at a low angle (22.5 2) in all Ca non-loaded
Tix SiMCM-41 (x = 0, 15, 35, and 50) samples, highlighting the typical
hexagonal SiMCM-41 structure [29]. On the other hand, this peak
was absent in the Ca(5.0 wt.%)/Ti50 Si50 MCM-41 sample after Caloading. Fortunately, the sign of a very small peak remained until
35 mol.% Ti-insertion in the Ca(5.0 wt.%)/Ti35 Si65 MCM-41 sample.
This was attributed to the larger mesopores due to the insertion of
many larger sized titanium ions than silicon ions into the SiMCM-41
framework. Eventually, the loaded calcium ions penetrated further
into the pores, which led to pore clogging. In addition to the main
reection peak, three reection peaks, which were indexed to the
(1 1 0), (2 0 0) and (2 1 0) planes, were clearly visible at 37 2 in the
XRD patterns of the Ca(5.0 wt.%)/Ti15 Si85 MCM-41 sample. The presence of well-dened and intense XRD peaks indicates the excellent
degree of ordering of the mesoporous molecular sieves. In addition, slight decreases in inter planar spacing d1 0 0 with increasing Ti
content were observed. This could be related to the probable incorporation of Ti atoms into the silica framework. Because the ionic
radius of Ti4+ (0.068 nm) is larger than that of Si4+ (0.041 nm), the
substitution of Si4+ with Ti4+ should invariably distort the geometry around Ti from an ideal tetrahedral coordination. No peaks
assignable to CaO were observed in the high-angle region (gure
not shown). Therefore, the metal ions are either dispersed atomically in the framework of TiSiMCM-41 or achieve amorphous form
outside the framework. On the other hand, in wide angle range
of Fig. 1(b), the anatase TiO2 tetragonal structured peaks were
clearly observed in the Ca(5.0 wt.%)/Ti15 Si85 MCM-41 sample. In the
Ca(5.0 wt.%)/Ti50 Si50 MCM-41 sample, however, the peaks disappeared and new some small peaks assigned to the perovskite cubic
CaTiO3 structure [30] were observed. These results suggest that the
loaded Ca ions exist in close proximity to the Ti ions.
Fig. 3 presents the TEM images of the four samCa(5.0 wt.%)/SiMCM-41,
Ca(5.0 wt.%)/Ti15 Si85 MCM-41,
ples,

Ca(5.0 wt.%)/Ti35 Si65 MCM-41, and Ca(5.0 wt.%)/Ti50 Si50 MCM41. The hexagonal array of the mesoporous materials could be
observed clearly with an electronic beam passing through both
the parallel and vertical directions of the axis of channels, which
further indicates the order of the hexagonal structure [31]. When a
small amount of Ti ions was introduced, the ordered structure was
disturbed slightly, but some uniform pore collapse was observed
with increasing Ti content. This conrms that incorporating Ti
ions interrupts the Si O framework and weakens its integrity.
Generally, when the Si/Ti ratio decreases, the regular arrays are no
longer observable. These observations are in good agreement with
XRD. On the other hand, the loaded CaO particles were observed
as dark spots on the surface of the mesoporous TiSiMCM-41
depending on the Ti level. This might due to the decreases in
inter-planar spacing, d1 0 0 , with increasing Ti content, resulting in
CaO ingredients only partially penetrating into the meso-pores.
EDAX conrmed the presence of metals on the surface of the
Ca(5.0 wt.%)/Tix SiMCM-41 particles, as illustrated in Fig. 4 and
Table 1. EDAX revealed the presence of O, Si, Ca, and Ti, showing
that the other components in the precursors were not present in
any of the samples. Table 1 lists the atomic compositions on the
surface of all the samples determined by EDAX. The Ti/Si and Ca/Ti
atomic molar ratios in the samples did not appear to be quantitative. EDAX is a very good surface analytical method, but it is prone to
error, because the composition may vary according to the location.
In particular, the variation is large when the sample is non-uniform.
On the other hand, the actual Ti amounts in the samples increased
gradually with increasing amount of Ti added in the synthesis steps.
Fig. 5 presents the N2 adsorptiondesorption isotherms of the
Ca(5.0 wt.%)/Tix SiMCM-41 samples, and results are listed in Table 2.
All samples gave typical irreversible type IV adsorption isotherms,
as dened by IUPAC [32]. N2 adsorption at low relative pressure
(p/p0 < 0.25) accounted for the monolayer adsorption of N2 , followed by multilayer adsorption on the walls of the mesopores, and
did not indicate the presence of micropores [33]. As the relative
pressure increases, all samples exhibited sharp inections at relative pressures ranging from 0.25 to 0.45, which is characteristic of
capillary condensation inside the primary mesopores, showing that
all the samples have a typical meso-structure with a regular and
uniform pore size distribution. The relative pressure position of the
inection point is clearly related to the size of the mesopore, and the
sharpness of these steps indicates the uniformity of the mesopore
size. With the exception of the Ca(5.0 wt.%)/Ti15 Si85 MCM-41 sample, the isotherms of the other Ca/Tix SiMCM-41 samples showed
similar inection points with a slight shift toward higher relative

