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Bis(selenobenzoato)dibutyltin(IV) as a single source precursor for

Dalton Transactions Accepted Manuscript

the synthesis of SnSe nanosheets and their photo-electrochemical
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Received 00th January 20xx,

Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
study for water splitting
Malik Dilshad Khan,a,f Mohammad Aamir,b Manzar Sohail,c Mohammad Sher,b Nadeem Baig,d
Javeed Akhtar,e Mohammad Azad Malik f* and Neerish Revaprasadua*

A new organo-tin complex has been synthesized and used as a single source precursor for the synthesis of SnSe
nanosheets by the hot injection method and thin films by the aerosol assisted chemical vapor deposition (AACVD) method.
The films were deposited on glass substrates at three different temperatures. The textural quality and preferential growth
was found to be significantly altered by the changes in deposition temperature. Oleylamine capped nanosheets and as
deposited thin films by AACVD, were characterized by powder X-Ray diffraction (p-XRD) and microscopic techniques. The
thin films were also studied by Raman spectroscopy. The stoichiometry is marginally affected by temperature, all films
were slightly selenium deficient. The synthesized material was also evaluated for the photoelectrochemical (PEC) splitting
of water. The PEC study revealed the bifunctional nature of the material, which can be applied for both the hydrogen
evolution reaction (HER) and oxygen evolution reaction (OER), by switching the applied potential.

Introduction
Nanomaterials with sheet-like morphology are important
2D materials with diverse applications in catalysis, solar cells
1-3
and batteries. Nanosheets are also suitable for dimension
dependent studies, which can provide new insight to
unanticipated applications. One such example is graphene,
4,
where its 2D geometry is responsible for unique applications.
5 another by weak Van der Waals forces (where the separation
Further research on the layered 2D materials, revealed an
important finding that the band gap of layered semiconductors
can be drastically changed by reducing the thickness to a
6 the [100] direction (Figure 1).
monolayer. Hence, layered semiconductors when thinned
down to the atomic level, comprise an interesting class of
materials with tunable electronic properties.
SnSe is a p-type narrow bad gap semiconductor which has
both a direct and indirect band gap (1.30 eV direct and 0.90 eV
indirect) and falls within the optimum range for solar cells (i.e.
7-9
Eg = 1.0-1.5 eV). Furthermore it has an advantage of
chemical stability, earth abundance and comparatively low
toxicity. SnSe adopts a layered structure with atoms arranged
in a GeS-type crystal structure which favours 2D structural
10
growth. Similar to other layered semiconducting members of
the IV-VI group (SnS, GeS and GeSe etc), SnSe has covalent
bonding within the layers and the layers are linked to one
11, 12
between adjacent layers is ≈ca. 1 Å). The layered structure
of orthorhombic SnSe is favourable by preferred growth along
Various routes have been used for the synthesis of SnSe
nanoparticles and thin films. Wang et al. investigated the
effect of a range of alkaline solutions on the morphology and
orientation of SnSe nanocrystals using SnCl2 and elemental
13
selenium. Ning and co-workers prepared colloidal SnSe by
injecting selenourea into the solution of Sn6O4(OH)4 in oleyl
14
amine-oleic acid mixture at 140 °C. SnSe with tunable
thickness and uniform lateral dimensions, was reported by
Vaughn et al. by reacting SnCl2 with trioctylphosphine selenide
15
(TOPSe) in oleyl amine at 240 °C. Nanowires of SnSe with
sizes larger than 10 μm and a mean diameter of 20 nm was
synthesized by Liu et al. by the reaction of Sn[N(SiMe3)2]2 and
16
TOPSe in oleyl amine. Achimovacova et al. synthesized SnSe
and SnSe/SnSe2 composites at room temperature by the high
17
energy milling method. Irregular shaped SnSe nanocrystals
were prepared by Baumgardner and co-workers by
thermolysis approach using Sn[N(SiMe3)2]2 and TOPSe as

