Accepted Manuscript

Title: Photoelectrochemistry of n-type bismuth oxyiodide

Authors: Przemysław Kwolek, Konrad Szaciłowski

PII: S0013-4686(12)01604-0
DOI: doi:10.1016/j.electacta.2012.10.001
Reference: EA 19350

To appear in: Electrochimica Acta

Received date: 2-8-2012

Revised date: 25-9-2012
Accepted date: 1-10-2012

Please cite this article as: P. Kwolek, K. Szacilowski, Photoelectrochemistry of n-type

bismuth oxyiodide, Electrochimica Acta (2010), doi:10.1016/j.electacta.2012.10.001

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Photoelectrochemistry of n-type bismuth oxyiodide

Przemysław Kwoleka, Konrad Szaciłowskia,b*

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a
AGH University of Science and Technology, Faculty of Non-Ferrous Metals, al. A.

Mickiewicza 30, 30-059 Krakow

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b
Jagiellonian University, Faculty of Chemistry, ul. Ingardena 3, 30-060 Krakow

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Abstract
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Highly-crystalline powder of bismuth oxyiodide in the form of micro-platelets was

synthesized by a microwave assisted hydrothermal process. Application of this novel and

d

environmentally friendly technique in the synthesis of BiOI has never been reported before.
e

Electronic structure of the obtained semiconducting compound was characterized by the

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spectroscopic methods i.e. the reflectance and fluorescence spectroscopy as well as the
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electrochemical impedance spectroscopy. Mott-Schottky analysis of this material was

performed for the first time and indicated the n-type conductivity of the sample.
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Photoelectrochemical properties were determined using the pulsed photocurrent spectroscopy

technique which is also a novel approach in the case of BiOI. Bismuth oxyiodide exhibits the

Photoelectrochemical Photocurrent Switching Effect. The anodic-to-cathodic photocurrent

transition occurs at ca. 0.5 V vs. NHE. The switching effect arises due to the presence of

oxygen dissolved in the electrolyte and makes this material promising from the point of view

of optoelectronic applications.

1
Page 1 of 24
Keywords: bismuth oxyiodide, photoelectrochemical photocurrent switching effect,

semiconductor, photoelectrochemistry, microwave assisted synthesis

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1. Introduction

Bismuth oxyiodide is a V-VI-VII type semiconductor and belongs to the family of oxyhalides.

Recently, this compound has been extensively studied towards photocatalytic decomposition

of organic pollutants from wastewater [1, 2] and photovoltaic applications [3, 4]. This interest

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arises due to the relatively narrow value of the band gap (the narrowest amongst other

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bismuth oxyhalides [5]), low toxicity, stability in water, cheap and environmental friendly

synthesis and notable photocatalytic activity [2] .

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Bismuth oxyiodide crystallizes in the tetragonal matlockite layered structure (space group
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P4/nmm) which consists of the alternate Bi2O22+ sheets and the double I− slabs [5-7]. The

electronic structure of bismuth oxyiodide was calculated by Zhang et al. [8] and Huang et al.
M
[5, 9]. Both the valence and the conduction bands are composed mainly of hybridized Bi 6p,

O 2p and I 5p orbitals. The top of the valence band consists of I 5p orbitals with the small
d

contribution of the O 2p and Bi 6s states. The contribution of I 5p orbitals to the valence band
e

results in the band gap narrowing, due to the increased value of the valence band edge
pt

potential as compared with other oxyhalides. The bottom of the conduction band in turn
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consists of the Bi 6p orbitals in antibonding interaction with the O 2p and I 5p orbitals. [5, 8,

9]. Contribution of the Bi orbitals to the valence band and I and O ones to the conduction
Ac

band indicates a significant covalent character of bonds in studied material. Bismuth

oxyiodide is an indirect semiconductor, the bulk value of the band gap is in the range between

1.92 and 1.94 eV, whereas for nanoparticles this value is much higher and reaches 2.96 eV [5,

10]. Indirect character of the intraband transition is preferential for the photocatalytic

applications, since it hinders the recombination processes. In addition, the band structure of

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Page 3 of 24
the BiOI exhibits flat positions for the fundamental electron transition from the valence to the

conduction band, that may facilitate the process of electron-hole pair generation [5].

