Applied Surface Science 525 (2020) 146596

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Applied Surface Science

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

Experimental and DFT insights into an eco-friendly photocatalytic system T

toward environmental remediation and hydrogen generation based on
AgInS2 quantum dots embedded on Bi2WO6
Patrycja Parnickaa, Alicja Mikolajczyka,b, Henry P. Pintoc, Wojciech Lisowskid,
Tomasz Klimczuke, Grzegorz Trykowskif, Beata Bajorowicza, Adriana Zaleska-Medynskaa,
⁎

a
Department of Environmental Technology, University of Gdansk, 80-308 Gdansk, Poland
b
Laboratory of Environmental Chemometrics, Faculty of Chemistry, University of Gdansk, 80-308 Gdansk, Poland
c
CompNano Group, School of Physical Sciences and Nanotechnology, Yachay Tech University, 100119 Urcuqui, Ecuador
d
Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland
e
Department of Solid State Physics, Faculty of Applied Physics and Mathematics, Gdansk University of Technology, 80-233 Gdansk, Poland
f
Instrumental Analyses Laboratory, Faculty of Chemistry, Nicolaus Copernicus University, 87-100 Torun, Poland

ARTICLE INFO ABSTRACT

Keywords: Bismuth tungstate (Bi2WO6) can work as a photocatalyst but suffers from rapid recombination of photogenerated
Photocatalysis charge carriers. Herein, density functional theory (DFT) simulations revealed that the formation of a thermo-
Bismuth tungstate dynamically stable AgInS2(112)/Bi2WO6(010) heterojunction could promote charge separation and enhance the
AgInS2 quantum dots photoactivity of Bi2WO6. To confirm these theoretical predictions, a new type of photocatalysts in the form of
Hydrogen evolution
Bi2WO6 flower-like microspheres decorated with different amounts of AgInS2 quantum dots (QDs) was obtained
Phenol degradation
DFT calculation
using a three-step procedure. The optimized system, obtained by embedding 1 wt% AgInS2 QDs on a Bi2WO6
matrix, possessed an enhanced photocatalytic activity for both phenol degradation and water splitting under
visible light irradiation (λ > 420 nm), as well as good reusability and stability during prolonged storage.
Finally, DFT calculations of the adsorption energies of reagents (O2, H2O, and H2 molecules) on Bi2WO6 and
AgInS2/Bi2WO6 surfaces showed that the surface of the AgInS2(112)/Bi2WO6(010) interface was more active,
allowing this system to strongly interact with surrounding species such as H2, O2, and H2O and thereby inducing
photocatalytic oxidation of OH– to •OH, reduction of O2 to O2•– or reduction of H+ to H2.

1. Introduction oxidation reaction [5–7].

The growing importance of energy and environmental sustainability
has motivated many research groups to investigate the rational design
of effective visible-light photocatalysts for environmental remediation
and artificial photosynthesis [1–4]. Bismuth tungstate (Bi2WO6) stands
out as an attractive semiconductor because of its suitable band gap (BG)
of ~2.7-2.9 eV and stability under visible light irradiation. As the
simplest member of the Aurivillius family, the crystal structure of
Bi2WO6 consists of accumulated layers of corner-sharing [WO6] octa-
hedral sheets and [Bi2O2] layers. Density functional theory (DFT) cal-
culations show that the empty W 5d orbitals are used to build the
conduction band (CB) of Bi2WO6, whereas the valence band (VB) is
mostly composed by O 2p orbitals hybridized with Bi 6 s orbitals. This
not only reduces the forbidden bands, but also gives a widely dispersed
VB and promotes the mobility of photoinduced holes for specific
Like other single-component semiconductor materials, Bi2WO6 ty-
pically demonstrates unbalanced electron (e–) and hole (h+) mobilities,
and suffers from rapid recombination of charge carriers [8,9]. Hence,
different strategies have been applied to overcome these drawbacks,
such as coupling with other semiconductors and co-catalysts or surface
modification [10–15]. One of the most accessible approaches is the
deposition of quantum dots (QDs) onto the semiconductor surfaces,
which is beneficial due to their noteworthy properties, including high
charge separation efficiency and quantum confinement effects. Thus,
QDs are widely used as a visible-light sensitizers to fine-tune the be-
haviours of photogenerated charge carriers in multi-component semi-
conductor materials, which could modify the optical and electronic
behaviours of the original material [16–18].
In recent years, there has been considerable interest in the mod-
ification of Bi2WO6 using CdS or CdSe QDs, resulting in improved

⁎
Corresponding author.
E-mail address: adriana.zaleska@ug.edu.pl (A. Zaleska-Medynska).

