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Materials Chemistry A
PAPER
and UV-visible spectroscopy and could be involved in the cathodic O2 photoreduction in the PFC.
Furthermore, amorphous-like BiO1xCl species were observed on the surface of the BiOCl crystallites in
high-resolution transmission electron microscopy. Importantly, this PFC that comprises TiO2 and BiOCl
is sustainable, recyclable, and has a series resistance that can be controlled by adjusting the BiOCl
DOI: 10.1039/c4ta06824f
particle size, and exhibits a more ecient charge ow because of band bending than that of a previously
www.rsc.org/MaterialsA
Introduction
Fossil fuels have been utilized as the essential energy source for
industrialization. However, industrial CO2 emissions have led
to an increase in the atmospheric CO2 concentration (400 ppm),
and thus the eects of this increase in terms of global warming
cannot be underestimated. The development of renewable
energy as a replacement for fossil fuels has been slow.1,2 Among
these renewable energies, solar energy has the greatest potential; the solar energy that reaches the earth in 1 h is equivalent
to the energy consumed on the earth in 1 year.1,2 Although
c
Department of Mechanical Engineering, Graduate School of Engineering, Chiba
University, Yayoi 1-33, Inage-ku, Chiba 263-8522, Japan
Paper
(A) UV-visible absorption spectra for solvo-BiOCl (a) as-synthesized, irradiated under UV-visible light in Ar for (b) 1 min and (c) 1.0 h, (d)
sample c in the dark for 24 h, and (e) sample d exposed to air for 5 h. (B) Fitting to the DavisMott equation for the data in (A-a). The values for (a
hn)2, (a hn)2/3, (a hn)1/2, or (a hn)1/3 versus hn were plotted, and the intercept with the x-axis estimated the Eg value. (C) UV-visible
absorption spectra for solvo-BiOCl (a) as-synthesized, (b) irradiated under UV-visible light in air for 1.0 h, and sample b in the dark (c) for 24 h and
(d) 92 h. XRD patterns for solvo-BiOCl (D) as-synthesized, (E) irradiated with UV-visible light under Ar for 9 h, and aqua-BiOCl (F) as-synthesized.
(G and G0 ) Raman spectra for BiOCl (a) as-synthesized and (b) irradiated using UV-visible light for 12 h under vacuum.
Fig. 1
Paper
Scheme 2 Components and chemical reactions in a PFC and Type 14 PECs. The dotted arrow indicates the possible use of a photoelectrode or
a general electrode, and the dotted line at the middle of the cell indicates the possible use of a PCP for separation.
2 Experimental
2.1 Sample syntheses and preparation of the
photoelectrodes
TiO2 powder [1.00 g; P25, Degussa; anatase/rutile phases 7/3;
BrunauerEmmettTeller (BET) surface area (SBET) 60 m2 g1]
was suspended in 3.0 mL of deionized water (<0.06 mS cm1)
and then stirred well. The obtained suspension was dried at 373
K for 24 h and heated in air at 673 K for 2 h. The resultant
powder was suspended in 75 mL of deionized water and placed
on an indium tin oxide (ITO, thickness 1.2 to 1.6 mm)-coated
Pyrex glass plate. The TiO2/ITO/Pyrex was dried at 373 K for 18 h
and heated in air at 573 K for 30 min. The amount of TiO2
deposited on the ITO-coated glass plate was 5.0 mg and covered
an area of 1.3 cm2.
BiOCl was synthesized using a solvothermal procedure.34
Bismuth nitrate pentahydrate (2.00 g; >99.5%, Wako Pure
Chemical) was dissolved in 80 mL of ethylene glycol (>99.5%,
Wako Pure Chemical), and then cetyltrimethylammonium
chloride (1.30 g; >95%, Wako Pure Chemical) was added to the
mixture. The solution was magnetically stirred at a rate of 900
rotations per minute (rpm) at 290 K for 1 h. Next, ethylene glycol
solution (4.5 mL) of potassium hydroxide (1.0 mol L1; 85%,
Wako Pure Chemical) was added. The solution was then introduced into a Teon-lined autoclave (Model TVS-N2-100, Taiatsu
Techno) and maintained at 433 K for 12 h. This solution was
ltered using a polytetrauoroethene membrane lter (Model
Omnipore JGWP04700, Millipore) with a pore size of 0.2 mm,
and the collected white powder was subsequently washed with
deionized water (total 450 mL) and ethanol (total 450 mL) and
dried at 323 K for 12 h. The obtained white BiOCl powder is
denoted as solvo-BiOCl (or simply BiOCl).