It is widely accepted, that the properties of material are in close relationship with its size and

morphology. Particularly, the high surface-to-volume ratio may facilitate the transfer of

electrons and holes to the surface. For the photocatalytic applications great effort is taken to

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obtain three-dimensional micro-scale architectures. So far, bismuth oxyiodide with various

morphologies was obtained, namely nanoparticles [10], nanosheets [11], nanolamellas, or 3D

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flower-like microspheres [7]. A predominant approach to the BiOI synthesis are the

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hydrothermal and solvothermal processes [6, 7, 12], chemical vapour deposition technique

[13, 14], synthesis of nanoparticles in the reverse microemulsions [10], chemical bath
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deposition [15], successive ion layer adsorption and reaction [4] and electrochemical method

[16].
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In the present study we report environmental friendly microwave-assisted hydrothermal route
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of synthesis of highly-crystalline bismuth oxyiodide in the form of micro-platelets along with

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the spectroscopic and photoelectrochemical studies.

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Experimental
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The synthesis was performed in a microwave heated, high pressure autoclave. Bismuth iodide
Ac

(Alfa Aesar 99.999%) was employed as a substrate. 0.7 g BiI3 was placed in a Teflon vessel,

then 40 ml of deionized water was added. The reaction vessel was tightly sealed in the

autoclave. The reaction mixture was heated by microwave radiation and kept at 500 K for 2

hours, whereas the pressure was in the range of 22 and 25 bar. The product was formed due to

the hydrolysis of bismuth iodide according to the equation 1:

BiI3 + H2O = BiOI + 2HI (1)

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 BiOI was obtained in the form of fine, brown powder, then rinsed several times with

deionized water, centrifuged and dried in air. The crystalline phase was identified by the X-

ray diffraction (XRD) technique using the Rigaku Miniflex II diffractometer with Cu Kα

radiation (λ=0.15406 nm). The morphology of the obtained material was studied by a

scanning electron microscopy (SEM) technique on Hitachi SU 70 instrument. Diffuse

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reflectance spectra in turn were recorded on Lambda 950 (Perkin Elmer, USA)

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spectrophotometer equipped with 150 mm integration sphere. The sample was dispersed in

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spectrally pure BaSO4 in 1:50 weight ratio whereas the pressed BaSO4 pellet was used as a

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reference. Photoluminescence spectra were recorded on Fluoromax 4P spectrofluorimeter

(Horiba Jobin Yvon, France), the sample was excited at 250 nm, cut-off 300 nm filter was
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employed to eliminate second order reflections of the excitation line. Photovoltage spectra

were recorded on a Kelvin probe-based surface photovoltage spectrometer (Instytut

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Fotonowy, Poland and Besocke Delta Phi, Germany) with the 2 mm gold grid reference

electrode. The sample was illuminated through the electrode using a 150 W xenon arc lamp
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and a computer-controlled monochromator. Electrochemical impedance spectra were

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measured on SP-300 potentiostat (Bio-Logic, France). Electrodes were prepared as follows:

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BiOI powder was deposited onto indium-tin oxide (ITO) coated polyethylene terephthalate
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foil and covered by thin film of Nafion. 0.1M KNO3 was used as a supporting electrolyte.

Photoelectrochemical characterization was performed using a photoelectric spectrometer

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(Instytut Fotonowy, Poland) equipped with the 150 W xenon arc lamp and coupled with the

SP-300 potentiostat.

2. Results and discussion

The XRD pattern of the BiOI sample obtained by the hydrothermal process confirmed, that

this simple route of synthesis enables obtaining phase-pure, highly crystalline tetragonal

structure bismuth oxyiodide (ICDD PDF 2010, space group P4/nmm). No obvious impurities
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Page 5 of 24
were detected in the sample. In addition, microwave assisted hydrothermal route may be

classified as the “green” technique since no organic solvents were utilized and no volatile

products of the reaction were emitted. Moreover, application of microwaves is an energy

efficient way of heating the reaction mixture.