https://doi.org/10.1016/j.apsusc.2020.146596
Received 9 March 2020; Received in revised form 30 April 2020; Accepted 2 May 2020
Available online 08 May 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
P. Parnicka, et al.
photocatalytic efficiencies that are attributed to inter-particle electron
transfer in composite samples [19–21]. Unfortunately, the cadmium
composite raises concerns about carcinogenicity and other chronic
health risks, as well as disposal hazards [22]. Therefore, en-
vironmentally friendly alternatives are required for producing new
visible-light-driven photocatalysts. The newly developed I-III-VI2
semiconductor QD, silver indium disulfide (AgInS2), has a narrow direct
band gap of ~1.5-1.8 eV and an excellent absorption coefficient
of ~105 cm−1. The material has already been employed in light-emit-
ting diodes and biomolecular tags and has demonstrated great potential
in many fields, including photocatalysis [23,24]. The number of re-
search papers published on the topic of QD-based hybrid photocatalysts
has increased from 44 in 2009 to 1729 in 2019 (data from Web of
Science). However, AgInS2 QDs have been less explored as a sensitizer
in hybrid photocatalysts (especially when combined with Bi2WO6), and
there have been few reports on its use for photoelectrochemical con-
version, removal of pollution, or hydrogen evolution [25–27].
The rational design, fabrication, and implementation of new pho-
tocatalytic systems that are efficient, durable, and yet cheap is still a
challenge. Ab initio calculations performed via DFT offer a theoretical
framework that can predict a significant portion of the properties of a
given material. Therefore, it can help to quantitatively predict the
stable atomic arrangements of new photocatalysts that will be obtained
in the laboratory in a relatively short time and with minimal costs. Ab
initio simulations are becoming an integral tool in materials investiga-
tions and have initiated the concept of “materials by design” [28,29].
Herein, the AgInS2/Bi2WO6 system was investigated using the DFT
method to give an in-depth understanding of the heterojunction for-
mation and the photocatalytic capabilities of the material. After this,
the experimental part of this work concerned the preparation of AgInS2
QD-decorated Bi2WO6 heterojunctions via a multistep route to verify
the results of the theoretical calculations. The hot-injection method was
used to synthesize the QDs, while hydrothermal precipitation was em-
ployed to prepare Bi2WO6, and the two materials were coupled together
via low-temperature annealing. Furthermore, this work focuses on de-
veloping a comprehensive understanding of the role played by QDs in
modifying Bi2WO6, and provides theoretical insights into the entire
photocatalytic process, from photoexcitation to the redox reactions at
the surface. Moreover, the photocatalytic degradation efficiency and
hydrogen evolution were correlated with the structural, optical, and
electronic properties of the hybrid material.
2
Applied Surface Science 525 (2020) 146596
2. Computational and experimental details
2.1. Computational details
The calculations of the BiWO6, AgInS2, and BiWO6/AgInS2 inter-
faces and their interactions with water, H2, and O2 molecules were
performed using the plane-wave basis Vienna ab initio simulation
package (VASP) [30–32], implementing the strongly constrained and
appropriately normed (SCAN) meta-generalized gradient approximation
[33,34]. Core electrons were described by projected augmented wave
(PAW) potentials [35], where the potential for the Ag, Bi, H, In, O, S
and W atoms were generated in the electron configurations [Kr] 4d10
5s1, [Xe, 4f14] 5d10 6s2 6p3, 1s2, [Kr] 4d10 5s2 5p1, [1s2] 2s2 2p4, [Ne]
3s2 3p4, and [Kr, 4d10, 4f14] 5s2 5p6 5d5 6s1, respectively, and where
square brackets denote the core electron configurations. Using a kinetic
energy cut-off of 700 (600) eV and a Γ-centred Monkhorst-Pack k-point
meshes with a separation of 0.035 (0.039) Å−1, we converged the en-
ergy to < 1 meV/atom for the BiWO6 and AgInS2/BiWO6 interfaces
(for AgInS2) systems. In all the systems, ionic optimizations were per-
formed until all the atomic forces were < 0.02 eV·Å−1. The SCAN-
predicted crystal structure for orthorhombic BiWO6 (tetragonal AgInS2)
yielded a system with lattice parameters of a = 5.466 Å, b = 16.559 Å,
c = 5.477 Å (a = b = 5.864 Å and c = 11.333 Å) and symmetry Pca21
No. 29 (I-42d No. 122). The experimental lattice parameters for or-
thorhombic BiWO6 (tetragonal AgInS2) are a = 5.457 Å, b = 5.436 Å,
and c = 16.427 Å [36], and are in good agreement with those predicted
using SCAN. Inspired by the HRTEM images showing the formation of
AgInS2(112) facets (See Fig. 5), the AgInS2 QD-decorated Bi2WO6 het-
erojunction was modelled with a Bi2WO6(010)-2×2O-terminated slab
with a thickness of ~ 8.3 Å along the [001]-direction (see Fig. 1a). On
top of this, we built a AgInS2(112) bilayer along the z-direction (see
Fig. 1b). In all these systems, we included a vacuum with a thickness of
15 Å along the [001]-axis. The adsorption energies (ΔEads) of H2, O2,
and H2O molecules at the Bi2WO6(010)-2×2 and AgInS2(112)/
Bi2WO6(010) interfaces were computed using Eq. (1):
isolated
Eads = Etot (Esyst Emolecule ) (1)
where Eads is the adsorption energy of the molecule, Etot is the total
energy of the system (Bi2WO6(010) or AgInS2(112)/Bi2WO6(010) in-
terface) including the adsorbed molecules, and Emolecule
isolated
is the total en-
ergy of the single molecule. See Supporting Information for more details
regarding DFT computational configurations.
Fig. 1. Fully relaxed SCAN-computed
structure of (a) a pristine Bi2WO6(010)-2×2
slab and (b) the AgInS2(112)/Bi2WO6(010)
interface. The boxes represent the supercell
lattice, and Ag, Bi, In, O, S, and W atoms are
represented by cyan, violet, brown, red,
yellow, and blue spheres, respectively. (For
interpretation of the references to color in
this figure legend, the reader is referred to
the web version of this article.)
P. Parnicka, et al.
2.2. Preparation of photocatalysts
2.2.1. Materials
All reagents used in this study were of analytical grade and were
used without further purification. Bi(NO3)3·5H2O, Na2WO4·2H2O,
AgNO3, oleic acid (OA), In(acac)3, benzoquinone, phenol, 1-Octadecane
(ODE), 1-dodecathiol (DDT), oleylamine (OLA) and sulfur were pur-
chased from Sigma-Aldrich, Germany. Ethanol and chloroform were
purchased from POCh S.A, Poland. Nitric acid and sodium hydroxide
were provided by STANLAB, Poland. Deionised water (0.05 mS) was
used for all reactions and treatment processes.
2.2.2. Synthesis of Bi2WO6
Bi2WO6 was synthesized via the hydrothermal method in a 200 mL
Teflon-lined stainless-steel autoclave. Details of the preparation process
were as follows: Bi(NO3)3·5H2O (2.254 g) was dissolved in nitric acid
(92 mL, 0.3 M), then Na2WO4·2H2O (46 mL, 0.05 M) and NaOH (46 mL,
0.2 M) solutions were added slowly to the stirring mixture. The sus-
pension was agitated by a magnetic stirrer at 550 rpm for 24 h.
Subsequently, the mixture was put in a reactor and kept at 160°C for
8 h. After cooling the autoclave to room temperature, the precipitate
was separated from the suspension by centrifugation and washed five
times with water, followed by drying at 60°C overnight.
2.2.3. Synthesis of AgInS2 QDs
AgInS2 QDs were synthesized by the hot-injection method, fol-
lowing a previously reported procedure [37]. A mixture of AgNO3
(0.1 mmol), In(acac)3 (0.5 mmol, 0.21 g), OA (1.5 mmol, 0.45 mL), and
ODE (25 mmol, 8 mL) were mixed in a three-necked flask under an inert
(nitrogen) atmosphere. After 30 min, the mixture was heated to 90°C,
and then 1-dodecathiol (4 mmol, 1 mL) was injected into the hot re-
action mixture via a syringe. Afterward, the mixture was heated to
130°C. A sulfur solution (0.80 mmol of S powder dissolved in 1.3 mL
OLA (3.1 mol/L)) was quickly injected into the reaction solution, and
the solution continued reacting for 2 min. The solution was purified by
adding anhydrous ethanol to remove the unreacted precursors, and this
washing process was repeated three times. The final AgInS2 QDs were
dispersed in chloroform.
2.2.4. Preparation of AgInS2/Bi2WO6
AgInS2/Bi2WO6 nanocomposites were prepared by a deposition
method. Bi2WO6 powder (0.5 g) and a certain amount of AgInS2 QDs
were dispersed in chloroform (total volume 4 mL), and then simulta-
neously mixed and heated to 40°C to evaporate the solvent. Finally, the
powders were calcinated at 200°C for 1 h in a muffle furnace under air
atmosphere (with a temperature gradient of 2°C/min). Schematic dia-
grams for the fabrication of Bi2WO6 and AgInS2 QDs and a description
of the prepared photocatalysts are shown in Fig. 2 and Table 1.
2.3. Characterization techniques
Powder X-ray diffraction (pXRD) was used to confirm the crystal
structure and calculate the lattice parameters of Bi2WO6. The pXRD
patterns were collected using a D2 Phaser (Brucker) diffractometer with
CuKα radiation (λ = 1.54056 Å), a scanning angle 2θ = 10°–90°, and a
step size of 0.01°. The lattice parameters were estimated by the Le Bail
profile method using High Score Plus software. A simulated pattern for
AgInS2 QDs was rendered using structural analysis (PowderCell) soft-
ware. The diffraction peaks were modelled with the full width at half-
maximum of ~ 3° at a crystallite diameter of 6 nm, which enabled the
conclusive assignment of the nanoparticle phases. X-ray photoelectron
spectroscopy (XPS) measurements were performed using a PHI 5000
VersaProbe (ULVAC-PHI) spectrometer with monochromatic Al Kα ra-
diation (hν = 1486.6 eV). High-resolution (HR) XPS spectra were col-
lected with a hemi-spherical analyser at a pass energy of 23.5 eV, a step
size of 0.1 eV, and a photoelectron take-off angle of 45° with respect to
3
Applied Surface Science 525 (2020) 146596
the surface plane. The binding energy (BE) scale was referenced to the C
1s peak, with BE = 284.8 eV. The PHI Multipak sensitivity factors and
determined transmission function of the spectrometer were used for
quantification of the results. The morphologies of the as-prepared
samples were investigated by field emission scanning electron micro-
scopy (FE-SEM, JSM-7610F, JEOL) and transmission electron micro-
scopy (TEM, FEI Europe, Tecnai F20 X-Twin). To characterize the
photoabsorption properties of the bare and modified photocatalysts, the
diffuse reflectance spectra (DRS) were recorded on a Shimadzu UV–Vis
spectrophotometer (UV 2600) equipped with an integrating sphere.
BaSO4 was used as the reference. The obtained absorption spectra were
recorded in the range of 250–850 nm with a scanning speed of 200 nm/
min at room temperature. Photoluminescence (PL) properties were
measured in the 300–700 nm range using a Perkin Elmer Ltd. LS50B
spectrophotometer equipped with a xenon discharge lamp as an ex-
citation source and an R928 photomultiplier as a detector. The spectra
were recorded with an excitation wavelength of 315 nm directed to-
ward the sample surface at an angle of 90°.
2.4. Measurement of photocatalytic activity
The photocatalytic performances of the samples for the degradation
of phenol under visible light irradiation were investigated using a
1000 W Xenon lamp (Oriel 66021) equipped with an optical filter
(GG350 and GG420) and a water IR cut-off filter. The temperature in
the reactor during the process was maintained at 10 ± 0.5°C using a
thermostatically controlled water bath. Experiments were performed in
a reactor at initial phenol and photocatalyst concentrations of 0.21 mM
and 5 g/l, respectively. Phenol solution samples (0.5 mL) were taken at
specific time intervals, filtered using a 0.2 μm syringe filter, and then
analysed. A high-performance liquid chromatography system (HPLC,
Shimadzu) equipped with a Kinetex C18 column (150 mm×3 mm;
particle size 2.6 µm; pore diameter 100 Å) and an SPD-M20A diode
array detector (λ = 205 nm) was used to determine the concentration
of phenol in the solution. The mobile phase was composed of acetoni-
trile and 0.1% formic acid using isocratic elution (20/80 v/v) with a
constant flow rate equal to 0.4 mL/min. The injection volume was
20 µL. Radical scavenging experiments using benzoquinone, silver ni-
trate, ammonium oxalate and tert-butanol (solution of scavenger and
phenol 1/1C/C) were performed using the same procedure. Hydrogen
evolution from water under UV–Vis and visible irradiation using a
sulfur solution as the sacrificial reagent was evaluated as follows: 0.1 g
of the as-prepared photocatalyst was dispersed in an 80 mL aqueous
solution containing 1 M NaOH, 0.1 M Na2S·9H2O, and 0.5 M Na2SO3.
The suspension was placed in a quartz photoreactor and tightly closed,
and then magnetically stirred and degassed with N2 for 1 h in the dark
to reach an adsorption–desorption equilibrium. The photoreactor was
irradiated using the same system used for phenol degradation. Before
starting the irradiation, a reference sample was taken. The concentra-
tion of H2 evolved was determined at regular time intervals of 1 h using
a gas chromatograph (TRACE 1300, Thermo Scientific) equipped with a
HayeSep Q (80/100) column and a thermal conductivity detector (TCD)
with N2 as the carrier gas. Samples (200 μL) were injected via a gas-
tight syringe.
3. Results and discussion
3.1. Density functional theory calculations of the interaction mechanism at
AgInS2/Bi2WO6 heterojunctions
To understand the interfacial electron transfer between AgInS2 QDs
and Bi2WO6, we computed the work function Φ of both the monolayer
Bi2WO6(010) slab and the bilayered AgInS2(112) facet. The calculation
Φ = EV-EF is useful to predict the electron transfer at the interface.
Fig. 3. displays the SCAN-computed electrostatic potential. The results
yield Φ values for of 7.23 and 5.81 eV for Bi2WO6(010) and the
P. Parnicka, et al. Applied Surface Science 525 (2020) 146596