For comparison, some of the experiments using BiOCl
synthesized from an aqueous solution were also performed.35
For this process, 3.15 g of Bi trichloride (>97%; Wako Pure
Chemical) was dissolved in 100 mL of deionized water. The
Paper
Characterization
(1)
Scheme 3
0:9l
:
Full width at half maximum cos qB
(2)
Raman spectra were obtained at 290 K using a model NRS5100 (JASCO) with the excitation wavelength of 532 nm for the
solvo-BiOCl samples as-synthesized and irradiated by UV-visible
light for 12 h under vacuum. The intensity of the laser was
1 mW and a CCD detector was used at 203 K.
X-ray photoelectron spectra (XPS) were obtained using a
Model AXIS-NOVA, Shimadzu/Kratos equipped with an X-ray
source Al Ka (1486.6 eV). O 1s, Bi 4f5/2, and Bi 4f7/2 regions were
narrowly scanned. The C 1s (284.8 eV) was used as a reference
for energy calibration for adventitious hydrocarbon on the
specimen surface.41 BiOCl sample irradiated by UV-visible light
for 2.5 h under Ar, and another BiOCl sample immersed in HCl
aqueous solution (pH 2.0) irradiated by UV-visible light for 2.5 h
under O2 were mounted on a sample holder and the sample
holder was introduced to a transfer vessel under Ar atmosphere.
The transfer vessel was connected to AXIS-NOVA, the gate valve
was opened, and then the sample was transferred inside AXISNOVA without any contact with air.
Bismuth L3-edge extended X-ray absorption ne structure
(EXAFS) spectra were obtained at 290 K in the transmission
mode in the Photon Factory Advanced Ring and Photon Factory
at the High Energy Accelerator Research Organization (Tsukuba) on beam lines NW10A and 9C.4245 The storage ring energy
was 6.5 and 2.5 GeV, and the ring current was 33.055.8 and 450
mA. A Si (311) and (111) double-crystal monochromator and a
platinum and rhodium-coated focusing cylindrical mirror were
inserted into the X-ray beam path. X-ray intensity was maintained at 65% of the maximum ux using a piezo translator
attached to the crystal. The slit opening size was 1 mm (vertical)
2 mm (horizontal) in front of the ionization chamber. The
samples were thoroughly mixed with boron nitride and pressed
to form disks. Some samples were in Pyrex glass cells equipped
with polyethene naphthalate lm (PEN; Q51-25, Teijin-Dupont;
25 mm thick) windows on both sides, purged with Ar or lled
with HCl aqueous solution (pH 2.0) with O2 gas. The PEN lm
was transparent for X-rays, visible light, and a portion of the UV
light region (>370 nm) and enabled in situ monitoring of the
photocatalysts.36,4649 The Bi L3-edge absorption energy was
calibrated to 13 426 eV for the spectrum of Bi metal.50
Paper
Table 1
2.3
PFC tests
BiCl
BiCl
BiBi
BiBi
R (nm)
N
Sample
(a) As-synthesized
0.244(0.002)
4.0(0.7)
2.7(5.5)
0.241(0.015)
1.9(0.9)
3.3(2.5)
0.250(0.001)
2.2(0.2)
1.4(0.5)
0.247(0.001)
4.2(0.6)
6.0(1.4)
0.247(0.012)
5.1(1.6)
3.6(1.9)
0.2330
5
0.2314
4
Goodness of t
3.5 104
0.307(0.011)
4.0(1.7)
1.2(3.7)
0.276(0.021)
3.7(0.2)
5.5(1.6)
0.329(0.012)
3.1(0.7)
2.2(1.7)
0.331(0.012)
4.6(1.9)
5.7(1.8)
0.301(0.009)
3.1(1.7)
2.2(3.6)
0.2500
3
0.3071
4
1.6 105
1.4 105
3.2 105
0.3500
1
0.3071
3
0.3529
3
Paper
(3)
where PO2,initial and PO2,nal are the initial and nal pressures of
O2, respectively.47
3 Results
3.1
Characterization of BiOCl
Fig. 2 XPS spectra in the Bi 4f5/2 and Bi 4f7/2 regions for as-synthesized BiOCl (a), BiOCl in Ar irradiated by UV-visible light for 2.5 h (b),
and BiOCl in HCl aqueous solution with O2 irradiated by UV-visible
light for 2.5 h (c).
