i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 7 0 6 3 e1 7 0 7 4

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Efficient hydrogen production from glycerol

photoreforming over Ag2OeTiO2 synthesized by a
solegel method

Chao Wang a,*, Xiaoyan Cai a, Ying Chen a, Zhengdong Cheng a,b,
Xianglong Luo a, Songping Mo a, Lisi Jia a, Riyang Shu a, Pengcheng Lin a,
Zhi Yang a, Sifan Sun a, Enqi Pu a, Yiran Shen a
a
Guangdong Provincial Key Laboratory on Functional Soft Condensed Matter, School of Materials and Energy,
Guangdong University of Technology, Guangzhou 510006, PR China
b
Artie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, TX 77843-3122, USA

article info abstract

Article history: Photoreforming hydrogen production from glycerol aqueous solutions has been investi-
Received 22 March 2017 gated over Ag2OeTiO2 catalysts with variable compositions (0.72e6.75 wt.% of Ag2O) syn-
Received in revised form thesized by a solegel method. The structural and morphologic characteristics were
23 May 2017 examined by means of X-ray diffraction (XRD), field emission scanning electron micro-
Accepted 25 May 2017 scopy (FESEM), high resolution transmission electron microscopy (HRTEM) and Brunauer
Available online 22 June 2017 eEmmetteTeller (BET) method etc. By comparing the results of FESEM and DLS, aggrega-
tions of all samples were found to occur in both dry powder and water suspension states.
Keywords: The TiO2 based catalyst with 2.82 wt.% Ag2O calcined under 500
C showed less average
Glycerol photoreforming particle size differences between in air and in aqueous state, suggesting better dispersion
Hydrogen production stability which could lead to a more efficient of using light. It was found that mixing certain
Ag2OeTiO2 amounts (0.72e2.82 wt.%) of Ag2O to TiO2 could reduce anatase grain size and increased the
specific surface area of the catalysts. The hydrogen production results indicated that the
photocatalytic activity and the reaction rate of TiO2 were significantly improved by mixing
Ag2O. The optimal Ag2O mixing amount and calcination temperature for H2 production
was found. With an appropriate catalyst composition, the heterostructures could be well
generated to enhance the separation of electrons and holes and it was also found that the
desirable heterostructure was likely to disappear after the calcination temperature of
700
C.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

from fossil fuel burning, clean renewable energy is being ur-

Introduction gently demanded [1]. Hydrogen, as an energy carrier, has been
attracting considerable attentions due to its high energy mass
With diminishing fossil fuel resources and related issues of density with the absence of toxic or greenhouse-responsible
energy security and the effects of increasing greenhouse gases emissions during combustion [2]. In recent years, great