Fig. 2. Schematic diagram for the fabrication of (a) Bi2WO6, (b) AgInS2 QDs, and (c) the AgInS2/Bi2WO6 composite.

AgInS2(112) QD facet, respectively. This means the Fermi level of the
QD facet is higher than that of the Bi2WO6(010) slab, implying that
some electrons would transfer from the AgInS2(112) facet to the
Bi2WO6(010) slab when the heterojunction is formed. Moreover, the
computed differential charge density between AgInS2(112)/
Bi2WO6(010) and the AgInS2(112) facet plus the Bi2WO6(010) slab is
displayed in Fig. 3c. This shows the charge transfer that occurs where
the electron density is depleted (accumulated), as depicted by blue
(green) isosurfaces; clearly, this charge transfer process produces an
effective electric field that appears within the interface (cf. Fig. 3c).
Bare Bi2WO6 has an orthorhombic structure with lattice parameters of
a = 5.457 Å, b = 5.436 Å, and c = 16.427 Å that belongs to symmetry

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P. Parnicka, et al. Applied Surface Science 525 (2020) 146596

Table 1
Description and physicochemical characterization of AgInS2/Bi2WO6 nanocomposites.
Sample label Assumed content of AgInS2 QDs (wt.%) Color of the photocatalysts Lattice parameters Crystal structure

a (Å) b (Å) c (Å)

Bare_Bi2WO6 None 5.4430(4) 16.438(1) 5.4479(5) Orthorhombic

0.5%AgInS2/Bi2WO6 0.5 5.4466(4) 16.446(1) 5.4498(5)

1%AgInS2/Bi2WO6 1 5.4464(5) 16.443(1) 5.4496(5)