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9
precursors in oleyl amine. Another solution based approach
for phase controlled synthesis of SnSe and SnSe2 was used by
Franzman et al. in which di-tert-butyl diselenide was treated
8
with SnCl2 in a mixture of dodecylamine and dodecanethiol.
SnSe microparticles were synthesized by Singh et al. by
reacting elemental selenium and tin at 1150 K in an evacuated
18
bomb. The microparticles were used to deposit thin films on
glass substrates by flash evaporation. Parkin and co-workers
prepared SnSe and SnSe2 thin films, using SnCl4 and Et2Se2 as
precursors by AP-CVD at a temperature range of 300 to 650
19
°C. Indirajith et al. deposited SnSe thin films, by thermal
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evaporation of SnSe nanoparticles, at different temperatures
20
(150-450 °C). Elemental Sn and Se were used in the form of
ingots, for the synthesis of single crystalline SnSe nanosheets
21
by the plasma assisted direct current discharge method.
Vertically aligned nanosheets were also deposited directly
from SnSe powders on different substrates, by physical vapour
22
deposition.
In contrast to multi source routes, single source precursors
(SSP) are often proven to be better candidates, as they are
equally suitable for the deposition of thin films and/or
23-25
nanoparticles. Control over phase, morphology and
26-33
stoichiometry is also advantageous. However, only a few
SSP’s have been used until now for the synthesis of SnSe
nanoparticles and deposition of thin films. Six membered cyclic
molecular precursors with the general formula (R2SnX)3 (where
R = Ph, Bn and X = S, Se) were used to deposit tin chalcogenide
34, 35
thin films. Similar type of molecular precursors in the
linear form i.e. (R2Sn)2X (where R = Ph, Bn and X = S, Se, Te)
were also used for the deposition of polycrystalline thin
36
films. 2-pyridyl selenolate complexes [R2Sn(2-SeC5H4N)2],
t
where (R = Me, Et or Bu), were used as a SSP but it was
observed that only the tert-butyl derivative was effective for
37
the deposition of SnSe thin films. Previously, we have
reported a new complex bis(diphenylphosphinediselenoato)-
tin(II) [Sn(Ph2PSe2)2] as a SSP for SnSe thin films by the AACVD
38
method. However, phosphines are expensive and toxic
reagents. They often result in phosphorus contamination
and/or formation of an entirely different product, such as
39, 40
metal phosphate or phosphide.
In this study we have now presented a new phosphorus
free molecular precursor bis(selenobenzoato) dibutyltin(II)
[Bu2Sn(PhCOSe)2], as a suitable candidate for the synthesis of
thin nanosheets and morphological controlled thin films by the
AACVD method. The electrochemical measurements indicate
the dual action of the electrocatalyst for hydrogen and oxygen
evolution reaction and shows potential of SnSe as a cost
effective and efficient bifunctional material for water
reduction.
Experimental
Materials
The reagents and solvents i.e. Bu2SnCl2, NaBH4, benzoyl
chloride, elemental selenium, oleylamine, trioctylphosphine
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and ethanol were purchased from Sigma Aldrich and were
used as received.
Synthesis of bis(selenobenzoato)dibutyltin(IV) complex
A solution of NaHSe was freshly prepared by adding 15.0
mL ethanolic solution of NaBH4 (0.5 g, 12.0 mmol) into an
ethanolic solution of metallic Se powder (0.5 g, 6.0 mmol)
under inert conditions using a Schlenk line at room
temperature. The solution was stirred vigorously and the
Dalton Transactions Accepted Manuscript
reddish solution becomes colourless within 5 min, which
indicates the formation of NaHSe. Benzoyl chloride (0.89 g, 6.0
mmol) was then added slowly into the freshly prepared NaHSe
solution and the colour of solution immediately changes from
colourless to yellow, indicating the formation of the
selenobenzoate ligand. The solution was stirred for 10 min,
after which Bu2SnCl2 (0.95 g, 3.0 mmol) in 15.0 mL ethanol was
added dropwise. After 30 min of continuous stirring, 50 mL
distilled water was added which results in the formation of
yellowish oily product. Chloroform was used to separate the
product by solvent extraction, followed by evaporation to
afford the product as a yellow oil. The reaction scheme for the
synthesis of selenobenzoate salt and its organotin complex is
shown in the supplementary information (Scheme S1).
Elemental analysis cal. (%) for C22H28O2SnSe2: C 43.96, H 4.69,
Sn 19.74; Found: C 44.32, H 4.74, Sn 19.45.
Synthesis of SnSe nanosheets
SnSe nanosheets were synthesized by dispersing (0.25 g, 0.42
mmol) [Bu2Sn(PhCOSe)2] complex in 2.0 mL of
trioctylphosphine (TOP) and injected into pre-heated
oleylamine (OLA) (8.0 mL) at 200 °C under a nitrogen
atmosphere. A slight delay in decomposition was observed and
after two minutes of injection, the solution changes colour to
brownish black, which indicates the decomposition of the
complex and formation of nanosheets. The temperature