* Corresponding author.
E-mail address: chaowang@gdut.edu.cn (C. Wang).
http://dx.doi.org/10.1016/j.ijhydene.2017.05.183
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
17064 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 7 0 6 3 e1 7 0 7 4
efforts have been made for the development of economical,
environmentally, friendly, and competitive methods for
hydrogen production from renewable resources [3e5]. As re-
ported, the most commonly used method for hydrogen pro-
duction is steam reforming of hydrocarbon feedstock [6,7].
However, this reforming process involves in highly ender-
gonic reactions which are great energy consumptions,
implying high pressure and high temperature conditions for
triggering the reaction of gaseous or vaporized hydrocarbons
and steam are demanded even in the presence of catalysts
[8,9]. Photocatalytic method using solar energy as drive force
to produce hydrogen is particularly compelling, because this
method combines solar energy and renewable sources utili-
zation with semiconductor materials as catalysts [10,11]. In
fact, photocatalytic hydrogen production from pure water is
challenging due to the high Gibbs-free energy (27 kJ/mol,
1.23 eV) for splitting water into H2 and O2, and the fast back-
reaction between H2 and O2 to form H2O. A practical and
viable approach for solar hydrogen generation is employing
photoreforming reaction involving oxygenated organic sub-
stances, such as methanol, ethanol, glycerol etc. Among those
renewable resources, glycerol is produced as a byproduct in
the production of biodiesel through the catalytic trans-
esterification process. As the production of biodiesel all over
the world increasing in recent years, a great increment of
crude glycerol has been occurred, this has led to a lower price
[12]. Glycerol has already been studied as an effective sacrifi-
cial reagent for photocatalytic H2 production [13,14]. In the
previous studies of glycerol photoreforming, the first oxida-
tion process is initiated by OH-radicals or holes, and the al-
cohols are oxidized to aldehydes or carboxylic acids [15,16].
The following CeC bond cleavage is attributed to decarbon-
ylation or decarboxylation. In most cases, the carbon radicals
are oxidized by molecular oxygen.
This photoreforming reaction could be catalyzed by a va-
riety of semiconductor materials in the presence of UVevi-
sible light. Titanium dioxide (TiO2), in different crystalline
forms-pure or properly modified, is currently receiving
intensified interests due to its strong resistance to a wide va-
riety of chemicals, as well as its low cost [17]. However, the
performance of bare TiO2 is not satisfactory for H2 production
due to its limited light absorption range of solar spectrum;
rapid electron-hole pair recombination in photocatalysis
process and fast backward reaction between hydrogen and
oxygen [18]. To improve TiO2 photocatalytic performance,
studies have been conducted to reduce the bandwidth of TiO2
into the visible light range through mixing other semi-
conductor metal oxides [19e21] or doping nonmetal/metal
[22]. Researchers found that TiO2 based heterojunction,
semiconductor metal oxides (Ag2O, Bi2O3, CuxO, NiOx) couple
with TiO2, could effectively improve photocatalytic efficiency
[14,23e30].
Recently, we have reported that mixing semiconductor
metal oxides to TiO2 using solegel method was responsible for
photocatalytic H2 production. Ag2O composite displayed the
most effective catalytic results when mixed to TiO2 among the
selected semiconductor metal oxides [31]. For expanding from
our earlier research on Ag2O and TiO2 mixture catalyst,
several of Ag2OeTiO2 catalysts were prepared using solegel
method with their structure and morphology characteristics
examined. Critical synthesis parameters (e.g., catalyst com-
positions and calcination temperatures) were systematically
investigated. UVevis spectroscopy analysis was employed to
investigate the light adsorption properties of the synthesized
catalyst. H2 production from photoreforming of glycerol
aqueous solution was conducted under xenon lamp irradia-
tion with the quantum efficiency and H2 evolution rates
calculated. Changes in hetero-structural and compositional
characteristics of the various Ag2OeTiO2 catalysts as a result
of the photoreforming reaction were studied. Multi-cyclic
photoreforming H2 production has been experimentally
evaluated by the superior heterogeneous structural Ag2Oe
TiO2 catalyst.
Experimental
Catalyst preparation
All the reagents were of analytical grade and were used
without further purification (Aladdin Industrial Corporation,
Shanghai, China). The deionized water was obtained from
Millipore Milli-Q ultrapure water purification systems with a
resistivity larger than 18.2 mU. In this study, all the samples
were synthesized by a solegel method [32]. In a typical syn-
thesis procedure, 20 mL tetrabutyl titanate was dissolved in
80 mL of anhydrous ethanol with stirring continuously for 1 h
at room temperature to give a clear solution, designated as
solution A. And certain amount of silver nitrate was dissolved
in a mixture of 10 mL acetic acid, 10 mL water and 20 mL
ethanol (The Ag2O weight ratios were 0.72, 1.43, 2.82, 4.16 and
6.75 wt.%, with the molar ratios of silver to titanate based on
the starting compositions were 0.5, 1, 2, 3, 5, respectively.
According to the molar ratio of silver and titanium of the
selecting raw materials, the mass ratio of silver oxide and ti-
tanium dioxide could be theoretically calculated when
assuming all silver and titanium are oxidized to Ag2O and TiO2
after preparation. Then, an appropriate amount of aqueous
ammonia was added dropwise to the solutions with moderate
stirring until a final pH value of 3 was obtained. The obtained
solutions were slowly added respectively to solution A with
continuously stirring to give transparent homogeneous sols.
The obtained sols were placed in a 50
C water bath for aging
to produce gels. The obtained products were dried at 100
C for
24 h, followed by being calcined in air atmosphere for 4 h, and
are denoted in the following as x Ag (C) (x refers to mixing ratio
and C was calcination temperature). To be noted, short
calcination duration may not enough to remove organic sub-
stances in the materials thoroughly and left a certain content
of organic substances existing on the surface of the materials
blocking active sites on the surface. On the other hand, if the
calcination time is too long, the structure of the material
would be destroyed leading to active sites reduction [33]. In
addition, over duration of calcination would lead to sintering
which could further reduce the catalytic activity. The bare
TiO2 sample was also prepared by the similar procedure
except adding the nitrate. Other detailed descriptions for the
catalyst synthesis process were introduced in our previous
work [31]. In Table 1, some details of the prepared samples
were listed.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 7 0 6 3 e1 7 0 7 4 17065

