Ceramics International 43 (2017) 11250–11259

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Characterization of core@shell-structured ZnO@Sb2S3 particles for MARK

effective hydrogen production from water photo spitting
⁎
Namgyu Son, Jeong Yeon Do, Misook Kang
Department of Chemistry, College of Natural Science, Yeungnam University, Gyeongsan, Gyeongbuk 38541, Republic of Korea

A R T I C L E I N F O A BS T RAC T

Keywords: In this study, Sb2S3-photosensitized ZnO photocatalysts (ZnO@Sb2S3) are used to enhance the production of
Core@shell structure hydrogen from water by photo-splitting. Various loadings of Sb2S3 are added to the surface of rod-shaped ZnO
ZnO@Sb2S3 nanoparticles (100–150 nm) as a photosensitizer to absorb visible light. The obtained particles show core@shell
Water photo-splitting structures in transmission electron microscopy images. The physicochemical characteristics of the Sb2S3, ZnO,
H2 production
and core@shell structured ZnO@Sb2S3 particles are confirmed using X-ray diffraction, UV–visible spectro-
Electron-hole recombination
scopy, high-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray
photoelectron spectroscopy. H2 evolution from water photo-splitting is enhanced for the core@shell structured
ZnO@Sb2S3 in a liquid system compared to that for pure ZnO and Sb2S3. Hydrogen gas is produced at a rate of
77.5 μmol/g after 10 h using the ZnO@Sb2S3 photocatalyst with a 7.0 mol% Sb2S3 loading. Based on cyclic
voltammetry results, the high photoactivity of ZnO@Sb2S3 is attributed to both the fast excitation of electrons
by increased absorption of visible light and the suppression of electron-hole (e--h+) recombination, which
results from the appropriate energy gap between the Sb2S3 and ZnO particles.

1. Introduction hydrogen by reducing water, and the resulting holes generated in the
VB oxidize water to produce oxygen. The energy required for this
Post-industrialization depletion of fossil energy sources and the process is ~ 1.23 eV. Therefore, the band gap of the photocatalyst
increase in carbon dioxide emissions owing to the use of fossil fuels should have a value of at least 1.23 eV to enable water decomposition
have led to global warming, which is becoming increasingly serious. and be within a range including both the reduction and oxidation
Therefore, new energy sources are being sought to replace fossil fuels. potentials of water [10]. Various photocatalysts have been developed to
Hydrogen offers a clean and abundant energy source that can solve satisfy these requirements. Among them, titanium dioxide (TiO2), with
energy supply and environmental issues simultaneously [1,2]. a band gap of 3.2 eV, has emerged as a typical photocatalyst after
Currently, most hydrogen is produced from crude oil refining and significant research [11]. Furthermore, particles of TiO2 with various
hydrocarbon reformation [3,4], which means that hydrogen production additional metal dopants, either added to the surface of the catalyst or
remains linked to fossil fuels and the associated problems of exhaustion within the TiO2 lattice, have been developed to improve the catalytic
of fossil energy sources and emission of carbon dioxide. In contrast, performance [12,13]. Despite the development of many TiO2-based
producing hydrogen by decomposing water would provide an almost catalysts, however, they have not yet reached the commercialization
infinite energy source. Hydrogen is most readily produced by electro- stage. Additionally, the photocatalytic decomposition of water over
lysis [5]. However, electrolysis uses electricity and the electrolytes and TiO2 is ineffective because the amount of hydrogen produced is limited
electrodes used in the process are expensive. To solve these problems, by the rapid recombination of holes and electrons, resulting in the
recently, research has been focused on producing hydrogen using formation of water. To overcome this rapid recombination in water
sunlight and a photocatalyst to decompose water or lower-chain-length splitting, studies have aimed to improve the hydrogen production by
alcohols [6,7]. the photodecomposition of methanol or ethanol instead of water
A typical mechanism of hydrogen production using a photocatalyst [14,15]. However, the decomposition of light alcohols eventually leads
is briefly described as follows [8,9]. When light energy is incident on a to the generation of carbon dioxide. Thus, a separation step with
photocatalyst, the electrons in the valence band (VB) are excited into hydrogen is essential, which, however, incurs an associated secondary
the conduction band (CB). The generated CB electrons produce cost. Therefore, it is necessary to design a breakthrough catalyst

⁎
Corresponding author.
E-mail address: [email protected] (M. Kang).