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S.W. Jo et al. / Applied Surface Science 355 (2015) 891901

Fig. 2. XRD patterns of the prepared Ca(5.0 wt.%)/Tix SiMCM-41 (x = 0, 15, 35, 50) powders.

Fig. 3. TEM images of the prepared Ca(5.0 wt.%)/Tix SiMCM-41 (x = 0, 15, 35, 50) powders.
Table 1
Atomic compositions over the Ca(5.0 wt.%)/Tix SiMCM-41 samples calculated from the EDAX results.
Ca/SiMCM-41
Elements
0
Si
Ca
Ti
Totals

wt.%
60.18
36.32
3.50

100

Atomic%
72.63
25.61
1.76

100

Ca/Ti35 Si35 MCM-41

Ca/Ti15 Si85 MCM-41

Ca/Ti50 Si50 MCM-41

wt.%

wt.%

wt.%

56.80
33.59
4.92
4.69
100

Atomic%
71.47
24.08
2.47
1.97
100

56.52
25.25
2.43
15.80
100

Atomic%
73.41
18.68
1.22
6.69
100

53.93
14.71
1.87
29.48
100

AtomicX
73.97
11.50
1.02
13.51
100

S.W. Jo et al. / Applied Surface Science 355 (2015) 891901

895

Fig. 4. EDAX patterns of the prepared Ca(5.0 wt.%)/Tix SiMCM-41 (x = 0, 15, 35, 50) powders.

pressures with increasing Ti-insertion, indicating an increase in the

adsorption pore volume and an increase in the size of the most
probable pore. Table 2 lists the structure parameters calculated
from N2 adsorptiondesorption isotherms. The specic surface area
(1149.40 m2 g1 for Ca(5.0 wt.%)/Ti35 Si65 MCM-41) increased with
increasing Ti content to 35 mol.%; the same tendency was also
observed for the pore volume and mean pore diameter. In contrast,
the BET surface area of the Ca(5.0 wt.%)/Ti50 Si50 MCM-41 sample decreased but the pore volume and pore diameter increased.
The lowest pore volume has the largest average pore diameter
because of the increasing nonstructural porosity consisting of some
irregular cavities that permeate the entire bulk and give rise to
secondary porosity.
X-ray photoelectron spectroscopy (XPS) analysis for two
samples, Ti35 Si65 MCM-41 and Ca(5.0 wt.%)/Ti35 Si65 MCM-41, was

employed to obtain detailed information on the oxidation states

of all of the elements. The high-resolution survey spectra exhibit
the presence of Ti 2p, Ca 2p, Si 2p, and O 1s photoelectron lines in
Fig. 6. For Ti 2p spectra, the ratio between the Ti2p doublet areas is
to Ti 2p3/2 /Ti 2p1/2 = 0.5: it was satisfactory in both samples. Generally, the binding energy of Ti 2p3/2 at 458.8 eV conrmed to the
presence of Ti(IV) in an octahedral coordination (extraframework
or anatase) [34]. However, the high binding energy contributions
in both samples of Ti35 Si65 MCM-41 and Ca(5.0 wt.%)/Ti35 Si65 MCM41, observed at 459.1 eV may be due to the presence of terminal
Ti(IV) associated with silica (Ti O Si) [35]. These species are
related to photocatalytic activity on Si O Ti systems, perhaps acting as adsorption sites of the reactants. Additionally the broad
Ti 2p peak suggests the presence of titanium with lower oxidation states, and the line slightly became broad with added calcium

Fig. 5. N2 adsorptiondesorption isotherms of the Ca(5.0 wt.%)/Tix SiMCM-41 powder samples.