maintained at 0.1 MPa to ensure an anaerobic condition. A

Table 1 e Physical properties of the prepared
continuous magnetic stirrer was applied at the bottom of the
photocatalysts.
reactor in order to keep the catalyst particles in a suspended
Sample SBET Pore Average Crystallite
state during the experiment. The produced gas (H2) was
(m2 g1) volume pore size size (nm)
analyzed by gas chromatographer (GC-2014c AT, Shimadzu,
(cm3 g1) (nm)
Japan, TCD, and nitrogen as a carrier gas and 5 Å molecular
Bare TiO2(500) 47.97 0.59 44.89 27.77
sieve column). The apparent quantum efficiency (AQE) and
0.72Ag2OeTiO2(500) 63.8 0.20 8.85 21.22
1.43Ag2OeTiO2(500) 76.67 0.37 13.0 21.31
light-to-hydrogen energy conversion efficiency (LTH) were
2.82Ag2OeTiO2(500) 56.38 0.24 9.67 22.30 calculated according to the following equations [34]:
4.16Ag2OeTiO2(500) 36.67 0.20 8.92 22.63
6.75Ag2OeTiO2(500) 28.50 0.14 16.41 23.81 P ¼ E  AR (1)
2.82Ag2OeTiO2(400) 60.92 0.30 13.44 17.19
2.82Ag2OeTiO2(600) 16.56 0.14 23.51 38.27 ptl
2.82Ag2OeTiO2(700) 2.229 0.03 39.51 46.51 Nip ¼ (2)
h$c