The morphology of the obtained material is shown in Fig. 1. The sample is composed of

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platelet-like microparticles, where the size distribution is highly non-uniform. 1 μm square

particles are observed together with rectangular 10 times bigger platelets. The average

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thickness of the single particle is around 500 nm. Obtained material may be characterized by a

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relatively high surface-to-volume ratio. Low thickness of a single platelet in comparison with

the dimensions of the facets should be beneficial for the photoelectrochemical applications
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(e.g. photocatalysis). Such a morphology may facilitate electron/hole transfer from the interior

of the particle to the surface, in addition there is plenty of space for adsorption of species from
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an electrolyte.
d

Fig. 1
e

Electrochemical impedance spectroscopy (Mott-Schottky analysis) was employed for the

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determination of the type of conductivity as well as the conduction band edge potential value
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of the sample. For the n-type semiconductor, the capacitance of the space charge layer

depends on the applied potential according to the formula [17] (equation 2):
Ac

1 2 ⎛ kT ⎞
= ⎜V − V fb − ⎟ (2)
C 2
εε 0 eN D ⎝ e ⎠

where ε is the dielectric constant of the sample, ε0 is the vacuum permittivity, e – electric

charge, ND – donor density, V – applied potential, Vfb – flatband potential, k – Boltzmann

constant, T – temperature and C – the capacitance of the space charge layer. Since the Mott-

Schottky analysis is often complicated by a frequency dispersion (caused by e.g.

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Page 6 of 24
microroughness of the electrode [17]) the modified Randles circuit (i.e. a constant phase

element CPE instead of a capacitor C) was used to fit impedance data (Fig. 2). The impedance

of the CPE is given by equation 3:

1
Z CPE = (3)
Q ( jω )
α

t
where ω is the frequency and α equals unity for an ideal capacitor. Using CPE instead of the

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capacitor, one should calculate the value of the capacitance from the Q value obtained from

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the fit. Approximating Q as the capacitance may creates large computational errors. To

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determine the accurate value of the capacitance from Q, Brug equation was employed [17]

(equation 4):

(
C = Q 1 / α R1−1 + R2−1 )(
1−1 / α )
an (4)
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Impedance spectra were recorded in the frequency range between 100 kHz and 10 mHz for

each potential step from 0.8 to 0 V vs. NHE. The potential step was equal to 0.05 V. The
d

validity of the measurements was confirmed by the Kramers-Kronig transformation [18, 19]
e

of the imaginary and real components of the impedance. Obtained results fit well the
pt

experimental data. The equivalent circuit parameters were fitted for each impedance spectrum
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and good fit was found (χ2 around 7.0×10−4) in the frequency range between 100 Hz and 10

mHz . Therefore, only one Q and α values were determined from a single impedance
Ac

spectrum. The medium value of α is equal 0.967 ± 0.001 which indicates almost purely

capacitive character of the space charge layer within BiOI. The dependence of thus calculated

capacitance (using equation 4) on the electrode potential is shown in Fig. 2. Calculated value

of the flatband potential is 0.036 V (R2 = 0.997). Taking into account kT/e correction for 298

K gives the 0.010 ± 0.003 V value. Since the equivalent circuit was fitted to the above

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Page 7 of 24
mentioned range of frequency (10 mHz - 100 Hz), the obtained flatband potential value is

frequency independent in the given range.

Fig. 2

Mott-Schottky plot clearly reveals the n-type conductivity of the obtained material contrary to

the p-type indicated by Poznyak et al. [16]. Due to authors’ best knowledge, the Fermi level

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and the conductivity type of hydrothermally prepared BiOI has never been determined

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experimentally before. In our work we present for the first time the flatband potential value of

the bismuth oxyiodide micropowder and the n-type conductivity determined from the

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impedance measurements. Comparison of previous [16] and current study indicates, that the

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conductivity type of bismuth oxyiodide can be easily affected by the preparative technique.

Diffuse reflectance spectroscopy is a simple and suitable method for the band gap Eg
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determination of the powdery samples. The BiOI powder was grated in a mortar with barium

sulphate, a reflection spectrum was measured and subsequently a Kubelka-Munk function was
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calculated as follows (equation 5):

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F KM =
(1 − R(hv ))2 = α (hv ) (5)
2 R(hv ) S
ce

where R(hν) is the reflectance of the sample measured vs. 100% reflectivity standard. For
Ac

very small particles the Kubelka-Munk FKM function is equal to the absorption coefficient α

(scattering factor S is equal to 1), whereas for bigger particles, when the thickness of the

sample is much bigger than of individual particles, the scattering factor is constant [20].

Subsequently, McLean analysis of the absorption edge was applied [21]. Since the indirect

band gap exists in BiOI crystals, the relation between the energy of an incident photon hν and

the FKM along the absorption edge can be described as follows (equation 6):

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Page 8 of 24
(F KM
hν )
1/ 2
= A(hν − E g ) (6)

where A is a constant.