2.5%AgInS2/Bi2WO6 2.5 5.4471(4) 16.441(1) 5.4503(5)

5%AgInS2/Bi2WO6 5 5.4469(4) 16.445(1) 5.4502(4)

10%AgInS2/Bi2WO6 10 5.4489(4) 16.445(1) 5.4516(4)

AgInS2_before_ calcination 100 Immeasurable Orthorhombic

AgInS2_after_calcination or Bare_AgInS2 100 Immeasurable Tetragonal

group No. 73. The Bi2WO6 structure is a layered material with [Bi2O2]
and corner-shared [WO6] layers. The bare Bi2WO6 has a coordinatively
unsaturated Bi atom on the surface (Fig. 4) that induces the interactions
responsible for the formation of multilayers. The computed band
structures of bulk Bi2WO6 and the monolayer Bi2WO6(010) slab yield
band gaps of 2.36 and 2.8 eV, respectively. Note that band gaps from
theoretical calculations are usually smaller than those derived from
experimental measurements; however, DFT calculations provide im-
portant insights into the physicochemical features of the system and its
modifications. The computed partial densities of states (PDOS) of the
Bi2WO6 crystal structure and the Bi2WO6 monolayer are presented in
Fig. 4b and d. The PDOS for both systems show that the upper valence
band (UVB) is composed mainly of O 2p character, while the lower
conduction band (LCV) has mainly Bi 6s and W 5d character. The
Bi2WO6(010) layered structure of the AgInS2(112)/Bi2WO6(010) in-
terface may be responsible for the space charge injection at the het-
erojunction interface, which promotes separation of the photogenerated
carriers [36]. Holes and electrons may be directly generated both on the
surface and in the middle layer, resulting in increased photocatalytic
activity. Compared with monolayered Bi2WO6(010), the electronic
structure of the topmost layer of the AgInS2(112)/Bi2WO6(010) inter-
face is characterized mainly by Ag 4d and S 3p peaks in the UVB and S
3p and In 5s + 5p peaks in the LCV. Moreover, we observed Bi-S, O-Ag,
O-S and O-In bond formation at the boundary of the interface, in
agreement with XPS observations. As shown Fig. 4d and f, the layered
structure of the AgInS2(112)/Bi2WO6(010) resulted in a decreased in
the band gap, from 2.8 eV for the Bi2WO6(010) monolayer to 1.1 eV for
the AgInS2(112)/Bi2WO6(010) interface (see Section 3.6 for more in-
formation).
3.2. Morphology
To validate our theoretical predictions, a series of Bi2WO6 photo-
catalysts decorated with different amounts of AgInS2 QDs were pre-
pared using a three-step preparation route (sample types are listed in
Table 1). The morphological characterization of the AgInS2 QD-mod-
ified Bi2WO6 was performed using scanning electron microscopy (SEM)
and high-resolution transmission electron microscopy (HRTEM), and
results are shown in Fig. 5 and Fig. S7. Bare Bi2WO6 exhibited highly
hierarchical flower-like microspheres with diameters of 4–6.5 μm. The

Fig. 3. SCAN-computed electrostatic

potentials of (a) a Bi2WO6(010) slab
and (b) the bilayered AgInS2(112) facet,
with both being averaged along the
[001] direction. The blue (red) dotted
line indicates the position of the va-
cuum (Fermi) level EV (EF), and the in-
sets display the atomic structures of the
fully relaxed systems. (c) Differential
charge density isosurfaces for fully re-
laxed AgInS2(112)/Bi2WO6(010) het-
erojunction, with values of ± 3×10-3
e·Å−3, where the negative in blue (po-
sitive in green) value represents the
depletion (accumulation) of electron
density. (For interpretation of the re-
ferences to color in this figure legend,
the reader is referred to the web version
of this article.)

5
P. Parnicka, et al. Applied Surface Science 525 (2020) 146596

Fig. 4. Crystal structures of (a) Bi2WO6, (c) a pristine Bi2WO6(010) monolayer, and (e) the AgInS2(112)/Bi2WO6(010) interface. SCAN-computed PDOS for (b) the
Bi2WO6 crystal structure, (d) a Bi2WO6 monolayer, and (f) the topmost layer of the AgInS2(112)/Bi2WO6(010) interface. The Ag, Bi, In, O, S, and W atoms are
represented by cyan, violet, brown, red, yellow, and blue, respectively. (For interpretation of the references to color in this figure legend, the reader is referred to the
web version of this article.)

microspheres consisted of numerous two-dimensional irregular na- when attacked by the high energy electron beam under the vacuum
nosheets with a thickness of 13 nm. Further evidence of the nanoplate conditions of the TEM chamber (see Video S1). This phenomenon is
morphology of Bi2WO6 was provided by the TEM image, which showed consistent with literature data, and was first observed and described by
rectangular nanoflakes with regular edges and smooth surfaces. It was Hsu et al. in 1998 [39].
found that the morphology of Bi2WO6 did not change after introducing
AgInS2 QDs. The HRTEM images of AgInS2 QD-modified Bi2WO6 clearly
3.3. Crystal structure and surface composition
shows two distinct domains; moreover, the images confirmed the for-
mation of a heterojunction between Bi2WO6 and AgInS2 via the thermal
Fig. 6 shows the powder XRD patterns of bare Bi2WO6 and AgInS2
annealing process, and showed intimate contact between the semi-
QDs (before and after the calcination process); diffraction patterns for
conductors. The size distribution of the AgInS2 QDs ranged from 4.5 to
all studied AgInS2/Bi2WO6 nanocomposites can be found in the SI. The
7 nm, and the average diameter was about 6 nm. In addition, the
reference Bi2WO6 sample was chemically pure, showing good crystal-
HRTEM images (inset) show lattice fringes that were well-matched to
linity and distinct diffraction peaks that corresponded to the orthor-
their XRD patterns (see the next section), in which the d values of
hombic (Pca21) crystal structure. Le Bail analysis was performed to
0.229 nm correspond to the (112) peaks of the tetragonal AgInS2 [38].
calculate the lattice parameters of Bi2WO6, and the obtained values are
More interestingly, it was possible to observe the movement of QDs
shown in Table 1. For bare Bi2WO6, the estimated values of