2RH2 NA t
Catalyst characterization Fa ¼ (3)
Nip

The textural properties (specific area, pore volume, and

average pore diameter) of the fresh catalysts were determined
with the Brunauer-Emmett-Teller (BET) method using a V-
Sorb X800 apparatus (Gold APP, Inc., China). The samples were
degassed prior to the measurement at 100
C for 1 h and then
at 120
C for 2 h. The X-ray powder diffraction spectra were
performed for diffraction angle 2q from 20
to 80
using Shi-
madzu XRD-6000 powder diffractometer, where a Cu target Ka
-ray (operating at 40 kV and 30 mA, with l ¼ 0.15406 nm), were
used to determine the phase structures of the obtained sam-
ples. A nominal step interval of 0.0025
2q with a step time of
100 s in continuous mode was routinely applied. The Scherrer
equation was performed to calculate the mean crystallite size
based on the diffraction peaks. A field emission scanning
electron microscopy (LEO 1530) was used to study the surface
morphology of catalysts. The particle sizes of the catalyst
samples were measured at 25
C using dynamic light scat-
tering (DLS) at a scattering angle of 173
with a Zeta sizer Nano
ZS particle size analyzer (Beckman Coulter, Inc., USA). The
morphology of the photocatalysts was investigated by trans-
mission electron microscopy (TEM) using JEM-2100. For the
TEM analysis, the samples were ground and dispersed with
ethanol, and deposited on a Cu grid covered with a perforated
carbon membrane. UVevis absorption spectra of the samples
were obtained by a UVevis spectrophotometer (UV-9000).
Photocatalytic H2 production
The photocatalytic H2 production experiments were conduct-
ed in a duplex Pyrex flask at ambient temperature, and open-
ings of the flask were sealed with a silicone rubber seals and
glass lid. A 300W Xe arc lamp (320e780 nm, Philae technology
co., Ltd, China), employed as light sources, was vertical fixed at
10 cm away from the photocatalytic reactor. The intensity of
radiation at the center of the reactor, as measured with a
radiometer, was approximately 350 Wm2, and the reactor
light receiving area was 0.28 cm2, which was calculated by the
spot diameter of xenon lamp. In each photocatalytic experi-
ments, 0.2 g catalyst was suspended in 100 mL glycerol
aqueous solution (with 7 vol.% of glycerol). Prior to irradiation,
the entire experimental system was evacuated to completely
remove the dissolve air/oxygen and the system pressure was
DH0c RH2
h¼ (4)
P
where P is radiation flux, E is average irradiance, AR is light-
receiving area of reactor; Nip is number of incident photons, t
is reaction time, l is equivalent wavelength, h is Planck con-
stant, c is constant speed of light; Fa is the apparent quantum
efficiency (AQE), RH2 is the obtained hydrogen production rate,
NA is the Avogadro constant; h is defined as the light-to-
hydrogen (LTH) energy conversion efficiency, DH0c is the
enthalpy of combustion of hydrogen.
Results and discussion
Characterizations of the synthesized catalysts
Generally, a catalyst with a high specific surface area and a
large pore volume is indispensable for a superior catalytic
performance [35,36]. The pore structure and BET surface areas
of as-prepared samples were investigated by the adsorption-
desorption measurement. The typical isotherms for nitrogen
adsorption and desorption of the samples were shown in
Fig. 1(a). The Barrett-Joyner-Halenda (BJH) method was
employed to analyze the pore size distributions, and the re-
sults were shown in Table 1 and Fig. 1(b). The bare TiO2 sample
had a specific surface area of 47.97 m2/g with a pore volume of
0.59 cm3/g. Actually, the surface area and pore size distribu-
tion of the Ag2O mixed TiO2 samples strongly depended on the
calcination temperature and the mixture amount. It can be
seen that all calcined samples show type IV adsorption iso-
therms according to IUPAC classification, indicating the
presence of mesopores (2e50 nm). The isotherm of bare TiO2
presented a typical hysteresis loop of type H3 (Fig. 1(a)) at a
high relative pressure range of 0.8e1.0, suggesting the pres-
ence of slit like pores due to the stacking of TiO2 particles [37].
After mixing Ag2O, the isotherms showed a typical hysteresis
loop of type H2 which was attributed to the difference in the
adsorption and desorption mechanisms occurring in the “ink-
bottle” pores [38]. Comparing to bare TiO2, the specific surface
area of the particle could be changed by mixing certain
amount of Ag2O. When the mixing ratio of Ag2O was over
17066 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 7 0 6 3 e1 7 0 7 4
Fig. 1 e Nitrogen adsorption-desorption isotherms (a) and
pore size distribution (BJH desorption) (b) of bare TiO2 and
the TiO2 samples mixed with different Ag2O ratios.
1.43 wt.%, the surface area decreased with the increasing of
Ag2O ratio. This kind of decrease in the surface area could be
attribute to the blocking of fine capillaries of parent TiO2
surface which was the deposition of Ag2O and partial
obstruction of the TiO2 void space when Ag2O was growing on
the surface of TiO2 [14,39]. The pore size distribution curves
(Fig. 1b) were derived from desorption branches of the nitro-
gen isotherms by Barrett-Joyner-Halenda (BJH) method. The
pore size distribution curve of bare TiO2 was spread more
evenly throughout a wider range of pore diameters. Table 1
depicted the physical properties of the prepared photo-
catalysts. The bare TiO2 sample showed a bigger pore volume
and porosity compared with those of Ag2OeTiO2 samples. It
can be ascribed to the formation of more aggregates of TiO2
crystallites in Ag2OeTiO2 samples. In general, such aggregated
porous structures might be of great benefit to the photo-
catalytic process since they might provide efficient transport
pathways to reactant and product molecules [40,41].
The crystal structures of the prepared samples were
characterized by XRD illustrated in Fig. 2. For the calcination
temperature of 500
C (Fig. 2(a)), TiO2 in the XRD patterns of all
samples showed only the anatase phase. The average crys-
tallite sizes of particles are estimating from the widths of
anatase (101) reflection obtained from the XRD results by the
Scherrer formula and the results are shown in Table 1. It
Fig. 2 e XRD spectra of (a) Ag2OeTiO2 with different
composition ratios calcined at 500
C; and (b) 2.82Ag2Oe
TiO2 with various calcination temperatures.
showed that with an increasing weight ratio of Ag2O
(0.72e6.75 wt.%), the crystallite size of TiO2 was increased
from 21.22 nm to 28.82 nm. Obviously, the addition of Ag2O to
TiO2 did not affect the crystal form. However, the addition of
Ag2O decreased the crystallite size of anatase compared with
that of bare TiO2. In addition, the absence of the diffraction
peaks corresponding to Ag2O implies a good dispersion of
sliver species in relatively low ratio of Ag2O [42,43]. Fig. 2(b)
showed the XRD patterns of 2.82Ag2OeTiO2 with different
calcination temperatures. At lower calcination temperatures
(i.e. 300e600
C), only anatase phase was detected. When the
calcination temperature reached 700
C, the rutile phase
appeared. And the anatase crystallite size increased with
increasing calcination temperature (300e700
C).
The surface morphologies and grain sizes of the as-
prepared photocatalysts with different composition ratios
were characterized by FESEM shown in Fig. 3. Small and
irregular bare TiO2 particles with an average size of 49.87 nm
(analyzed by software Nano Measurer 1.2.0) was observed in
Fig. 3(a), and some agglomerates were randomly formed with
the estimated size around 140e210 nm. Compared with bare
TiO2, the observation of bright Ag2O nanoparticles attached on
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 7 0 6 3 e1 7 0 7 4 17067

that some Ag2O particles are too small to be observed at the

resolution of the used microscope.
The catalyst size was also measured in aqueous suspen-
sion with a certain concentration using dynamic light scat-
tering (DLS) technique. Fig. 4 showed the DLS histogram of