Paper
Fig. 3 (a) Bi L3-edge EXAFS spectra for as-synthesized BiOCl, (b) sample a under Ar and UV-visible light for 19 h, and (c) sample a immersed in
a pH 2.0 HCl solution under O2 and UV-visible light for 35 min, (d) 12 min after UV-visible light was o for sample c, and (e) sample c was
directly exposed to ambient air. (1) k3-weighted EXAFS c-function, (2) its associated Fourier transform, and best-t results in (3) k-space and (4) Rspace to the Fourier-ltered transformed data. The red and blue lines represent the experimental and calculated values, respectively. The solid
line represents the magnitude, and the dotted line indicates the imaginary part in panels 2 and 4.
Fig. 4 HR-TEM images observed for the (a) as-synthesized BiOCl and
(b) a BiOCl irradiated with UV-visible light for 9 h in Ar atmosphere.
Paper
from the lower BiOCl particles to the amorphous-like, oxygendecient BiO1xCl species to enable crystallization as BiOCl
from the boundary toward the BiO1xCl nanoparticles.
The observed reversible phase transformation should not be
an artifact because the amorphous-like spherical nanoparticles
(Fig. 4b3, right, bottom and 4b6, center, right, and bottom, and
Fig. 4b7) were rarely observed for the as-synthesized BiOCl
(Fig. 4a13). The adjustment of astigmatism was sucient as is
shown in the video (ESI material).
3.1.3 BiOCl irradiated under O2/air and/or HCl aqueous
solution. Corresponding to the conditions of PFC tests, the on/
o exposure of BiOCl to UV-visible light in air was performed,
and the UV-visible absorption spectra were monitored (Fig. 1C).
When fresh BiOCl was irradiated with UV-visible light for 1 h,
the color changed to black, and its light absorption increased
over the entire visible light region (Fig. 1C-b). The maximum
absorbance at 540 nm was 80% of that following irradiation
with light for 1 h under Ar (Fig. 1A-c). When the black sample
was stored in air in the dark for 24 h, the color faded to gray, and
the absorbance was 65% of that of the corresponding sample
stored under Ar in the dark for 24 h (Fig. 1C-c and A-d).
In addition, the BiOCl irradiated in air remained gray in the
dark, even aer 92 h (Fig. 1C-d), which is in clear contrast to the
behavior of the BiOCl irradiated under Ar, which completely
turned white within 5 h upon exposure to air (Fig. 1A-e). Thus, it
can be concluded that the BiO1xCl formed when the BiOCl was
irradiated in air (or O2) with UV-visible light was stabilized by
the outer oxidized layers (Scheme 3e).
XP spectrum in Bi 4f5/2 and Bi 4f7/2 regions was also obtained
for BiOCl irradiated by UV-visible light for 2.5 h immersed in an
HCl aqueous solution (pH 2.0) saturated with O2 (Fig. 2A-c).
Although the Bi3+ peaks were again predominant at 164.8 and
159.5 eV, weaker peaks appeared centered at 162.2 and 157.0 eV
(arrows in Fig. 2A-c and B-c) similar to reduced Bi sites at the
valence between 3 and 0 for irradiated BiOCl in Ar atmosphere
(Fig. 2B-b). The peak intensity of 4f5/2 and 4f7/2 peaks for
reduced Bi sites was dicult to compare between Fig. 2B-b and
B-c because the intensities of these peaks were quite weak.