dropped slightly (≈ 10 °C) upon injection, but then re-adjusted
to 200 °C quickly. The temperature was maintained for 10 min
with constant stirring, after which the reaction was quenched
and nanosheets were precipitated by adding 30.0 mL (1:1)
mixture of acetone and methanol. The nanoparticles were
separated from solution by centrifugation and washed three
times with acetone to remove excess capping agent.
Deposition of SnSe thin films by AACVD
Thin films of tin selenide were deposited on borosilicate glass
substrates (approx. 1 x 3 cm). The substrates were cleaned
ultrasonically in nitric acid, distilled water and finally in
acetone. The setup for aerosol assisted chemical vapour
deposition comprised of a carbolite tube furnace and
ultrasonic equipped humidifier (deurer living LB44) for the
generation of the aerosol. For deposition of thin films, 0.2 g of
precursor was dissolved in 20.0 mL of THF in 100 mL two
necked round bottom flask and placed in water bath above the
piezoelectric modulator of an ultrasonic humidifier. Six glass
substrates were loaded into the reactor tube, which was
placed inside the tube furnace. A gas inlet was attached to one
neck of the flask for flow of the carrier gas and other neck was
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Fig. 1 (a) Layered structure of SnSe held by weak intermolecular
forces viewed along [001] and (b) [100] direction.
attached to the reactor tube containing the substrates by
reinforced tubing. The aerosol was generated by the ultrasonic
humidifier and was carried towards the heating zone of the
furnace with the help of carrier gas (argon). Thermally induced
decomposition of the precursor took place on heated surface
of the substrates and resulted in the deposition of SnSe thin
films.
Characterization
Microanalysis was performed using a Thermo Scientific Flash
2000 Organic Elemental Analyzer. Thermogravimetric analyses
were performed using Mettler-Toledo TGA/DSC. The X-ray
diffraction was performed using a Bruker D8 Discover
diffractometer using CuKα radiation (λ = 1.54178 Ǻ), in a 2ϴ
range from 10ᵒ to 70ᵒ. The data collected were used to
determine the lattice parameters and crystalline phase. TEM
and HRTEM images were collected on Talos F200X at 200 kV
using FEI Ceta camera. Scanning electron microscopy (SEM)
was carried out using a Philips XL30 FEG SEM. Energy-
dispersive X-ray (EDX) spectroscopy was performed using a
DX4 detector. All samples were carbon coated using an
Edwards coating system E306A prior to SEM analysis. Raman
spectra were measured using a Renishaw 1000 Micro-Raman
System equipped with a 514 nm laser operating at 1 mW. The
electrochemical work station (Auto Lab, Netherland) was used
for all photo electrochemical measurements (PEC). The three
electrode system was used for the PEC measurements, which
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Fig. 2 Overlapped thermogravimetric and differential thermo-
gravimetric curves for bis(selenobenzoato)dibutyltin(IV) complex.
consisted of SnSe coated FTO the as working electrode,
platinum as the counter electrode and Ag/AgCl reference
electrode.
Electrode preparation
PEC studies were carried out using fluorine doped tin oxide
(FTO) conducting glass substrates. FTO substrates were ultra-
sonicated, first in acetone and then in deionized water for 10
minutes each. A slurry of SnSe nanosheets, was made in iso-
propanol and sonicated for 10 minutes. Two increments of 25
2
μL of the SnSe were drop casted over 1 cm of the FTO glass
substrate. The resulting SnSe/FTO electrode was then
annealed at 80 °C for two hours to harden the substrate layer.
10 μL of 1% nafion solution was then drop casted over the
SnSe layer to make it withstand during the PEC measurements.
Once dried SnSe/FTO electrode was used as a working
electrode for subsequent PEC studies.
Results and discussions
The synthesis of the bis(selenobenzoato)dibutyltin(II) complex
was carried out in two steps by modifying a previously
reported synthetic protocol,41 using NaBH4 instead of the
highly pyrophoric metallic sodium. In the first step, the ligand
was formed by the dropwise addition of an equimolar quantity
of benzoyl chloride in a freshly prepared ethanolic solution of
NaHSe. The ethanolic salt solution i.e. Bu2SnCl2 was then
added slowly to the ligand solution. The purity of the complex
was determined by elemental analysis and thermogravimetric
analysis (TGA) was performed to observe the thermal stability.
The complex is thermally stable and no mass loss was
indicated up to 230 °C, after which rapid mass loss was
observed and complete decomposition occurs at 310 °C in a
single step (Figure 2). The final residue was ca. 17.5 % of the
original mass, which is less than what is required for the
formation of SnSe (theoretical mass = 32.8 %). The
experimental weight loss does not correspond to any oxide of
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of the injection, hence a pre-requisite of rapid injection is not a