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S.W. Jo et al. / Applied Surface Science 355 (2015) 891901

Table 2
BET surface area, pore volume, and mean pore diameter analyzed from the N2
adsorptiondesorption isotherms curves of the Ca(5.0 wt.%)/Tix SiMCM-41 samples.

BET multipoint surface

area [m2 g1 ]
Total pore volume
[cm3 g1 ]
Average pore diameter
[nm]

BET multipoint surface

area [m2 g1 ]
Total pore volume
[cm3 g1 ]
Average pore diameter
[nm]

Ca/SiMCM-41

Ca/Ti15 Si85 MCM-41

1102.60

1128.80

1.04

0.72

3.79

2.56

Ca/Ti35 Si65 MCM-41

Ca/Ti50 Si50 MCM-41

1149.4o

493.5o

1.04

1.42

4.19

11.55

element [34]. For the survey of Ca 2p, two feature peaks of Ca

2p1/2 and Ca 2p3/2 emerged clearly at round 346.5 eV and 350.1 eV
[36], respectively, this implies that Ca element exists as Ca2+ in
Ca(5.0 wt.%)/Ti35 Si65 MCM-41. The binding energies of Si 2p were
shown at 103.0 eV [34], and the peak shifted with the Ca loading to
high binding energy, which meaning more oxidized state. Generally
the O 1s binding energies are located in the 530.9536.2 eV regions
[35]. In this study, the binding energy at 530.9 eV and 533.7 eV can
be assigned to TiO2 and SiO2 , respectively. These peaks were seen
in both samples, but the calcium is considered to be loaded onto
the oxygen in Si O, from which the O 1s peak of TiO2 is larger than
that of SiO2 .
Fig. 7(a) and (b) shows the diffuse reectance-UVvis absorption spectra of the synthesized Ca(5.0 wt.%)/Tix SiMCM-41 powders
and their Taucs plots [37]. All samples had a maximum band
located in the region, 250280 nm, suggesting that the polymerized Ti O Ti species in higher coordination, such as hexahedral
coordination Ti species, co-exist with the tetrahedral Ti sites
[38]. Therefore, in all the synthesized Ca(5.0 wt.%)/Tix SiMCM-41

samples, most of the Ti(IV) species are located at the tetrahedral

positions in the framework. UVvis spectroscopy showed that the
Ti atoms entered the silica framework and no extra framework
titanium formed during the microwave irradiation synthesis. In
addition, the absorption intensity increased depending on the
amount of Ti inserted. On the other hand, the absorption spectra
showed a steeper absorption edge, which was similar to the results
obtained by the Tauc equation. The band gap was estimated using
the Tauc equation: (h)n = B(h Eg ), where h is the photon
energy, is the absorption coefcient, B is a constant relative
to the material, and the exponent n is a value that depends on
the nature of the transition (2 for a direct allowed transition, 2/3
for direct forbidden transition and 1/2 for indirect allowed transition). The estimated band-gaps of the Ca(5.0 wt.%)/SiMCM-41,
Ca(5.0 wt.%)/Ti15 Si85 MCM-41, Ca(5.0 wt.%)/Ti35 Si65 MCM-41, and
Ca(5.0 wt.%)/Ti50 Si50 MCM-41 particles were 2.76, 2.70, 2.58, and
2.45 eV, respectively; the band-gap decreased with increasing
Ti-insertion. Moreover, different band-heights were also affected
by Ti-insertion. Generally, a lower band gap is better for enhancing
the photocatalytic performance under weak solar radiation [39],
but this principle is not always true because there is less band gap
to facilitate recombination between the electrons and holes.
Fig. 8 shows the PL spectra of the Ca(5.0 wt.%)/Tix SiMCM-41
particles with different Ti contents. The Ca(5.0 wt.%)/SiMCM-41
particles exhibited a wide and strong PL signal in the range,
380600 nm, with the maximum excitation wavelength of 444 nm,
whereas the intensities of the Ca(5.0 wt.%)/Tix SiMCM-41 curves
decreased gradually with an increase of Ti insertion except for completely collapsed Ca(5.0 wt.%)/Ti50 Si50 MCM-41 sample. Generally,
due to the formation of new oxygen vacancies by metal-doping, the
photogenerated electrons in the conduction band initially reach the
vacant space and then recombine with the photogenerated holes
in the valance band to produce uorescence emission [40]. The
relatively strong emission peak was also observed in the Ca-non
loaded TiSiMCM-41 samples, indicating the higher electronhole
recombination. After loading CaO, the PL emission peak decreased,
suggesting a decrease in electronhole recombination. This