Fig. 3 e FESEM images and average particle size of: (a) bare
TiO2; (b) 2.82Ag2OeTiO2 (500); (c) 6.75Ag2OeTiO2 (500).

the surface of TiO2 indicated the formation of Ag2OeTiO2

heterostructure shown in Fig. 3(b) and (c). The formed Ag2Oe
TiO2 heterostructure structures largely gathered on the sur-
face of the catalyst particle may accelerate the separation of
photo-generated electron-holes leading to an enhancement of
the photocatalytic performance [44]. Fig. 3(b) showed that the
2.82Ag2OeTiO2(500) sample was also consisted with agglom-
erated nanoparticles with the size of 60e160 nm, and the
average size of those individual small particles were 36.08 nm.
During the elimination of the impurities and crystallization of
anatase phase by drying and calcination process, the uni-
formly dispersed Agþ ions would gradually migrate from the
bulk anatase grains to the surface of the TiO2 particle. In this
case, those Agþ ions would compete with Ti4þ and O2 for
diffusion and reorganization, and anatase crystallization and
grain growth are then suppressed [19]. For samples with
higher Ag2O compositions, serious agglomeration would Fig. 4 e Particle size distribution histograms based on DLS
occur. Fig. 3(c) showed that Ag2O mixed to TiO2 catalyst con- data for the TiO2 based particles (average particle size and
tained irregular shaped particles which are the aggregation of standard deviation are calculated from the Gaussian
clustered crystals, and the average size of those individual fittings of the histograms): (a) bare TiO2; (b) 2.82Ag2Oe
small particles were 36.37 nm. However, it cannot be ruled out TiO2(500); (c) 6.75Ag2OeTiO2(500).
17068 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 7 0 6 3 e1 7 0 7 4

Fig. 5 e Typical TEM and HRTEM images of: (a) bare TiO2; (b) 2.82Ag2OeTiO2(400); (c) 2.82Ag2OeTiO2(500); (d) 2.82Ag2Oe
TiO2(700).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 7 0 6 3 e1 7 0 7 4 17069

particle size distributions. Compared with the results ob-

tained from FESEM, the average catalyst sizes measured by
DLS technique increased for all samples. This may due to that
the measured environments were different. Generally
speaking, the individual particles were the objects being
measured for FESEM analysis and both individual and aggre-
gated particles suspended in water were the objects being
measured for DLS. The curves of the size distributions peaked
with relatively large tails toward either larger or smaller
values shown in Fig. 4. These observations indicated both
irregular size nanoparticles and clusters coexist in all sam-
ples. The average particle size differences of the FESEM and
DLS results could reflect the dispersion stability properties of
the catalysts in the aqueous suspension which could strongly
influence their performances in photoreforming reactions
[45,46]. As calculated, the differences of particle size distri-
bution in different media of bare TiO2, 2.82Ag2OeTiO2(500),
6.75Ag2OeTiO2(500), were 47.65%, 46.60%, 83.05%, respec-
tively. Among those, 2.82Ag2OeTiO2(500) showed a relatively
small average size differences between powder and suspen-
sion state which may lead to a more efficient of using light.
And better dispersion stability in suspension could exhibit
more advantages to surface contact between catalyst particle
and reactants.
Typical HRTEM images were used to further investigate the
formation of the Ag2OeTiO2 heterostructures. The Ag2O
nanoparticles were tightly coupled on the surface of TiO2
nanoparticles to form Ag2OeTiO2 heterostructure were shown
in Fig. 5, which was propitious to electron transmission be-
tween the two phases. By measuring the lattice fringes, the
resolved interplanar distances were 3.5 Å corresponding to the
(101) plane of anatase TiO2, and 2.7 Å corresponding to the
(111) plane of Ag2O. These results also suggest that the pre-
pared sample behaved as a well-crystallized heterostructure
with Ag2O nanoparticles and TiO2 nanoparticles on nanoscale.
The distinguished interfaces between lattice fringes of Ag2O Fig. 6 e UVevis absorption spectra of: (a) bare TiO2 and the
and TiO2 indicated the formation of a heterostructure, which mixed samples at different Ag2O amount; (b) 2.82
was expected significantly promote the charge separation ef- Ag2OeTiO2 calcined at various temperatures suspended in
ficiency, therefore enhance the photocatalytic activity [47]. aqueous solutions.