The BiOCl lm immersed in HCl aqueous solution (pH 2.0)
irradiated by UV-visible light at beamline was analyzed using Bi
L3-edge EXAFS (Fig. 3c). The color of the lm was light gray. The
coordination number of both BiO and BiCl decreased (from
4.0 to 2.2 and from 4.0 to 3.1, respectively; Table 1c and Fig. 3c).
The oxygen vacancy could be formed similar to the conditions of
under Ar and with UV-visible irradiation.
Then, UV-visible light was turned o aer 60 min of irradiation. A Bi L3-edge EXAFS spectrum was obtained at 12 min in
the dark (Fig. 3d). The shape of EXAFS oscillation was similar to
that for the sample irradiated by UV-visible light (Fig. 3c1), but
the reduced amplitude in the whole spectrum region irradiated
by light (Fig. 3c1) seemed to recover to the level for the assynthesized sample (Fig. 3a1). In fact, the N(BiO) and N(BiCl)
values recovered to 4.2 and 4.6 (Table 1d), respectively, similar
to that for as-synthesized BiOCl (4.0; Table 1a). Thus, the O
and Cl vacancy formed in HCl aqueous solution irradiated by
UV-visible light is suggested to be transformed to the original
BiOCl crystalline state soon aer the light was turned o.
Paper
rst cycle, but did not fully stabilize in the following cycles. The
current nearly converged from 102 to 118 mA in ve cycles.
Separately, photocurrents converged to 106 mA within 60 min at
pH 2.0 when the irradiation was continued for 3 h (Fig. 5A0 ),
suggesting reversible structure/state changes for BiOCl photocatalyst when the light was o. Throughout this study, the pH
values of the electrolyte changed negligibly (within a variation
of 0.02) over 5 h.
When the UV-visible light was o, the photocurrent values
quickly decreased to zero within 0.844.1 min at pH 2.0, but
decreased more slowly (1420 min) at pH 3.0, and most slowly
(2526 min) at pH 4.0. This trend suggests limited diusion at
lower proton concentrations. Thus, the nearly converged PFC
photocurrent values were plotted as a function of the electrolyte
solution proton concentrations (Fig. 5B), and it was found that
the values increased proportionally to the square root of the
proton concentration.
When sulfuric acid solution (pH 2.0) was used as the electrolyte for the photoanode (TiO2) instead of HCl solution, the
converged photocurrent was 76 mA in the rst cycle, but gradually decreased to 77, 63, 64, and 64 mA with ve cycles
(Fig. 5A00 ). When the UV-visible light was o, the photocurrents
decreased to zero within 3.06.5 min under this condition. This
response was signicantly slower than the relaxation of currents
in HCl solution for the photoanode (0.844.1 min; Fig. 5A, pH
2.0).
3.2.2 Reactivity of BiOCl with O2 gas. For comparison, assynthesized solvo-BiOCl ne powder was irradiated with UVvisible light for 12 h in vacuum and then placed into contact
with O2. The quantity of O2 (2.91 kPa) in a closed glass system
Fig. 5 (A) Time course of the photocurrents in the PFC comprised of the TiO2 and solvo-BiOCl photocatalyst electrodes, which were immersed
in HCl solutions at a pH of 2.0 (circle, ), 3.0 (square, ), and 4.0 (diamond, ). (A0 ) Continuous test at a pH of 2.0 (circle, ) was also plotted. (A00 )
Time course of the photocurrents in the PFC comprised of the TiO2 and solvo-BiOCl photocatalyst electrodes, which were immersed in H2SO4
and HCl solutions, respectively, both at a pH of 2.0 (circle, ) (B) correlation between the converged photocurrents within 5 h and the H+
concentrations of the acidic water in the PFC or the square root of the H+ concentrations. The ttings were to the linear function (lower x-axis) or
to the kinetic model equation i A[H+]c1/2 B[H+]c1/2 (eqn (7), see text; upper x-axis). (C and C0 ) Time course of the O2 pressure in contact with
solvo-BiOCl (C) and aqua-BiOCl (C0 ) previously irradiated with UV-visible light for 12 h. (D) iV dependence of the PFC comprising TiO2 and
solvo-BiOCl immersed in a pH 2.0 HCl solution. (E) iV dependence of the PFC comprising TiO2 and aqua-BiOCl immersed in a pH 2.0 HCl
solution.