Fig. 6. X-ray photoelectron spectroscopy curves for the elements of Ti 2p (a), Ca 2p (b), Si 2p (c), and O 1s (d) in two samples of Ti35 Si65 MCM-41 and Ca(5.0 wt.%)/Ti35 Si65 MCM41.

S.W. Jo et al. / Applied Surface Science 355 (2015) 891901

897

Fig. 7. Diffuse reectance-UVvis absorption spectra (a) of the synthesized Ca(5.0 wt.%)/Tix SiMCM-41 powders and their Taucs plots (b).

suggests that the CaO species are more effective in CO2

absorption. Therefore, the photocatalytic activities over these
Ca(5.0 wt.%)/Tix SiMCM-41 materials can be correlated and rationalized by the photoluminescence studies. The reduced PL intensities
for the Ca loaded Tix SiMCM-41 samples might be due to defects
(regardless of the chemical stoichiometric or non-stoichiometric)
generated by Ca ions partially incorporated into the SiMCM-41
structure. In other words, Ca-ions suppressed the recombination
of photogenerated carriers via a transition from the structural
defects or oxygen vacancies to Ca(5.0 wt.%)/Tix SiMCM-41 conduction band. Consequently, a lower PL intensity means the hindering
of electronhole pair recombination on the Tix SiMCM-41 surface
as well accelerating electron transfer in this study. In addition, the
mesoporous Ca(5.0 wt.%)/Ti35 Si65 MCM-41 material did not show
any signicant emission, as indicated in this gure, suggesting
that electronhole recombination is signicantly minimized in
this material compared to nano-sized Ca(5.0 wt.%)/Ti35 Si65 O200
composite, possibly due to their pore effect. Accordingly, the photocatalytic activity of mesoporous Tix SiMCM-41 is superior to that
of the nano-sized Tix SiO2 composite.

According to the CO2 photoreduction mechanism, water and

CO2 gases are adsorbed onto the surface of the photocatalysts in
the rst step, and the photoreduction reaction then progresses [41].
Therefore, the photocatalytic performance depends on the absorption capacities of these two gases, which are injected from outside
the reactor. Here, the CO2 adsorption ability was determined for all
samples. In this study, the CO2 adsorption proles were obtained
at high temperatures (>700 C) corresponding to CO2 desorption
on the metal oxide species, as shown in Fig. 9. The curve intensity
increased signicantly in the Ca(5.0 wt.%)/Ti35 Si65 MCM-41 sample,
which means considerably more CO2 molecules were adsorbed on
the surface of the exposed Ca O Ti than on the Ca O Si surface.
In general, a rapid catalytic reaction occurs when many reactants
are well-adsorbed over the catalyst. The harmonic presence of Ca
and Ti ions most likely caused the relative increase in the number
of CO2 molecules.

Fig. 8. PL spectra of the Ca(5.0 wt.%)/Tix SiMCM-41 particles with different Ticontents.

Fig. 9. CO2 -TPD curves corresponding

Ca(5.0 wt.%)/Tix SiMCM-41 samples.

to

CO2

desorption

on

the

898

S.W. Jo et al. / Applied Surface Science 355 (2015) 891901

Fig. 10. Photocatalytic reductions of CO2 with H2 O to CH4 over the Ca(5.0 wt.%)/Tix SiMCM-41 samples.