UVevis analysis
UVevis is an important method for optical characterization of
semiconductor materials. The UVevis absorption spectra of
the prepared samples at room temperature were shown in
Fig. 6. The absorption onsets were determined by linear
extrapolation from the inflection point of the curve to the
base-line. All the TiO2 based photocatalysts showed strong
absorption band at 350 nm which may be associated with
excitation of O2p electron to Ti3d level [14]. As shown, the
samples of TiO2 mixed with Ag2O showed better UVevis light
absorption performance with certain degrees of red-shift
compared to that of bare TiO2. It has been reported that the
extended absorption in visible region was ascribed to inter-
action of Agþ ions with TiO2 [48]. As observed, the mixing of
Ag2O to TiO2 extended the band of light absorption. The ab-
sorption above 400 nm in Ag2OeTiO2 heterostructure photo-
catalyst was attributed to the presence of Ag2O nanoparticles
as visible-light sensitization, which had a strong and wide
absorption band in the visible-light region [47]. Fig. 6(b)
showed UVevis spectra of 2.82Ag2OeTiO2 particles with
different calcination temperatures. The mixing of 2.82 wt.%
Ag2O was found to have a significant impact on the absorption
at wavelength>350 nm. With an increasing calcination tem-
perature, the heterostructure was more fully formed with a
significant increase in absorbance of light. However, the ab-
sorption peak an obvious decrease at a temperature higher
than 500
C, which may due to that the heterostructure was
destroyed by high temperature calcination.
Photocatalytic activity tests
In the present study, 200 mg catalyst was suspended in 100 ml
with 7 vol% of glycerol and the hydrogen production experi-
ments were proceed under the Xenon lamp irradiation. The
maximum rates of H2 evolution obtained for the calcined
500
C samples were plotted as functions of Ag2O mixture in
Fig. 7. From the results, all Ag2OeTiO2 catalysts showed higher
H2 evolution rates of than that of bare TiO2 due to the presence
17070 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 7 0 6 3 e1 7 0 7 4
Fig. 7 e Maximum H2 production rate over: (a) bare TiO2; (b)
0.72Ag2OeTiO2(500); (c) 1.43Ag2OeTiO2(500); (d) 2.82Ag2Oe
TiO2(500); (e) 4.16Ag2OeTiO2(500); (f) 6.75Ag2OeTiO2(500).
of Ag2O composition that could enhance the harvest of visible
light. Actually, the electrons were excited from the valence
band to the conduction band and then they could migrate to
Ag2O preventing the direct recombination of electrons and
holes. The formed heterostructure composite of Ag2O and
TiO2 can act as rapid separation sites for the photo-generated
electrons and holes due to the difference in the energy levels
of their conduction and valence bands. The rate of H2 pro-
duction was increased with the increasing the ratio of Ag2O in
hetero composite catalyst and decreased beyond the optimum
level of 2.82 wt.% (2.82Ag2OeTiO2(500)). In our previous study,
Fig. 8 e Typical time course of: (a) H2 production amount, (b) hydrogen evolution rate, (c) quantum efficiencies and (d) Light-
to-hydrogen energy efficiency over 0.2 g the as-prepared photocatalysts of 2.82 Ag2OeTiO2 calcined at various temperatures
in 7 vol.% aqueous solutions of glycerol aqueous solutions.
we have found the optimized conditions for glycerol photo-
reforming hydrogen production [31]. At such conditions, the
H2 production rate over the synthesized 2.82Ag2OeTiO2(500)
catalyst was found to be 336.7 mmol h1 g1, and the values
exceed that of bare TiO2 by a factor of 63. At lower Ag2O mixing
ratios (0.72 and 1.43 wt.%), the H2 production was directly
proportional to the amount of catalytic active sites. With
2.82 wt.% Ag2O composition ratio, agglomeration of Ag2O
nanoclusters tended to form nanoparticles which could be
observed in the related FESEM results. This phenomenon
could lead to mismatch the band potential resulting in poor
visible light sensitization and hence lower catalytic activity
[14]. Glycerol acted as a sacrificial agent by removing rapidly
and irreversibly photogenerated holes, oxidants (e.g., OH)
and/or oxygen produced by cleavage of water. The result of
the photoreforming reaction was actually the conversion of
glycerol and reaction intermediates into CO2 and H2. These
intermediates can be formed via a series of transformation
steps involving dehydration, dehydrogenation, decarbon-
ylation and hydrogenation reactions [15].
Based on the study of catalyst composition ratio, the
selected ratio of 2.82 wt.% Ag2O was further studied for the
calcination temperatures (300e700
C). Fig. 8(a) demonstrated
the results of photoreforming H2 production changed with
time over the catalysts calcined at various temperatures. It was
found that the photocatalytic activity of the catalyst calcined at
500
C was higher than those catalysts calcined at other tem-
peratures. The catalysts showed poor photocatalytic activities
with lower calcination temperatures could be due to the poor
crystallinity which lead to poor formation of heterostructure
between Ag2O and TiO2. The decrease in photocatalytic activity
of the catalyst calcined at higher calcination temperature was
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 7 0 6 3 e1 7 0 7 4 17071