6
P. Parnicka, et al.
Fig. 5. SEM and TEM photos of bare Bi2WO6 and AgInS2 QDs-modified Bi2WO6, and the size distribution of the quantum dots.
a = 5.4430(4) Å, b = 16.438(1) Å, and c = 5.4479(5) Å are in good
agreement with the reported values [36]. The values for the nano-
composites remained statistically unchanged. The diffraction patterns
of AgInS2 QDs are shown in Fig. 6b and c. Broad, low intensity reflec-
tions can be seen at 2θ = 27°, 45°, and 53°. The peak broadening was
caused by the small size of the AgInS2 nanoparticles. To better fit the
experimental profiles of the AgInS2 QDs, the simulated patterns were
modelled using structural analysis software to refine important struc-
tural parameters such as particle size, which enabled the conclusive
assignment of the nanoparticle phase (Fig. S7) [40,41]. The calcination
process resulted in two peaks at high angles, suggesting that the process
transformed the orthorhombic (Pna21) phase to the tetragonal (I-42d)
phase [41]. Further studies focus on the tetragonal phase of AgInS2,
because hybrid materials were prepared using the thermal annealing
process.
The elemental surface compositions of the AgInS2/Bi2WO6 nano-
composites were evaluated by XPS, and are presented in Table 2. The
high resolution (HR) XPS spectra of Bi 4f/S 2p, W 4f, O 1s, Ag 3d, In 3d/
Bi 4d, and S 2s were used for identification of bismuth, tungsten,
oxygen, silver, indium, and sulfur, respectively. Exemplary sets of these
spectra, collected for the 1% AgInS2/Bi2WO6 sample, are shown in
Fig. 7, and the corresponding HR spectra of bare Bi2WO6 and AgInS2
samples are presented as well. The W 4f7/2 signals at 35.4 and 33.5 eV
show the coexistence of the main W(+6) oxidation state and a small
contribution from W(+4), respectively [42]. The Bi 4f spectrum con-
sisted of two states, Bi(+3) and Bi(+3-x), represented by Bi 4f7/2 sig-
nals at 159.1 and 157.2 eV, respectively [42–45]. The main W 4f7/2 and
Bi 4f7/2 signals were in good agreement with the Bi2WO6 components
[43,44], and the small amount of W(+4) can be considered as W-S
7
Applied Surface Science 525 (2020) 146596
bonds [42] formed as a result of interactions between Bi2WO6 and
AgInS2. This interaction also affected the bonding environment of the Bi
atoms. We observed a significant shift of the Bi 4f7/2 peak to a lower BE
for samples doped by AgInS2 (Table 2). The largest shift was noted for
the 1%AgInS2/Bi2WO6 sample (Fig. 8), and was likely a result of the
formation of Bi-S bonds [42] during the preparation of the AgInS2/
Bi2WO6 nanocomposites. The Ag 3d5/2 and In 3d3/2 signals located at
368.1 and 452.4 eV described the doped AgInS2 QDs well [23,46,47].
Inspection of the data presented in Table 2 revealed that the Bi, W, and
O content systematically decreased as the amount of the other elements
increased. The Ag, In, and S contents increased relative to their nominal
contributions, confirming the successful preparation of mixed-AgInS2/
Bi2WO6 nanocomposites. The presence of carbon and nitrogen as ad-
ditional elements are attributed to the use of oleylamine and dode-
cylthiol as surface capping molecules. Consequently, capping ligands
can coordinate with the dangling bonds at the surface of QDs to prevent
uncontrolled growth and agglomeration and providing stability.
Moreover, the literature data revealed that the high-temperature an-
nealing (Ta > 200 °C) causes a sintering growth of QDs and ag-
gregation [48]. The largest amount of these molecules was found at the
surface of bare AgInS2 QDs, what is confirmed by high surface con-
centration of carbon atoms (77.2 at.%, Table 2). It should be noted that
the annealing of AgInS2 QDs at 200 °C decreases the carbon content by
about 11% but it is still the main component of surface atoms (68.45 at.
%). The XPS spectra of bare Bi2WO6 and AgInS2 QDs appear to be very
useful in interpretation of the XPS spectra recorded for the mixed-
AgInS2/Bi2WO6 nanocomposites. The HR spectra of Bi 4f and S 2p
originated from bare Bi2WO6 and AgInS2 QDs, respectively, allow
identify bismuth and sulphur in the Bi4f/S2p overlapped spectra
P. Parnicka, et al. Applied Surface Science 525 (2020) 146596

Bi2WO6 samples. Compared to bare Bi2WO6, which was yellowish in

Fig. 6. (a) Powder XRD patterns of bare Bi2WO6. Open circles represent ex-
perimental data, the solid red line is the Le Bail fit, while the vertical bars show
the expected Bragg reflection positions for the model used. The black line is the
difference between the experimental data and the model. (b) and (c):
Diffraction patterns of AgInS2 QDs before and after the calcination process,
respectively. (For interpretation of the references to color in this figure legend,
the reader is referred to the web version of this article.)
recorded for the 1% AgInS2/Bi2WO6 sample (Fig. 7). Similarly, the In
3d spectrum of bare AgInS2 QDs allows identify the In 3d signals con-
tributed to Bi 4d spectra of the mixed-AgInS2/Bi2WO6 nanocomposites.
3.4. Optical and photoluminescence properties
Fig. 9 shows the UV–Vis DRS of the bare and AgInS2 QD-modified
colour, the QD-modified powders were orange or reddish-orange de-
pending on the concentration of QDs used as a dopant (see Table 1).
The absorption edge of the unmodified Bi2WO6 was estimated to be
460 nm, which can be assigned to the transition from the hybrid O 2p
and Bi 6s orbitals to the W 5d orbital. Although bare Bi2WO6 absorbs
visible light, the significant increase in absorption up to the yellow-
orange region when doped with QDs, i.e. an extension of absorption up
to 800 nm, highlights the importance of AgInS2 QDs as effective light-
harvesting antennae [49,50]. It should be noted that the absorption
edge of the modified photocatalyst red-shifted as the amount of AgInS2
QDs was increased, and that the samples exhibited a gradual increase in
visible light absorption under these conditions. Ge et al. and Kadeer
et al. [19,21] reported that Bi2WO6 sensitized with CdS QDs exhibited
an enhanced absorption coefficient compared to bare samples, in-
dicating interactions between the CdS QDs and Bi2WO6 in the com-
posited samples, which was the main contributor to the narrowing of
the band gap [19,21].
AgInS2 QDs have unique optical and photoluminescence properties
because of the effects of quantum confinement. In general, the valence
band of AgInS2 consists of hybrid S 3p and Ag 4d orbitals, while the
conduction band is composed of In 5s 5p hybridized with S 3p orbitals
[51]. The band gap of the AgInS2 QDs was determined via DRS analysis,
and was tentatively estimated to be ~1.65 eV by extrapolating the
linear section of (αhv)0.5 in the absorption spectrum (see Fig. 10). Thus,
these results support the conclusion that AgInS2 QDs had the char-
acteristic band gap of the tetragonal phase [40]. The inset of Fig. 10
shows a photograph demonstrating the colour of the AgInS2 QDs when
excited via UV light.
To explore the excited-state interactions between Bi2WO6 and the
AgInS2 QDs in the heterojunction system, the PL properties of the
samples were investigated, and the results are presented in Fig. 11. As is
evident from the shape of the spectra, the presence of AgInS2 QDs did
not give rise to new PL phenomena. Moreover, the PL emissions of
samples containing more than 1 wt% QDs were lower than that of bare
Bi2WO6, which may be due to efficient charge dissociation and mi-
gration between AgInS2 and Bi2WO6. Interestingly, only the sample
modified with 0.5 wt% QDs exhibited a higher emission intensity than
that of bare Bi2WO6, meaning that a large number of photogenerated
charge carriers were present at the surface of the semiconductors;
however, lower amounts of QDs could not suppress, minimize, or in-
hibit charge-carrier recombination. Generally, both the electron-ac-
cepting and electron-transporting properties of AgInS2 QDs contribute
to the suppression of charge recombination in the hybrid system. The
above results demonstrate that the efficiencies of the generation, se-
paration, and transfer of photoinduced electron/hole pairs in the
AgInS2/Bi2WO6 QD system were significantly improved, and thus,