Fig. 3a shows the diffuse reflectance spectrum (in the form of the Kubelka-Munk function) of

the powdery sample of BiOI. The value of the band gap determined from this plot equals to

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1.78 eV ± 0.02 eV and is slightly lower than the value reported in literature (ca. 1.9 eV [5,

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16]). This difference can be attributed to the adsorption of iodide ions at the surface, which

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may further decrease the band gap due to the significant contribution of the iodide 5p orbitals

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to the upper part of the valence band. Deconvolution of this spectrum into Gaussian

components reveals also the presence of broad and weak transition at ca. 1.8 eV. This
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partially sub-bandgap absorption may be attributed to the electronic transitions involving

adsorbed iodide.
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Fig. 3
d

Photoluminescence spectrum (Fig. 3b) confirms this hypothesis. BiOI exhibits strong
e

luminescence in the blue and violet part of the spectrum. The most intense component
pt

corresponds to the emission from the states above the conduction band edge. The lower
ce

energy component, located at 1.93 eV may be attributed to the emission due to the transition

between the band edges, whereas the lowest band at 1.65 eV can be assigned to the transition
Ac

involving surface states resulting from the iodide adsorption. Observation of the emission

from the intraband states indicates relatively slow (as compared with the emission lifetime)

thermal equilibration of hot electrons within the conduction band. The position of the medium

emission band confirms the previously reported bandgap value of 1.94 eV and clearly

supports the concept of the surface states absorption at energies just below the bandgap

energy.

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Page 9 of 24
BiOI photoelectrodes generate anodic photocurrents over the large potential window.

However, photocurrent intensity dramatically decreases on the prolonged exposure to light

and this process is irreversible. Oxidation of water on such an electrode is not a favoured

process (ΔG = +10.6 kJ/mol), whereas iodide should efficiently scavenge a hole

photogenerated in the valence band (ΔG = −24.1 kJ/mol). Indeed, addition of 10 mM iodide

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prevents photocorrosion and all the photoelectrochemical experiments were performed in

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such electrolyte. Wang et al. [1] confirmed, that in the case of anodic photooxidation of

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methyl orange, direct hole oxidation of the electron donor in the electrolyte is the major way

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of the photocatalytic degradation, whereas the production of OH• radicals via OH− oxidation

is highly unfavoured. In the photocatalytic tests, in the electrolyte there is always present an
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efficient hole scavenger (e.g. methyl orange, methylene blue, rhodamine, sodium

pentachlorophenol or phenol [2]). Therefore, the hole in the valence band can be easy
M
neutralised and photocorrosion process is hampered. This process also was not observed in

the case of photovoltaic applications, since there were always iodide ions in the electrolyte [3,
d

4].
e
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Fig. 4 shows the photocurrent intensity as a function of the electrode potential under pulsed

illumination at 450 nm. BiOI clearly exhibits the Photoelectrochemical Photocurrent

ce

Switching Effect (so called the PEPS effect). It was described for the first time by
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Szaciłowski et al. in 2006 [22-25]. This phenomenon is observed on semiconducting

electrodes and is defined as a change in the photocurrent direction (i.e. anodic-to-cathodic

transition or vice versa) due to changes of the electrode potential or wavelength of incident

light. Such a behavior is very interesting from the point of view of nano- and molecular

electronics. When an incident photon is treated as a bit of information and potential of the

electrode controls the work of the device, such a system may process information as a logic

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Page 10 of 24
gate or 1:2 demultiplexer [26-28]. Thus, BiOI may be a promising compound for information

processing at the nanoscale.

Photocurrent switching potential is equal to 0.5 V vs. NHE in air. For more positive potential

values the anodic photocurrent is observed, the more positive potential, the higher intensity of

the generated current. For more negative potentials than the switching point, cathodic

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photocurrent is observed only in the presence of oxygen.

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Analysis of the shape of a photocurrent pulse (the inset in Fig. 4) may provide some

information about recombination processes. The regular, rectangular shape of the

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photocurrent profile indicates, that a steady state on the photoelectrode under illumination

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occurs i.e. photogenerated charge carriers are efficiently collected by the conductive support

and the recombination processes are insignificant as well as other side processes (e.g. surface
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charging due to high impedance of the semiconductor/conductor interface).