attributed to the sintering which could lead to low surface area the reactor was completely wrapped with aluminum foil and
and particle aggregation [49]. From XRD results, it was found kept overnight in the absence of light at room temperature.
that both anatase and rutile phases appeared for the catalyst From Fig. 10, it displayed that the activity of 2.82Ag2Oe
calcined at 700
C. Although the coexist of anatase and rutile TiO2(500) did not undergo a significant decline in 7 vol%
phases was very likely to enhance the photocatalytic perfor- glycerol-water solution for the first three consecutive recycles
mance [50,51], the decrease in specific surface area caused by and minor decrease in amount of H2 production in the last 2
sintering obviously had a greater effect on reducing the cata- cycles were found. This was mainly attributed to the increase
lytic activity. In Fig. 5(b) and (c), the observed particle size of of the adsorbed oxidation intermediates on the catalyst sur-
2.82Ag2OeTiO2(400) and 2.82Ag2OeTiO2(500) were smaller face that influenced the light penetration to the surface [54].
than that of bare TiO2 and 2.82Ag2OeTiO2(700). The individual In order to compare the band gap of bare TiO2 and Ag2Oe
Ag2O particles were very small and viewed as dark patches on TiO2(500), Kubelka-Munk diagram was presented in Fig. 11. For
the surface of transparent TiO2 particles for 2.82Ag2Oe bare TiO2, the band gap was estimated to be 3.22 eV and Ag2Oe
TiO2(400), 2.82Ag2OeTiO2(500) and 2.82Ag2OeTiO2(700) (Fig. 5b, TiO2(500) was 2.98 eV. The decrease in the band gap energy of
c and d). When the calcination temperature was increased to Ag2OeTiO2(500) may be one of the main factors responsible
700
C (Fig. 5d), the nanoparticles may be promoted the for- for the enhancing H2 production rate. As the phase of TiO2 did
mation of larger and more irregularly shaped crystals ranging not change when mixing Ag2O (Fig. 2), the decrease in the
from 30 to 70 nm. In addition, the HRTEM image also showed band gap observed should result from the formation of Ag2Oe
the desirable heterostructure was likely to disappear after the TiO2 heterojunction.
calcination temperature of 700
C. Actually, Ag2O nanoparticles were unstable and could be
The QE and LTH energy conversion efficiency results could reduced to metallic Ag by photogenerated electrons, this was
be calculated based on the experimental data and equations
(1)e(4). From the results were shown in Fig. 8(c) and (d), the QE
value increased with the increasing irradiation time while the
LTH energy conversion efficiency reached its maximum value
in the first few hours under the total experimental duration of
6 h. The maximum value of the QE was 8.73% for 2.82Ag2Oe
TiO2(500), and only 0.14% for bare TiO2. The maximum LTH
energy conversion efficiency was 0.45% for 2.82Ag2Oe
TiO2(500) and 0.007% for bare TiO2. Compared to other studies
using TiO2 based catalysts and organic solution as the sacri-
ficial reagents for hydrogen production, the LTH value ob-
tained of our study for photoreforming was acceptable and
competitive [52,53]. The obtained 2.82Ag2OeTiO2(500) catalyst
showed a better catalytic activity, was further subjected for a
longer time test with the same experimental conditions. Fig. 9
indicated the continuous H2 production lasted for 12 h. From
the result, the catalyst activity started to decay its activity at
the time of 7 h and this slow decay continued more than 12 h. Fig. 10 e Cycling tests of photocatalytic activity of
The cyclic stability of the photocatalysts was also investigated 2.82Ag2OeTiO2(500) under xenon lamp irradiation.
by performing the experiments with 2.82Ag2OeTiO2(500)
catalyst for 5 times with 5 h test for each time. After each test,