Paper
(4)
(5)
CV for BiOCl
Table 2
Entry
Anode
Cathode
VOC (V)
iSC (mA)
Pmax (mW)
Source
A
B
C
1.76
1.69
1.59
77.7
92.4
73.7
10.5
21.1
14.0
This work
This work
Ref. 7
a
The pH of each HCl solution was 2.0. The area of each photocatalyst was 1.3 cm2. b Mean particle size estimated from the XRD pattern; anatase: 21
nm, rutile: 35 nm, anatase/rutile ratio 7 : 3.
Paper
Table 3
Reduction wave
Oxidation wave
Center
0.19
0.75
0.28
0.3172 @ pH 0
0.39
0.39
0.39
0.57
0.57
0.09
0.09
4 Discussion
4.1
transformed back to BiOCl when the light was o (Fig. 3d, Table
1d, and Scheme 3a), which is in accordance with literature.34 In
relation to the EXAFS results, a reduction peak due to Cl loss via
eqn (4) was observed at 0.39 V in HCl aqueous solution with N2
or O2 (Fig. 6a and b).
In summary, amorphous-like BiO1xCl spherical nanoparticles (Scheme 3b) would be present in the BiOCl samples
irradiated with UV-visible light under Ar and for which the UVvisible spectra (Fig. 1A-bd), XRD patterns (Fig. 1E), Bi 4f5/2 and
4f7/2 XPS peaks (Fig. 2b), and Bi L3-edge EXAFS measurements
(Fig. 3b) were obtained. Both O and Cl-decient BiO1xCl1y
species could be present for the BiOCl lm on the photocathode
irradiated by UV-visible light immersed in HCl solution under
O2 gas for XPS (Fig. 2c), Bi L3-edge EXAFS (Fig. 3c), and during
the PFC tests (Fig. 5A).
It is thought that the O and/or Cl-decient BiO1xCl1y or
BiO1xCl nanoparticles were covered with thin Bi2O3 layers
(Scheme 3e) in samples subjected to UV-visible (Fig. 1C) and
EXAFS (Fig. 3e) analyses and used in the PFC tests in HCl with
light irradiation and direct exposure to air.
4.2
Paper
(6)
The rate and rate constant for this reaction are denoted as rox
and kox, respectively. The O2 photoreduction at BiOCl was in
equilibrium with the product (water), and the constant is
denoted as Kred. Based on the principles of PFCs, the forward
electron ow rate from TiO2 to BiOCl via the external circuit
could be proportional to both the excited electron concentration in TiO2 and the hole concentration in BiOCl (Scheme 1). In
addition, the reverse electron ow rate could be proportional to
both the unreacted excited electron concentration at BiOCl and
the unreacted hole concentration at TiO2. Thus, the eective
electron ow rate (photocurrent i) is formulated in eqn (7). The
derivation is shown in eqn (S1)(S4) (ESI).
ik
0
Ka0 kox
1
4
Kc0
1
1
rox 4
0
Kred
1
8
O2 c
1
8
1
1
1
rox 4 Kc0 6
1
k
1 0 1
1
1 ;
0
4 K
8 O 8 H 2
kox
2 c
red
c
0
(7)
where [O2] and [H+] with a subscript c denote the concentrations of O2 and H+ in the acidic solution around the cathode,
and the rate and equilibrium constants with the prime symbol
denote the constants multiplied with essentially constant
concentrations for the predominant species in the acidic solution/photocatalysts (see ESI for a detailed denition).