http://dx.doi.org/10.1016/j.ceramint.2017.05.175
Received 1 May 2017; Received in revised form 24 May 2017; Accepted 25 May 2017
Available online 31 May 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
N. Son et al. Ceramics International 43 (2017) 11250–11259

researchers have found that metal oxide/sulfide composites exhibit

high photochemical activity [21,22]. Thus, we loaded Sb2S3 on the
surface of ZnO. Antimony(III) sulfide, Sb2S3, has a band-gap (Eg =
1.7 eV) that closely matches the maximum of the solar spectrum at
Earth's surface and is known as a visible-light-sensitive photocatalyst
in redox processes. For example, Kozytskiy et al. reported [21] the
photochemical formation and photoelectrochemical properties of TiO2/
Sb2S3 heterostructures, the photocurrent density of which is higher
than that of a bare titania film by a factor of 3.6. Their heterostructures
inhibited electron-hole recombination and reduced the loss of photo-
generated electrons through unwanted reactions with the electrolyte.
Huang et al. found that the bimetallic Sb2S3/Bi2S3-doped TiO2 and
doped TiO2 powders show a much higher reaction rate for the
photodegradation of 4-nitrophenol (4-NP) than bare TiO2 under UV–
vis illumination [22]. However, most Sb2S3 sensitizers are limited to
organic decomposition catalysts and are rarely used as water decom-
position catalysts. Furthermore, we found no reports on the photo-
catalytic formation of Sb2S3-based heterostructures and their photo-
Fig. 1. A liquid photoreactor designed in our laboratory for the photocatalytic splitting electrochemical properties.
of water. The present paper demonstrates the feasibility of loading Sb2S3 on
the surface of nanocrystalline ZnO and focuses on the characterization
capable of decomposing water in an environmentally friendly manner of the structure, morphology, and optical and photoelectrochemical
to obtain hydrogen. properties of the resulting catalysts using X-ray diffraction (XRD),
For this purpose, many researchers have shifted their attention to high-resolution transmission electron microscopy (HRTEM), X-ray
alternative TiO2-free catalysts. Thus, we first synthesized ZnO, which photoelectron spectroscopy (XPS), energy-dispersive X-ray spectro-
has a band gap = 3.0 eV and shows excellent optical activity, as a core scopy (EDX/mapping), UV–visible spectroscopy, photoluminescence
catalyst [16]. However, the use of ZnO alone is insufficient to overcome (PL), and cyclic voltammetry (CV). Additionally, we propose that this
the redox potential for water decomposition, necessitating the devel- catalyst overcomes the rapid recombination of electrons and holes
opment of a sulfur-containing photosensitizer dopant that can react during water splitting, leading to improved hydrogen production.
sensitively to visible light and can extend the CB energy of ZnO. Many Furthermore, we present the mechanism of electron transport during
reports have described the progression of metal sulfide photocatalysts, the photocatalytic reaction of this catalyst.
such as ZnS, CuS, SnS2, and Bi2S3, from synthesis to applications as a
new photocatalytic reaction mechanism. These materials have narrow 2. Experimental
band gaps that allow the absorption of longer wavelengths, unlike
conventional metal oxide semiconductor systems [17–20]. Although 2.1. Synthesis of ZnO, Sb2S3, and Sb2S3-photosensitized ZnO (ZnO@
many sulfur-containing catalysts have been introduced and some Sb2S3)
satisfactory catalytic activity has been shown, the scope of research is
still very limited compared to that of metal oxide catalysts. Recently, ZnO was synthesized by a typical hydrothermal method, as follows:

Fig. 2. XRD patterns of ZnO, Sb2S3, and Sb2S3-photosensitized ZnO catalysts.

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Fig. 3. SEM (A) and TEM (B) images of Sb2S3, ZnO, and Sb2S3-photosensitized ZnO catalysts.