Table 2
Elemental content and chemical characters of Bi atoms in the surface layers of Bi2WO6 samples doped with AgInS2.
Sample label Bi Fraction Bi 4f7/2 state (%) W O Ag In S content Ʃ (Ag + In + S) Other (C,
content content content content content (at.%) N)
(at.%) Bix (+3-x) Bi(+3) (at.%) (at.%) (at.%) (at.%) content
157.2 ± 0.2 eV (at.%)
159.1 ± 0.2 eV BE
shift* Δ
(eV)

Bare_Bi2WO6 24.62 10.06 89.94 0 10.61 62.17 0 0 0 0 2.60

0.5%AgInS2/Bi2WO6 22.95 10.13 89.87 −0.01 9.45 60.71 0.06 0.51 0.38 0.95 5.94
1%AgInS2/Bi2WO6 22.98 4.37 95.63 −0.32 9.39 59.01 0.11 0.57 0.46 1.14 7.48
2.5%AgInS2/Bi2WO6 21.80 4.85 95.15 −0.28 8.90 55.22 0.13 0.48 0.68 1.29 12.79
5%AgInS2/Bi2WO6 19.98 6.75 93.25 −0.20 8.21 51.71 0.14 0.50 0.80 1.44 18.66
10%AgInS2/Bi2WO6 18.40 4.00 96.00 −0.16 7.52 47.97 0.18 0.65 1.03 1.86 24.70
AgInS2_before_ calcination 0 0 0 0 0 5.33 1.87 4.68 10.92 17.47 77.20
AgInS2_after_calcination 0 0 0 0 0 8.21 2.40 6.80 14.14 23.34 68.45

* BE shift: Δ = Bare_Bi2WO6 – AgInS2/Bi2WO6.

8
P. Parnicka, et al.
Fig. 7. Bi 4f/S2p, W 4f, O 1s, Ag 3d, In 3d/Bi 4d, and S 2s XPS results for the 1 wt% AgInS2 QDs-modified Bi2WO6 and bare AgInS2 before and after calcination (b.c.
and a.c. respectively).
higher photocatalytic performances should be achievable [52].
3.5. Photocatalytic water splitting and phenol decomposition
The photocatalytic behaviours of bare and AgInS2 QD-modified
Bi2WO6 nanoflowers were evaluated by observing phenol decomposition
in the liquid phase and hydrogen production under UV–Vis and visible
light irradiation. The obtained kinetic results and calculated rates are
displayed in Table 3 and Fig. 12. The efficiency of phenol photo-
degradation in the presence of Bi2WO6 modified with 0.5–10 wt% of
AgInS2 QDs is presented in Fig. 12a. No degradation of phenol was ob-
served in the absence of either photocatalysts or illumination, which ex-
cluded the possibility of photolysis and adsorption of phenol in the present
system. Bare Bi2WO6 showed a relatively low photocatalytic activity, with
9
Applied Surface Science 525 (2020) 146596
only 21% and 15% of phenol being photodegraded after 60 min of ex-
posure to UV–Vis and visible light irradiation, respectively. Additionally,
bare AgInS2 QDs sample exhibited poor photoactivity (~6%). Our ex-
perimental results revealed that the photocatalytic activity of the hybrid
materials (AgInS2 QDs/Bi2WO6) was significantly improved compared
with the bare samples. The phenol degradation efficiency of the hetero-
junctions increased as the QDs loading was increased up to 1 wt%, and
then decreased (UV–Vis: 1 > 2.5 > 5 > 0.5 > 0 > 10 wt%; visible light:
1 > 2.5 > 0.5 > 5 > 0 > 10 wt% AgInS2 QDs). The 1 wt% AgInS2 QD-
modified Bi2WO6 photocatalyst exhibited the highest activity, reaching
62% and 27% degradation when irradiated with UV–Vis and visible light
for 60 min. Moreover, the samples possessed maximum degradation rates
of 2.18 and 0.99 µmol·dm−3·min−1, which were 2–3 times higher than
those of bare Bi2WO6. The modification of Bi2WO6 with a high amount of
P. Parnicka, et al.
Fig. 8. Bi 4f XPS results for the bare Bi2WO6 and 1%AgInS2/Bi2WO6 samples.
Fig. 9. UV–Vis absorbance spectra of bare Bi2WO6 and AgInS2 QDs-modified
Bi2WO6.
Fig. 10. Absorption and emission spectra of red-emitting AgInS2 QDs in
chloroform solutions. The inset shows the Kubelka-Munk transformation of the
AgInS2 QDs and the corresponding real colour when excited with UV light. (For
interpretation of the references to color in this figure legend, the reader is re-
ferred to the web version of this article.)
10
Applied Surface Science 525 (2020) 146596
Fig. 11. Photoluminescence spectra of bare Bi2WO6 and AgInS2 QDs-modified
Bi2WO6.
AgInS2 QDs (10 wt%) resulted in lower photoactivity than that of bare
Bi2WO6, which may be due to blocking on the surface by the adsorbed
QDs aggregates (see Fig. S5), which would reduce light absorption, as well
as energy losses caused by radiative energy transfer. Liang et al. [53] and
Liu et al. [54] in their study also observed decrease in photocatalytic ac-
tivity of Bi2WO6 once the loading of QDs increased beyond a critical value.
Furthermore, active species trapping experiments (Fig. S8) were con-
ducted and revealed a great deal of information about the various path-
ways by which species were generated, leading to the photodegradation of
phenol under visible light irradiation. In this study benzoquinone, silver
nitrate, ammonium oxalate and tert-butanol were employed for quenching
the superoxide radicals, electrons, holes and hydroxyl radicals. The de-
creased of degradation efficiency indicates the formation of appropriate
active species. Results indicated that •OH radicals were the main active
specie produced by bare Bi2WO6 photocatalyst, while AgInS2/Bi2WO6
composite system primarily photodegraded phenol via both •OH and O2•–.
Hydrogen evolution from water under UV–Vis and visible light ir-
radiation using a sulfur solution as the sacrificial reagent to quench the
photoinduced holes (SO32– + H2O + 2 h+ → SO42– + 2H+; 2S2– +
2 h+ → S22–; SO32– + S2– + 2 h+ → S2O32–) was evaluated, and the
results are presented in Fig. 12b. It was observed that H2 could be
generated via direct photolysis of Na2S and Na2SO3 solutions, i.e., in the
absence of any photocatalyst; this is consistent with the literature to
date [55]. No appreciable H2 evolution was detected when using
Bi2WO6 in the absence of AgInS2 QDs, and moreover, bare Bi2WO6 and
bare AgInS2 suppressed the H2 generation efficiency of the sacrificial
reagent itself, which takes place via photolysis. The same trend was
observed for H2 generation as that seen for phenol photodegradation
when using the AgInS2 QD-modified Bi2WO6 samples, with the H2
production rate decreasing in the following order:
1 > 2.5 > 5 > 0.5 > 0 > 10 wt% AgInS2 QDs. Remarkably, the
highest photocatalytic H2 production rate of 1 wt% AgInS2/Bi2WO6 was
611 µmol·g−1, a 2.4-fold enhancement when compared with that of
bare Bi2WO6. Again, Bi2WO6 loadings of up to 10 wt% resulted in a
decline in activity, probably ascribable to the sheltering effect of the
AgInS2 QDs. The stability and reusability of the 1 wt% AgInS2 QD-
modified Bi2WO6 was investigated over three consecutive runs with
total length of 12 h and additionally after storage for three months. For
the reusability study, the powder photocatalyst was separated by cen-
trifugation after each run, washed with water, and dried at 60°C before
reuse. As shown in Fig. 12c, the sample showed a modest decrease in
photoactivity when reused. The structure of the sample prior to and
after the photocatalytic reaction was also examined by XRD, and it was
found that no phase changes or structure damage occurred. The long-
P. Parnicka, et al. Applied Surface Science 525 (2020) 146596