3.2. Catalytic efciencies of CO2 photoreduction over

Ca/Tix SiMCM-41s
Photocatalytic reduction processes require a catalyst, feed (CO2
and H2 O) and light source. All the photocatalytic CO2 reduction
experiments were repeated at least in triplicate and the average
results are reported. Generally, the mechanism for methane
production from CO2 reduction [42] can be divided into three subprocesses: proton production from H2 O photodecomposition, CO
radical production from CO2 photo cleavage and methane production from photosynthesis between the CO radical and proton. The
photogenerated electrons on the photocatalysts by UV-radiation
induce CO2 reduction to produce CO2 radicals, whereas the holes
react with the adsorbed H2 O molecules to perform oxidation. The
intermediate photogenerated species undergo different reactions
to produce CO and CH4 . The production of CH4 from methyl radicals ( CH3 ) was conrmed because all of the above products were
detected experimentally. These radicals are dependent directly on
the formation of the intermediate product, CO. From the reaction
summary and the above observations, there is the possibility of
producing hydrocarbons using photocatalysts with good reduction
potentials. Fig. 10 presents the photocatalytic reduction of CO2 with

H2 O vapor to CH4 over the Ca(5.0 wt.%)/Tix SiMCM-41 catalysts. The

higher Ti-insertion into the SiMCM-41 framework led to higher
photoactivity for CO2 photoreduction. CH4 was not produced
over pure Ca(5.0 wt.%)/SiMCM-41, but the level of production
increased gradually with increasing Ti-content. On the other
hand, in Ti35 Si65 MCM-41 sample without Ca ingredient loading,
the methane generation did not signicantly increase compared
to the Ca loaded Ti35 Si65 MCM-41 sample. This is an evidence
that the Ca ingredient affects the photoreaction of CO2 perhaps
increasing the amount of adsorption of carbon dioxide on the
calcium surfaces. The maximum CH4 yield was 9.8 mol g1 cat L1
over the Ca(5.0 wt.%)/Ti35 Si65 MCM-41 catalyst after 8 h compared to 2.6 mol g1 cat L1 using the Ca(5.0 wt.%)/Ti35 Si65 O2
nanocomposite (reference material, hydrothermal synthesis, 2050 nm particle size, 80.0 m3 g1 specic surface
area); however, the yield was lower in the more Ti-inserted
Ca(5.0 wt.%)/Ti50 Si50 MCM-41 catalyst due to pore collapse. These
results show that the effects of the mesopores are more extensive in
photoreaction.
On the other hand, Fig. 11 shows the effect of the Ca
loading (1.0, 5.0, 10.0, and 15.0 wt.%) in the Ti35 Si65 MCM41 sample on CO2 photoreduction. The CH4 yield increased

Fig. 11. Effect of the Ca loading (1.0, 5.0, 10.0, and 15.0 wt.%) on the Ti35 Si65 MCM-41 sample on CO2 photoreduction.

S.W. Jo et al. / Applied Surface Science 355 (2015) 891901

remarkably and reached 82 mol g1 cat L1 after 8 h over

Ca(10.0 wt.%)/Ti35 Si65 MCM-41; this value was 8 times higher
than that over Ca(5.0 wt.%)/Ti35 Si65 MCM-41. This means that
CO2 absorption increased stably over the 10 wt.% CaO, which
led to an increase in the proportion of methane. In contrast,
when Ca(15.0 wt.%)/Ti35 Si65 MCM-41 was used, the CH4 yield
decreased to 8 mol g1 cat L1 after irradiation for 8 h. This was
attributed to an increase in the number of photons from the
light source that reached the large pores over the surfaces of
the Ca(10.0 wt.%)/Ti35 Si65 MCM-41 catalyst, allowing the electrons generated from the catalysts to be transferred efciently
to the CO2 gas. In the case of the 15% Ca-loading, however, the
Ti35 Si65 MCM-41 surface was covered with CaO; hence, the number of photons from the light source that reached the large pores
decreased.
The efciency for the photogenerated electronhole production in Ti35 Si65 MCM-41 and Ca(10.0 wt.%)/Ti35 Si65 MCM-41 lms
was measured by photocurrent response under solar light irradiation at an applied potential of 0.7 V versus SCE. Fig. 12 shows
the typical real time photocurrent response of the Ti35 Si65 MCM41 and Ca(10.0 wt.%)/Ti35 Si65 MCM-41 lms, when the light source
is switched on and off, exhibiting rapid photocurrent rise and
decay. In semiconductor systems, when an irradiation provides
energy higher than the band gap of semiconductor, the energy
excites the electrons from valence band to conduction band
and leaves a hole in valence band. The electronhole is responsible of the photocurrent. When the light was turned on, a
rapid increase in the photoreduction current was observed, and
the photocurrent then turned to a steady state after a few
seconds, as light off, the photocurrent dropped to nearly zero