4.3.2 Comparison of kinetics to experimental data. Fitting
of the experimental data for the pH dependence in eqn (7) is
presented in the upper x-axis of Fig. 5B. The second term was
negligible in the tting to eqn (7) (i 1182[H+]1/2 0.07458
[H+]1/2), demonstrating that the reverse electron ow from the
CB of BiOCl to the VB of anodic TiO2 via the external circuit was
minimal. Moreover, the net photocurrents were in fact
proportional to [H+]1/2 (Fig. 5B, lower x-axis), which is in
accordance with eqn (7).
A kinetic equation similar to eqn (6) was reported for the PFC
comprising TiO2 and AgTiO2.7 The tted equation for the pH
dependence was i 626.7[H+]1/2 0.009977[H+]1/2. The coefcient of the second term was even smaller than that for the pn
type PFC of the present study because of the rectication by the
Paper
(8)
(9)
(10)
Paper
Table 4 Suggested active species using BiOCl and the derivatives as photocatalysts
Substrate
Medium
Type of light
Catalyst
Ref.
Rhodamine B
Rhodamine B
Methyl orange
Methyl orange
Phenol
Rhodamine B
2-Naphthol degrad.
Methylene blue
Methyl orange
Rhodamine B
Methyl blue
Eosin B
Coomassie brilliant blue
Acetophenone
p-Chlorobenzaldehyde
Rhodamine B
Rhodamine B
O2 reduction
O2 reduction
UV (254 nm)
Vis (>420 nm)
High P Hg
High P Hg
High P Hg
High P Xe (>400 nm)
Vis
W-halogen (>420 nm)
Wideband
Vis
Vis
Vis
Vis
Vis
Vis
UV (365 nm)
Xe (>420 nm)
(DFT)
(DFT)
(001)-preferred BiOCl
(001)-preferred BiOCl
BiOCl
BiOCl
BiOCl
BiOCl under UV in Ar
(010)-preferred BiOCl
UV-reduced BiOCl
C2O42-reduced BiOCl
EtOH/HCl-reduced BiOCl
EtOH/HCl-reduced BiOCl
EtOH/HCl-reduced BiOCl
EtOH/HCl-reduced BiOCl
EtOH/HCl-reduced BiOCl
EtOH/HCl-reduced BiOCl
Ultrathin BiOCl
Ultrathin BiOCl
(001) face
(010) face
BiOCl
BiOCl
BiOCl1x(OH)x
BiOCl1x(OH)x
BiOCl1x(OH)x
BiO1xCl
BiO1xCl
BiO1xCl
Bi0BiOCl
Bi0BiO1xCl
Bi0BiO1xCl
Bi0BiO1xCl
Bi0BiO1xCl
Bi0BiO1xCl
Bi0BiO1xCl
Bi-defect
Bi-defect
O-defect to form cO2
O-defect to form O22
60
60
34
34
34
35
60
58
10
63
63
63
63
63
63
72
72
71
71
4.4
10:5 106
1
ln 0:091 mW;
4 9:65 104 2
(11)
and
TDSmix 8:31 290 2
18:3 106
1
ln 0:16 mW;
4 9:65 104 2
(12)
5 Conclusions
A PFC comprising two photocatalysts (TiO2 and BiOCl) was
demonstrated to achieve VOC values of 1.691.76 V on the basis
of the dierence in the CB minimum of TiO2 and the VB
maximum of BiOCl, which are larger than those for PECs, dyesensitized SCs, and a PFC comprising TiO2 and AgTiO2.7 The
larger particle size (mean 115 nm) of aqua-BiOCl was advantageous by facilitating electron transfer from particle to particle,
Paper
Acknowledgements
The authors are grateful for nancial support from the Feasibility Study Stage of A-STEP (AS251Z00906L, AS231Z01459C)
from the Japan Science and Technology Agency, the Iwatani
Naoji Foundation (20112012), and a Grant-in-Aid for Scientic
Research C (26410204, 22550117) from the Japan Society for the
Promotion of Science. X-ray absorption experiments were conducted under the approval of the Photon Factory Proposal
Review Committee (2013G159). We appreciate Dr Takeo Soejima at JASCO for Raman measurements and Yoshihide Yoshida and Tohru Maki at the Analytical & Measuring Instruments
Division, Shimadzu Corporation for XPS measurements.
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