requirement for the synthesis of reproducible monodispersed
nanocrystals. Figure 3(a) represents X-ray diffraction pattern of
OLA capped SnSe nanosheets synthesized at 200 °C. The peaks
match well with the orthorhombic tin selenide phase (ICDD #
03-065-6459) with the absence of any impurity peaks. The
intensity is an indication of superior crystallinity of the
nanosheets, whereas the slight broadness shows that the
nanosheets are quite thin.

Dalton Transactions Accepted Manuscript

The TEM analysis further confirms the thin nature of SnSe
nanosheets (Figure 3(c-d)). Large nanosheets in the order of
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microns were observed along with some comparatively small

sheets stacked on larger sheets. The thin layers can be
observed easily at the edges and can be differentiated on the
basis of change in complexion of the layers as some of them
appear quite transparent to the electron beam. The crystalline
nature of the sheets was confirmed by HR-TEM (Figure 3(b)),
where clear lattice fringes can be observed. Well defined
discrete spots were obtained by the selected area electron
diffraction (SAED) pattern (Figure 3(b) inset). The results are in
Fig. 3 (a) p-XRD pattern of OLA capped SnSe nanosheets, (b) HRTEM agreement with the intense peaks observed in the p-XRD
image showing lattice fringes and SAED (inset), (c-d) TEM images of patterns.
SnSe nanosheets.
SnSe thin films by AACVD
Tin selenide thin films were deposited on the glass substrates
tin, elemental selenium or tin. In order to investigate the using a THF solution of the bis(selenobenzoato)dibutyltin(II)
decomposition behaviour and nature of the residue, a small complex. The complex was soluble in solvents commonly used
amount of the precursor in a ceramic combustion boat was for AACVD, such as chloroform, toluene and THF. Toluene
placed in a glass tube, which was sealed and inserted in requires long deposition time, and to avoid chlorinated
carbolite tube furnace. The furnace was slowly heated to 500 solvent, THF was used for deposition. The precursor
°C, under constant nitrogen flow, for one hour. It was decomposes completely around 310 °C, therefore thin film
observed that above 200 °C, some of the precursor sublimates deposition was attempted at 325 °C. However, only slight and
and deposited at the end of the glass tube. It is reported in the
literature that the complexes of organotin are mostly volatile
and sublime at high temperature.42, 43 The black residue left
after one hour was characterized by p-XRD as shown in Figure
S1, which corresponds to the formation of SnSe. Hence, the
sublimation of the precursor during thermogravimetric
analysis does not give an accurate value of the residue.
SnSe nanosheets were synthesized by the hot injection
method at a temperature of 200 °C in oleylamine, which acted
as the capping agent and also aids in the decomposition of the
precursor. The decomposition of selenobenzoate complex may
follow the same mechanism as suggested by Chin et al. for
decomposition of metal thiocarboxylate complexes in primary
amines.44, 45 Vittal et al. also reported the synthesis of silver
selenide nanoparticles and observed that the precursor
decomposes easily at room temperature in the presence of
primary alkyl amine.46 The primary amine behaves as the
capping agent as well as a nucleation initiator and accelerates
the decomposition of the precursors.47, 48 However, in our case
the decomposition proceeded with slight delay, primarily due
to high thermal stability of the precursor. The relative stability
lowers the rate of nucleation step, which is particularly Fig. 4 p-XRD spectra of SnSe thin films deposited on glass substrates,
desirable in injection based synthesis,49 as injection at (a) 375 °C, (b) 425 °C and (c) 475 °C by AACVD.
temperature need not to be very high i.e. ≥ 300 °C. Similarly,
the nucleation and growth steps become almost independent

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SEM images of SnSe thin film deposited at (a-d) 375 °C, showing plate like morphology, (e-h) at 425 °C, thin plates and presence of some
rods and (i-l) at 475 °C, indicating cubic rod like morphology.