Table 3
Photoactivities of AgInS2/Bi2WO6 photocatalysts under UV–Vis and visible light irradiation.
Sample label Phenol degradation rate under irradiation Amount of hydrogen generation under Hydrogen production rate under UV–Vis
(µmol·dm−3·min−1) UV–Vis irradiation after 240 min (µmol) irradiation (µmol·g−1·h−1)

UV–Vis (λ > 350 nm) Vis (λ > 420 nm)

Photolysis 0.15 < Detection limit 29.72* 74.31*

Bare_Bi2WO6 0.71 0.45 25.19 62.97
0.5%AgInS2/Bi2WO6 1.04 0.64 39.65 99.14
1%AgInS2/Bi2WO6 2.18 0.99 61.10 152.75
2.5%AgInS2/Bi2WO6 1.86 0.69 55.21 138.02
5%AgInS2/Bi2WO6 1.58 0.45 48.76 121.90
10%AgInS2/Bi2WO6 0.58 < Detection limit 15.63 39.07
Bare _AgInS2 0.19 0.22 19.76 49.42

* H2 generated via direct photolysis of sacrificial agent (Na2S and Na2SO3 solution).

term stability study revealed that the photocatalytic hydrogen pro-
duction rate decreased only by 4% after storage for three months. Re-
actions using bare Bi2WO6 and a sample containing the optimum
AgInS2 content (1 wt%) were also carried out under 420 nm light ir-
radiation. In this case, it can be seen in Fig. 12f that Bi2WO6 alone was
inert for hydrogen generation, despite Bi2WO6 being able to absorb
visible light successfully (as shown by the DRS/UV–Vis measurements,
Fig. 9). The most common theory for this is that the CB edge of Bi2WO6
was more positive than the reduction potential of H+/H2, resulting in
the excited electrons failing to reduce H2O into H2 [56]. However, the

Fig. 12. (a) Phenol degradation efficiency of AgInS2/Bi2WO6 under irradiation with UV–Vis and visible light. Photocatalytic H2 generation under (b) UV–Vis and (f)
visible light irradiation in the presence of AgInS2/Bi2WO6. (c) Reusability and (e) stability during prolonged storage of 1 wt% AgInS2-modified Bi2WO6. (d) XRD
pattern of 1 wt% AgInS2-modified Bi2WO6 before and after 3 cycles of photocatalytic hydrogen generation.

11
P. Parnicka, et al. Applied Surface Science 525 (2020) 146596

Fig. 13. Crystal structures of Bi2WO6(010) monolayers with adsorbed (a) H2, (d) H2O, and (g) O2. SCAN-computed PDOS for adsorbed (b) H2, (e) H2O, and (h) O2 on
Bi2WO6(010) monolayers. Computed PDOS of the most stable configurations for adsorbed (c) H2, (f) H2O, and (i) O2 at the AgInS2(112)/Bi2WO6(010) interface. In all
the cases, the PDOS was computed for the topmost layer of each slab, including the absorbed molecule. Cases (f) and (i) correspond to absorptions at surface In and
Ag sites, respectively (cf. Table 4).

band alignment between Bi2WO6 and AgInS2 allows the electrons Table 4
generated on the Bi2WO6 to transfer to the QDs and reduce protons to Computed band gaps (Eg) and adsorption energies (ΔEads) of H2, H2O, and O2
H2. The H2 evolution rate increased from 2 to 79 µmol·g−1 (39.5-fold molecules on the Bi2WO6(010) monolayer and at the AgInS2(112)/
increase) after loading the QDs, which can be assigned to the stronger Bi2WO6(010) interface. The values corresponding to H2O– and
redox ability of the prepared photocatalyst system, which is discussed O2–AgInS2(112)/Bi2WO6(010) refer to configurations where the nearest ab-
sorption surface site is Ag or In.
in the next section.
System type ΔEads (eV) Eg (eV)

Bi2WO6(010) – 2.8
3.6. Origin of photocatalytic performance
H2–Bi2WO6(010) −0.09 2.7
H2O–Bi2WO6(010) −1.09 2.6
To understand the mechanisms of photocatalytic degradation of O2–Bi2WO6(010) −0.90 1.9
phenol and hydrogen production, DFT calculations of the adsorption AgInS2(112)/Bi2WO6(010) – 1.1
energies of O2, H2O, and H2 molecules on Bi2WO6 and AgInS2/Bi2WO6 H2–AgInS2(112)/Bi2WO6(010) −1.08 1.1
H2O–AgInS2 (112)/Bi2WO6(010) −1.37, −1.95 1.2, 1.0
surfaces were performed (Fig. 13). To investigate the adsorptions of the
O2–AgInS2 (112)/Bi2WO6(010) −1.76, −0.63 0.6, 1.2
molecules onto both a bare Bi2WO6(010) monolayer and AgInS2/
Bi2WO6 interfaces, we employed 2×2 surface supercells containing 72
and 104 atoms, respectively (cf. Fig. 4 c and e). Table 4 displays the AgInS2(112)/Bi2WO6(010) system significantly. However, adsorption
SCAN-computed adsorption energies (ΔEads) of H2, O2, and H2O mole- of O2 molecules induced additional O 2p surface states within the band
cules on Bi2WO6(010) and AgInS2(112)/Bi2WO6(010). For the gap regions of both Bi2WO6(010) and AgInS2(112)/Bi2WO6(010)
Bi2WO6(010) system, the adsorption energies ranged from −0.09 to (Fig. 13h and i). Interestingly, in the O2-AgInS2(112)/Bi2WO6(010)
−1.09 eV, suggesting that H2 and O2 were physisorbed at the system additional Ag 4d states with a small contribution from In 4p S 3p
Bi2WO6(010) surface. On the other hand, the adsorption energies for states were also observed (Fig. 13i). The obtained results confirmed that
the AgInS2(112)/Bi2WO6(010) interface ranged from −0.93 to the surface of the AgInS2(112)/Bi2WO6(010) interface was more active,
−1.95 eV and increased in the order O2-AgInS2(112)/ thus the system can strongly interact with surrounding species such as
Bi2WO6(010) > H2O-AgInS2(112)/Bi2WO6(010) > H2-AgInS2(112)/ H2, O2, and H2O and induce the photocatalytic oxidation of OH– to •OH,
Bi2WO6(010). The absorptions of H2 and H2O molecules did not change the reduction of O2 to O2•– or the reduction of H+ to H2 (i.e. H2O
the position of the VBs and CBs of the Bi2WO6(010) monolayer and