Fig. 4
e d

In order to explain the PEPS phenomenon observed on the BiOI electrode, pulsed
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photocurrent spectroscopy was employed. This technique enable to determine how the

photocurrent depends on the wavelength of incident light and the electrode potential.
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Fig. 5
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Fig. 5 shows the photocurrent spectra in the presence of oxygen in the electrolyte. Under such

condition, the cathodic photocurrent is observed and the photoelectrochemical photocurrent

switching occurs around 0.6 V vs. NHE. Photocurrent intensity reaches zero at 700 nm. This

value stays in a good agreement with the value of the band gap determined from the

spectroscopic measurement (the absorption edge is located at ca. 700 nm). Removal of

oxygen from the electrolyte results in diminished cathodic photocurrents. This observation

11
Page 11 of 24
indicates crucial involvement of dissolved molecular oxygen in generation of cathodic

photocurrents at n-type photoelectrodes.

Fig. 6

The surface photovoltage response (Fig. 6) is observed in the visible region of the spectrum. It

also stays in a good agreement with the absorption spectrum, since the photovoltage

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diminishes at 700 nm, but NIR illumination within 700-1000 nm still produces weak

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response. When the sample is under illumination the Fermi level of electrons splits to two

quasi levels – one for electrons and one for holes. For the n-type semiconductor, the quasi

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Fermi level of electrons is shifted towards more negative potential values than the Fermi level

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of electrons in the dark. Therefore, negative surface photovoltage values confirm, that the

obtained material shows the n-type semiconducting properties. Furthermore, the NIR sub-
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bandgap illumination also results in the noticeable charge separation, which involves

excitation of iodide-based surface states.

d

Fig. 7 shows the mechanism of the photocurrent generation. One should consider only one-
e

electron reduction/oxidation reactions, since only one photon with sufficient energy is enough
pt

to create the electron/hole pair and induce the photocurrent generation. Therefore, anodic
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photocurrent is probably generated due to the direct oxidation of the iodide in the solution by

the hole from the valence band. Photocurrent generation in the absence of iodide can be
Ac

attributed to the oxidation of the iodide adsorbed onto the surface of BiOI crystals and/or

photocorrosion. Cathodic photocurrent in turn is observed, when the conduction band edge of

the semiconductor is higher (in the energetic scale) than the reduction potential of the

molecular oxygen from the electrolyte. For the obtained material, the flatband potential value

is higher, than the formal potential of the oxygen reduction (−0.16 V vs. NHE) [29], thus it

may seem, that the cathodic photocurrent generation is impossible. However, the real oxygen

12
Page 12 of 24
 reduction potential under these conditions depends on the concentration of oxygen dissolved

in the electrolyte as well as the concentration of superoxide. Therefore, the formal potential

value should only be treated as an estimation. As it was observed, oxygen dissolved in the

electrolyte is a key factor of generation of the cathodic photocurrent. Oxygen reduction was

also postulated by Poznyak et al. as the mechanism responsible for the cathodic photocurrent

t
generation by the BiOI electrode [16]. Wang et al. in turn stressed the role of the

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photogenerated electrons in the OH• radicals generation via the multistep process, where the

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reduction of molecular oxygen to superoxide was an intermediate step [1].

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Fig. 7

3. Conclusions an
Bismuth oxyiodide in the form of the microplatelets was obtained by the hydrothermal route.
M
Adopted method is environmentally friendly and enabled obtaining material with the

beneficial morphology for the photoelectrochemical applications. In addition, BiOI is the n-

d

type semiconductor, probably due to the non-stoichiometric composition. It exhibits the

e

Photoelectrochemical Photocurrent Switching Effect due to the appropriate values of the

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conduction band edge potential and the band gap.

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Photocurrent switching at the bismuth oxyiodide photoelectrodes was for the first time
Ac

described by Poznyak et al. and defined as an anomalous anodic photocurrent generation for

the potential values above the certain anodic-to-cathodic transition value [16]. In this work we

report the same phenomenon for the n-type BiOI sample. This is an interesting case, as BiOI

can show photocurrent switching effect both in p- and n-type variants. Thus, BiOI may be a

promising compound for the information processing at the molecular- or nanoscale.