non-uniform deposition was observed at this temperature. To
obtain uniformly deposited crystalline thin films, the
temperature was then varied between 375 and 475 °C, using
argon as a carrier gas at a flow rate of 200 sccm. The deposited
films at all temperatures were black, it was observed that
uniform deposition took place on the substrates which were
placed in the middle and at the end of the tube. The deposited
thin films were uniform and moderately adherent.
The p-XRD patterns of the thin films deposited at 375, 425 and
475 °C, are shown in Figure 4. The peaks match well with the
orthorhombic SnSe (ICDD # 03-065-6459). The intensity profile
matches well with the standard pattern at deposition
temperature of 375 °C, however it varied significantly with
change in temperature. A prominent change in intensity was
observed along the (111) plane, which was the most intense
peak at 375 °C, whereas the increase in temperature results in
decrease in intensity of the (111) plane. Preferential growth in
direction of the (040) plane was observed, which appears as
the most intense plane at deposition temperature of 475 °C.
The intensity variation indicates that the alignment of particles
in a particular plane changes by the changes in deposition
temperature, and substantially affects the morphology of the
deposited thin films.
SEM images for thin films deposited at 375 °C is shown in
Figure 5(a-d). The films were covered with large and thick SnSe
plates randomly oriented on the substrate. The size and
thickness of the plates is roughly the same (with few
exceptions). The elemental mapping was performed to
observe the homogeneity of the deposited thin films and it
indicates that the tin and selenium were distributed uniformly
throughout the film (Figure 6(a-c)). The thin film was slightly
selenium deficient as a mean Sn/Se ratio of 1.13 was observed
by EDX, which is close to the stoichiometric value of 1 (Figure
S2(a)). The higher partial pressure of selenium at elevated
temperatures, may result in slight removal of selenium,
causing the films to be selenium deficient.50
At 425 °C, it was observed that the thickness of the plates
decreases considerably and few rod like crystallites were also
present as indicated by the arrows (Figure 5(e-h)). The length
of the rods is in the range of microns and appeared randomly
throughout the film. A uniform distribution of elements in the
film was shown by elemental mapping (Figure 6(d-f)). The

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increase in temperature marginally affects the stoichiometric
ratio of Sn/Se to 1.19 as determined by EDS (Figure S2(b)),
which shows that the deposited thin films are slightly selenium
deficient. The thickness, as determined by the cross sectional
view of the film by SEM, is estimated to be 1.5 µm, as shown in
supplementary Figure S3.
The morphology of thin films deposited at 475 °C was
completely different showing cuboid rod-like crystallites
(Figure 5(i-l)). The change in the morphology was also
indicated by the p-XRD pattern, where a specified orientation
was observed by modification in the intensity profile of the
peaks. The cuboid rods were of similar diameter (≈ 0.4-05 µm)
and length is greater than 10 µm. A magnified SEM image
shows the end of a solid cuboid rod. Both thermodynamic and
kinetic parameters play the role in controlling the morphology,
as at higher temperature along with thermodynamic stability,
the rate of decomposition of the precursor also increases. The
layers are attached with van der Waals forces which can be
diminished at high temperature. At 375 °C, the plates were
thick and increase in temperature (i.e. 425 °C) results in
thinning of the plates, probably due to separation of attached
layers as van der Waals forces weakened. A further increase
results in the breakdown of these forces of attraction, leading
towards the formation of cubic rods. A further change in
elemental stoichiometry was observed by EDS (Figure S2(c)) as
the mean Sn/Se ratio was increased to 1.24, which shows
further deficiency of selenium in the deposited thin films. The
elemental distribution in the thin films however was still
uniform as shown in (Figure 6(g-i)).
The films were sonicated in acetone for an hour and the
solution was used to obtain the absorption spectra of the thin
films by UV-Vis-NIR spectroscopy (Figure S4). The absorption
behaviour of all films, was quite similar, however the band gap
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calculation indicates a slight increase in the band gap for the
films deposited at 475 °C (Figure S5).
The thin films were also characterized by Raman spectroscopy
51
and the peaks correspond well to earlier work (Figure 7).
Group theory calculations suggest that SnSe is expected to
have 12 Raman active modes i.e. 4 Ag, 2B1g, 4B2g, and 2B3g. A
detailed discussion on group theory studies was reported by
51, 52
Chandrasekha et al. and Nikolić et al. The studies indicate
that the visibility of the Raman-active vibrational modes
strongly depends on the particular orientations of the crystal
axes with respect to the incident and collected laser light and
its polarization. The Raman shift for thin films deposited at 375
°C was not prominent, only vibrational modes present at 70
-1 -1
cm and 108 cm were identified and the remainder were
difficult to assign because of the broadness of the peaks.
However, distinguishable peaks were emerged for thin films
deposited at 425 °C, with high intensity mode present at 108
-1
cm . The bands becomes sharper and intense as the
deposition temperature was further increased to 475 °C. The
broadening of the band is related to the presence of stress or
structural defects in scattering volume and shows low
53, 54
structural quality of the lattice. Similarly, the position,
width, and shape of the vibrational modes of SnSe (below 200
−1
cm ) change significantly as the SnSe layer thickness
increases. The shift in frequency and broadness can be due to
phonon softening and increase in extent of electron-phonon
55
coupling in a thin layered structure. As the crystallinity of the
material is enhanced with increase in temperature so the
highest intensity ratio was observed for the thin film deposited
at high temperature which shows the higher structural quality
of the film.
Photoelectrochemical studies
With a suitable electrode material sunlight photons can
actively derive splitting of water to generate H2 and O2. H2
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Schematic diagram showing switching of photocathode to
photoanode.
possesses high energy density (143 KJ/Kg) and thus is a very
attractive energy storehouse. Furthermore, the reverse
reaction of H2 with O2 is highly desirable because it produces
high energy (572 KJ/Mole) and an environment friendly H2O
Chronoamperometric measurements of SnSe coated FTO showing the photocurrent densities at (A) 0.0, (B) 0.1, (C) 0.2 V. (D) I-t stability
curves under light and darkness.
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product as shown in the equation S1-S3 (supplementary
56, 57
data). The water oxidation reaction is challenging,
considering that each oxygen molecule generation requires 4
electrons and 1.23 V of energy per electron while each H2
molecule generation needs 2 electrons and the reaction can
occur at 0 V vs NHE. Many metal oxide based nanomaterials
are reported effective for either the H2 evolution reaction
(photocathodes) or oxygen evolution reaction (photoanodes)
under sunlight. However, the development of a single material
Dalton Transactions Accepted Manuscript
that can possess sufficient photoactivity under solar light and
suitable band gap potentials for both water oxidation and
56,
reduction reactions is hindered due to synthetic challenges.
58
Our SnSe nanosheets, displayed the interesting behaviour of
switching from photocathode to photoanode just by changing
the bias voltages as shown schematically in Figure 8.
SnSe thin films were prepared on the surface of FTO for the
PEC investigation of the synthesized material. The SnSe coated
FTO was used as a working electrode in a conventional three
electrode system. The working electrode was exposed to 1 Sun
solar simulated light at regular intervals to explore the
behaviour of the SnSe coated films under dark and light in 0.5
M Na2SO4 medium at pH 7.0. Bare FTO had a negligible photo
response current, however, after coating with the SnSe slurry,
the photocurrent was significantly improved. The
photocurrent density was measured by using chrono-
J. Name., 2013, 00, 1-3 | 7
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amperometry, switching the light in ON/OFF approach, after Acknowledgements