Fig. 9 e Time profile of the H2 evolution in photocatalytic

reaction between glycerol and water with 2.82 Ag2OeTiO2 Fig. 11 e Kubelka-Munk diagrams obtained from the data
calcined at 500
C. (Fig. 6) of bare TiO2 and 2.82 Ag2OeTiO2(500).
17072 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 7 0 6 3 e1 7 0 7 4
Fig. 12 e (a) XRD spectra of the fresh and spent catalyst; (b)
HRTEM images of the catalyst after reaction.
confirmed by XRD and HRTEM results for the spent catalyst
(Fig. 12). In the experiments, the wavelength range of the lamp
was 320e780 nm, including the visible and ultraviolet light.
Under UV light irradiation, both TiO2 and Ag2O can be excited
to generate (electros) e and holes (hþ) according to (R1) and
(R2). The generated holes in TiO2 and Ag2O react with H2O and
produce reactive oxygen species OH (R3). The obtained e
reacts with Ag2O nanoparticles, which could be reduced to Ag
according to (R4). At the same time, the generated O2 from
Ag2O (R4) through (R5) to produce reactive oxygen species OH,
more reactive oxygen species could improve the photo-
catalytic activity under UV-light irradiation [47]. For solar
irradiation, only Ag2O can be excited to produce hþ and e,
and electrons from the conduction band of Ag2O are trans-
ferred to the conduction band of TiO2. And the biphasic Ag2Oe
Ag mixed TiO2 is highly active in photocatalytic hydrogen
production where Ag2O acts as a visible light sensitizer and
the metallic Ag formed acts as an electron sink [13].
hv þ
TiO2 !h þ e
hv þ
Ag2 O!h þ e
þ
h þ H2 O/OH þ Hþ
Ag2 O þ e /Ag þ O2
e þ O2 þ H2 O/OH þ OH (R5)
Conclusion
In summary, a solegel method was used to prepare various
Ag2OeTiO2 catalysts for the photoreforming H2 production
from glycerol aqueous solution. The HRTEM images confirmed
the interaction of Ag2O on the surface of TiO2 nanoparticles.
The heterostructure was formed between Ag2O and TiO2 with
extended absorption range. As shown in the obtained results,
the Ag2O mixture has a depression effect on the anatase grain
growth at certain ratios. The synthesized samples were found
to be active for the glycerol photoreforming reaction toward
H2 production. Under xenon lamp irradiation, 2.82 wt.%
Ag2OeTiO2 possessed a higher H2 production rate
(336.7 mmol h1 g1, 62 times of bare TiO2), a higher quantum
efficiency (10.9%, 43 times of bare TiO2) and a higher LeTeH
energy conversion (0.48%, 60 times of bare TiO2). This high
photocatalytic activity of the synthesized 2.82Ag2OeTiO2 may
be attributed to: the presence of Ag2O nanoparticles as visible
light sensitizer and heterojunction between Ag2O and TiO2
particles can act as rapid separation sites for the photo-
generated electrons and holes because of the difference in
the energy levels of their conduction and valance bands. The
results showed that specific surface area and crystallite size of
the synthesized catalysts may have little effect on their ac-
tivities. In addition, it was found that the catalytic perfor-
mance also depended on the calcination temperature. The
catalysts were shown low photocatalytic activities at low
calcination temperatures owing to the poor crystallinity
which was unfavorable for the formation of the heteroge-
neous structures. When the calcination temperature was too
high, photocatalytic activities would also take place because
of the low surface area and destruction of heterostructure
caused by high temperature sintering. 2.82 wt.% Ag2OeTiO2
with the calcination temperature of 500
C displayed a better
H2 production amount and rate were 2940.2 mmol g1 and
338 mmol g1 h1, with the calculated QE of 13.84% and LTH
energy conversion efficiency of 0.48% under the total experi-
mental duration of 12 h. As the increasing adsorbed oxidation
intermediates on the surface that influenced the light recep-
tion, the catalytic activity was found to suffer a significantly
decline after the 3rd test in the cyclic experiment.
Notes
The authors declare no competing financial interest.
(R1)
Acknowledgement
(R2)
This work was supported by Natural Science Foundation of
(R3) China (No. 51606046), and International Science & Tech-
nology Cooperation Program of Guangzhou, China
(R4) (2016201604030063).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 7 0 6 3 e1 7 0 7 4 17073

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