Therefore, authors intend further examination of this compound towards the construction of

the optoelectronic devices e.g. logic gates or a demultiplexer. So far, bismuth oxyiodide, is

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Page 13 of 24
mainly examined towards photocatalytic decomposition of organic pollutants. Thus, the

development of new and environmentally friendly methods of synthesis as well as

examination of its photoelectrochemical properties is very important also from this point of

view.

Acknowledgements

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Financial support from Ministry of Science and Higher Education (grant № UMO-

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2011/03/B/ST5/01495) and AGH University of Science and Technology (contract №

11.11.180.509) is gratefully acknowledged.

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[15] F.I. Ezema, Turk. J. Phys. 29 (2005) 105.

[16] S.K. Poznyak, A.I. Kulak, Electrochim. Acta 35 (1990) 1941.

[17] S.P. Harrington, T.M. Devine, J. Electrochem. Soc. 156 (2009) C154.

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[19] B.A. Boukamp, J. Electrochem. Soc. 142 (1995) 1885.

t
[20] M. Nowak, B. Kauch, P. Szperlich, Rev. Sci. Instrum. 80 (2009) 461071.

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[21] T.P. McLean, in: A.F. Gibson (Ed.), Progress in Semiconductors, vol. 5, Heywood &

cr
Company Ltd., London, 1960, Ch. 2.

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[22] K. Szaciłowski, W. Macyk, Comp. Rend. Chimie 9 (2006) 315.

[23] K. Szaciłowski, W. Macyk, M. Hebda, G. Stochel, ChemPhysChem 7 (2006) 2384.

an
[24] K. Szaciłowski, W. Macyk, G. Stochel, J. Mater. Chem. 16 (2006) 4603.

[25] M. Hebda, G. Stochel, K. Szaciłowski, W. Macyk, J. Phys. Chem. B 110 (2006) 15275.
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[26] S. Gawęda, R. Kowalik, P. Kwolek, W. Macyk, J. Mech, M. Oszajca, A. Podborska, K.

Szaciłowski, Isr. J. Chem. 51 (2011) 36.

d

[27] S. Gawęda, A. Podborska, W. Macyk, K. Szaciłowski, Nanoscale 1 (2009) 299.

e

[28] K. Szaciłowski, Chem. Rev. 108 (2008) 3481.

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[29] D.T. Sawyer, J.S. Valentine, Acc. Chem. Res. 14 (1981) 393.
ce

 
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Page 15 of 24
Figure captions:

Fig. 1. SEM images of the BiOI sample.

Fig. 2. Mott-Schottky plot in the frequency range between 10 mHz and 100 Hz. The

capacitance was calculated per arbitrary surface area unit since determination of the real

surface area of the electrode was impossible. The inset represents the modification of the

t
ip
Randles equivalent circuit used to fit impedance data, where R1 and R2 are the solution and

polarization resistance respectively and CPE is a constant phase element instead of a

cr
capacitor.

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Fig. 3. Absorption (a) and emission (b) spectra of bismuth oxyiodide along with tentative

an
photophysical diagram depicting main optical processes within this material (c). Absorption

and emission spectra are deconvoluted into Gaussian components, in the case of absorption
M
spectrum the McLean component with Urbach tail is also shown. FKM stands for the Kubelka-

Munk function.
d

Fig. 4. Linear sweep voltammetry of BiOI electrode under pulsed illumination at 450 nm,
e

scan rate 5 mV/s, 0.1 M KNO3 10 mM KI, scan in the air and under nitrogen. The inset shows
pt

the kinetics of photocurrent evolution under constant potential at 450 nm. Red line represents
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anodic photocurrent at 0.9 V vs. NHE, blue – cathodic photocurrent at 0.2 V vs. NHE.
Ac

Fig. 5. Photocurrent amplitude as a function of incident light wavelength and photoelectrode

potential in oxygenated electrolyte containing 10 mM KI.

Fig. 6. Differential surface photovoltage spectrum of the BiOI sample deposited on ITO

surface. Photovoltage is measured as a variation of the surface potential on pulsed

illumination vs. gold grid reference electrode.

16
Page 16 of 24
Fig. 7. Mechanism of photocurrent generation in the presence of oxygen in the electrolyte (a)

and in the absence (b). Reduction potential of oxygen was marked at more positive potential

than the formal potential value as it was indicated by experimental results.

t
ip
cr
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e d
pt
ce
Ac

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Page 17 of 24
 ed
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Page 18 of 24
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