regular intervals. The SnSe coated FTO demonstrated unique
The authors are grateful to the National Research Foundation
photoactive behaviour in the presence of light at different
(NRF) South African Research Chairs Initiative (SARChI) for
applied voltages. When the SnSe/FTO electrode was irradiated
financial support.
with solar light, the current decreased sharply towards the
negative value, but in the dark, it returned to the initial value.
This behaviour of SnSe coated FTO is indicative of the
Notes and references
hydrogen evolution reaction (HER) at 0 V (Figure 9A). At 0 V,
the photocurrent density for cathodic hydrogen evolution 1. W. J. Youngblood, S.-H. A. Lee, K. Maeda and T. E.
2 Mallouk, Acc. Chem. Res., 2009, 42, 1966-1973.

Dalton Transactions Accepted Manuscript

reaction was found to be 11 µA / cm . The PEC reaction at the
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surface of electrode was entirely changed when the applied
Domen and S. Hayashi, J. Am. Chem. Soc., 2003, 125,
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V, the photocurrent increased to about 30 µA/cm (Figure 9C).
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and S5. The absorption of light is high for all films in the whole
59
spectrum range. The band gap for SnSe nanosheets prepared
⁰ 8.
at 475 C was found to be 1.31 V which lies very close to the
voltage required for the oxygen evolution reaction (1.23 V vs 9.
NHE). Thus only a small bias voltage of 0.1 V switches the
cathodic water splitting to the anodic water splitting which 10.
improves further when the applied voltage is 0.2 V. Beyond
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light from the solar simulator (Figure 9D). It was revealed from
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efficient and durable bifunctional electrocatalyst, which can be 15.
used for both HER and OER just by switching the applied
potential. 16.
17.
Conclusions
18.
A new tin complex has successfully been used as a precursor
19.
for the synthesis of SnSe nanosheets and thin films by AACVD.
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of the material for water splitting.
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