12
P. Parnicka, et al.
Fig. 14. Schematics for band gap match and electron-hole pair separation in the AgInS2 QDs/Bi2WO6 composite (before and after contact).
molecules are oxidized to H+, then H+ is reduced to H2) [57].
The Mulliken electronegativity theory formulas (Eqs. (2) and (3))
were used to estimate the potentials of CB and VB edges of Bi2WO6 and
AgInS2 semiconductors, to give an in-depth understanding of the het-
erojunction formation and the energy band structure:
EVB = X Ee 0.5Eg
ECB = EVB Eg
where X is the absolute electronegativity of the semiconductor, which is
the geometric mean of the electronegativity of the constituent atoms,
and the EVB and Eg are the upper position of VB relative to the NHE
level and band gap of the semiconductor, respectively, and Ee is the
energy of free electrons on the hydrogen scale (4.5 eV vs. normal hy-
drogen electrode (NHE)). The X values of Bi2WO6 and AgInS2 were
calculated to 6.33 and 4.80 eV, respectively [58]. The BG energies of
Bi2WO6 and AgInS2 are given in Fig. 10 and S9, which are 2.8 and
1.65 eV, respectively. EVB of Bi2WO6 and AgInS2 is determined to be
0.43 and −0.53 eV relative to the NHE level, respectively. Corre-
spondingly, the ECB of Bi2WO6 and AgInS2 is obtained to be 3.23 and
1.13 eV, respectively.
According to both the theoretical analysis and the experimental
results, possible mechanisms for the photocatalytic processes (hydrogen
generation and degradation of contaminants) over AgInS2 QDs/Bi2WO6
materials can be proposed based on the energy levels and charge carrier
migration, as illustrated in Fig. 14. The diffusive driving force for the
charge carriers results from the well-matched band potentials of the two
semiconductors, which results in the formation of a well-developed
heterojunction interface. The energy bands of Bi2WO6 and AgInS2 shift
upward and downward, respectively, until the Fermi levels reach
equilibrium, aiding the diffusion of charge carriers. By combining the
results, it is proposed that a direct Z-scheme charge transfer route can
proceed over the AgInS2/Bi2WO6 p–n heterojunction composites. Under
irradiation, the photoinduced electrons from the more positive CB of
Bi2WO6 combine with the photogenerated holes on the VB of AgInS2
QDs. Meanwhile, the holes in the more positive VB of Bi2WO6 and the
electrons in the more negative CB of AgInS2 could be retained and take
part in the reduction and oxidation reaction. As a result, not only the
separation and transfer process of the photogenerated e–/h+ couples
were significantly enhanced, but also the strong redox ability was
preserved in the system [59]. The band alignment of AgInS2/Bi2WO6
composites with reference to the NHE revealed that AgInS2 CB potential
is more negative compared to the O2/O2•– and H+/H2 redox potentials.
In addition, the VB potential of Bi2WO6 is more positive compare to the
H2O/•OH and H2O/O2 redox potentials [1]. Therefore, the AgInS2/
Bi2WO6 heterostructures showed high photocatalytic performance on
organic pollutants degradation and hydrogen production under ultra-
violet and visible light irradiation.
Applied Surface Science 525 (2020) 146596
4. Conclusions
A series of first-principles DFT calculations were carried out in
combination with the experimental synthesis and characterization of
AgInS2 QD-decorated Bi2WO6 to investigate the change in the photo-
catalytic capability provided by the heterojunction formed between
(2)
Bi2WO6 and AgInS2. After introducing AgInS2 QDs into Bi2WO6, a
(3) useful Bi-S bond was formed. When the heterojunction was formed, a
high electron density around the Fermi level was achieved, which led to
inter-particle electron transfer in the composite samples. The PL spectra
showed that the QDs promoted the separation of the photogenerated
charge carriers and induced suppression of electron/hole pair re-
combination when compared to that in bare samples. Moreover, the
prepared photocatalysts showed broad-spectrum response, with in-
creased absorption and utilization of light. Consequently, AgInS2 QD-
modified samples had not only enhanced photocatalytic capability but
also improved long-term stability and reusability. Meanwhile, DFT
calculations showed that the adsorption of H2, O2, and H2O molecules
on the surface of the AgInS2/Bi2WO6 system could lead to high ad-
sorption energies, which contributed to the induced photocatalytic
oxidation of OH– to •OH and reduction of O2 to O2•– or reduction of H+
to H2, resulting in high photocatalytic efficiencies. The optimal 1 wt%
AgInS2 QDs/Bi2WO6 composite showed 62% and 27% phenol de-
gradation and 611 and 79 µmol·g−1 of evolved H2 under UV–Vis and
visible light irradiation, respectively. This work reveals that
AgInS2 QDs/Bi2WO6 could be used as a cheap and efficient multitasking
material for photocatalytic applications.
CRediT authorship contribution statement
Patrycja Parnicka: Conceptualization, Investigation, Methodology,
Data curation, Visualization, Writing - original draft, Writing - review &
editing. Alicja Mikolajczyk: Software, Methodology, Formal analysis,
Visualization, Writing - original draft. Henry P. Pinto: Software,
Formal analysis. Wojciech Lisowski: Investigation, Writing - original
draft. Tomasz Klimczuk: Investigation, Writing - original draft.
Grzegorz Trykowski: Investigation. Beata Bajorowicz: Project ad-
ministration. Adriana Zaleska-Medynska: Conceptualization, Funding
acquisition, Project administration, Supervision, Writing - review &
editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
13
P. Parnicka, et al.
Acknowledgments
This research was supported by the Polish National Science Centre,
under the grant titled: “Mechanism of quantum dots excitation in
photocatalytic reaction”, contract no.: 2016/23/B/ST8/03336, and was
also supported by the Foundation for Polish Science (FNP) (START
001.2019 and START 58.2019).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apsusc.2020.146596.
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