899

Fig. 12. Photocurrent responses under solar light irradiation at an applied potential
of 0.7 V versus SCE for Ti35 Si65 MCM-41 and Ca(10.0 wt.%)/Ti35 Si65 MCM-41 lms.

instantaneously [43]. When the light was turned on, the maximum
photocurrent was obtained for the Ca(10.0 wt.%)/Ti35 Si65 MCM-41
lm with 137 nA cm2 , which is 9.6% higher than that achieved
on Ti35 Si65 MCM-41 lm (113 nA cm2 ). Additionally there are no

Scheme 1. Model for CO2 photoreduction over Ca/Tix SiMCM-41s.

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S.W. Jo et al. / Applied Surface Science 355 (2015) 891901

current transients in both the light-on and the light-off regions

in samples falling off with time in 50 s to a steady state value
which indicates that there are few surface recombination processes happened. Therefore Ca ingredient has a benecial effect on
photocurrent: it plays a role as the intermediate for the efcient
separation of photogenerated holeelectron pairs. However, we
have conrmed that the increase of e /h+ recombination is rather
observed for 15% loading, thus this study suggests a suitable loading
amount of calcium is present.
Scheme 1 presents a proposed model for CO2 photoreduction
over Ca/Tix SiMCM-41. Photon excitation over Ca/Tix SiMCM-41 will
start fast because it has a very short band-gap, otherwise its photocatalytic activity will decrease due to rapid recombination of the
electronholes induced by the short band-gap. On the other hand,
if CaO is present on the surface of Ca/Tix SiMCM-41, photocatalysis is possible because of the ability of CaO to trap and release
electrons into the conduction band of TiO2 together with signicant CO2 absorption, resulting in a signicant increase in the CH4
yield over Ca/Tix SiMCM-41. Therefore, the Ca loading can promote charge pair separation of the Tix SiMCM-41 photocatalyst to
achieve higher CO2 reduction efciency. Photo-excited electrons on
the Ca/Tix SiMCM-41 conductance band can be accepted and transferred efciently to CO2 adsorbed on CaO, functioning as an efcient
reducing agent. The positive holes on the Ca/Tix SiMCM-41 valance
band can be trapped by OH or H2 O species. These processes
promote the separation of photogenerated electronhole pairs
(e /h+ ) to accelerate the CO2 reduction process, and enhance the
Ca/Tix SiMCM-41 catalytic performance. Note that an excess metal
content reduces the photoactivity, as observed with the 15.0 wt.%
loaded Ca/Tix SiMCM-41 sample, possibly due to the establishment
of charge recombination centers inside the semiconductor structure [44].

4. Conclusions
To enhance the photoreduction of CO2 to CH4 , this study evaluated a new type of photocatalyst, Tix SiMCM-41(x = 5, 15, 35, and
50 mol.%), in which Ti was partially incorporated into the SiMCM41 framework using a controlled hydrothermal method, and to
improve CO2 adsorption, Ca(1.0, 5.0, 10.0, and 15.0 wt.%) was
loaded on the surface of Tix SiMCM-41. XRD and TEM conrmed that
the Ca(5.0 wt.%)/Tix SiMCM-41 exhibited a hexagonal porous crystal
structure, approximately the hexagons 24 nm in size. The bandgap decreased according to Ti addition, whereas the PL intensities
exhibited an opposite trend. The photocurrent was improved by Ca
loading and an appropriate amount value, 10.0 wt.%, was existed
in there. The CH4 generation was enhanced dramatically, and it
was 3 times higher over mesoporous Ca(5.0 wt.%)/Ti35 Si65 MCM-41
after an 8 h reaction than over nano-sized Ca(5.0 wt.%)/Ti35 Si65 O200 .
In particular, the photoreduction of CO2 with H2 O revealed a
remarkable increase in CH4 generation over the Ca 10.0 wt.% loaded
Ti35 Si65 MCM-41 catalyst to 82.0 mol g1 cat L1 after an 8 h reaction. The enhanced photoactivity in mesoporous Ca/TiSiMCM-41
can be attributed to effective charge separation over the Ca and
Ti additives, which inhibited the recombination of photogenerated
electronhole pairs.

Acknowledgements
This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF)
funded by the Ministry of the Science ICT & Future Planning (No.
2015R1A1A3A04001268).

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