zinc acetate (Zn(O2CCH3)2, 0.2 mol, 99.9%, Junsei Chemical, Japan) molar ratio of Sb to S was adjusted to 2:3. The solution was stirred
was dissolved in water, and sodium hydroxide (0.3 mol, 99.9%, Junsei again for 1 h before it was placed in a dry oven at 180 °C, and aged for
Chemical, Japan) was added to promote hydrolysis. The mixture was 8 h to obtain a powdery sample. This sample was rinsed with ethanol
stirred vigorously for 1 h, after which the pH of the mixture was 10. three times to remove residual chlorine and other impurities from its
The homogeneously stirred solution was placed in an autoclave, and surface. The powder was dried at 100 °C for 24 h and then heat-treated
the temperature of the reactor was raised to 200 °C at a rate of 10 °C/ for 2 h at 300 °C to obtain the final Sb2S3-photosensitized ZnO product.
min and maintained at 200 °C for 12 h. After the reaction was In conclusion, six samples were used as catalysts in this study: ZnO,
complete, the final solution was separated into a powdered sample by Sb2S3, and Sb2S3-photosensitized ZnO (ZnO@Sb2S3) containing 2.5,
centrifuge, and the sample was washed with water until the pH was 5.0, 7.5, or 10.0 mol% Sb2S3.
near neutral. After drying for 24 h at 80 °C, the final ZnO powder was
obtained. 2.2. Characterization of ZnO, Sb2S3, and Sb2S3-photosensitized ZnO
Sb2S3 was also synthesized for comparison by a method similar (ZnO@Sb2S3)
with ZnO as follows: the Sb and S precursors SbCl3 and thiourea
(SC(NH2)2) were added to ethylene glycol in a ratio of 2:3, and mixed The synthesized ZnO, Sb2S3, and Sb2S3-photosensitized ZnO
well, before being aged at 180 °C for 8 h. The resulting powder was (ZnO@Sb2S3) catalysts were examined by XRD (MPD, PANalytical,
then treated at 300 °C for 2 h under an argon atmosphere. The color of at Yeungnam University Instrumental Analysis Center) with nickel-
the obtained pure Sb2S3 was black-gray. filtered CuKα radiation (30 kV, 30 mA). The samples were scanned at
Core@shell-structured Sb2S3-photosensitized ZnO samples (ZnO@ 2θ angles ranging from 10° to 80° at a scan speed of 10° min–1 and a
Sb2S3) were synthesized by an impregnation method, as follows: ZnO time constant of 1 s. The particle sizes and morphologies of the ZnO,
(5.0 g) was added to ethylene glycol (100 mL) containing 2.5, 5.0, 7.5, Sb2S3, and Sb2S3-photosensitized ZnO (ZnO@Sb2S3) materials were
or 10.0 mol% antimony chloride (SbCl3, 99.9%, Junsei Chemical, examined by HRTEM using a JEOL 2000EX TEM instrument operated
Japan). After stirring for 1 h, thiourea (SC(NH2)2, 99.9%, Junsei at 200 kV, and by scanning electron microscopy (SEM, JEOL 2000EX).
Chemical, Japan) was added to this solution as a sulfur source. The The Brunauer-Emmett-Teller surface area of the catalysts was mea-

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Fig. 4. HRTEM (A), selected-area electron diffraction (SAED) (B), and element mapping image (C) of [email protected] mol% Sb2S3. (For interpretation of the references to color in this figure,
the reader is referred to the web version of this article).

sured using a Belsorp II instrument. Nitrogen gas adsorption was UV-lamps (3 × 6 W cm–2 = 18 W cm–2, 20.0 cm length × 2.0 cm
measured using a continuous flow method with a nitrogen/helium diameter; Shinan, Sunchun, Korea) emitting radiation at 365 nm were
mixture as the carrier gas. X-ray photoelectron spectroscopy (XPS, used. The water photo-splitting reaction was carried out for 10 h with
AXIS Nova, Kratos Inc.) spectroscopy measurements of Zn3d, O1s, Sb4f, constant stirring. The amounts of evolved hydrogen and oxygen were
and S2P were performed using a non-monochromatic AlKα X-ray measured at intervals of 1 h. The hydrogen and oxygen gases produced
source to investigate the oxidation state of the components of the during water photo-splitting were analyzed using a thermal conductiv-
synthesized particles. The atomic distributions of the ZnO, Sb2S3 and ity detector (TCD)-coupled gas chromatograph (TGC, model DS 6200;
Sb2S3-photosensitized ZnO (ZnO@Sb2S3) were analyzed by elemental Donam Instruments Inc., Korea). The following GC conditions were
mapping images obtained via EDX (EX-250, Horiba). Diffuse reflec- used: TCD detector, Carbosphere column (Alltech, Deerfield, IL, USA),
tance UV–visible spectra were obtained using a Cary 500 spectrometer and the injection, initial, final, and detector temperatures of 413, 393,
with a reflectance integration sphere. The recombination tendency of 393, and 423 K, respectively.
the photogenerated electron–hole pairs was estimated by PL (Perkin
Elmer) measurements using a He–Cd laser source at a wavelength of
3. Results and discussion
325 nm. CV results were obtained using a BAS 100B instrument at
room temperature and a scan rate of 100 mV/s with KCl (0.1 M) as the
3.1. Physical properties of ZnO, Sb2S3, and Sb2S3-photosensitized
supporting electrolyte, platinum wires as the working and counter
ZnO (ZnO@Sb2S3)
electrodes, and Ag/AgCl as the reference electrode.
Fig. 2 shows the XRD patterns of the ZnO, Sb2S3, and Sb2S3-
2.3. Hydrogen production by photo water splitting using ZnO@Sb2S3 photosensitized ZnO particles. All the peaks in the XRD pattern of
catalysts Sb2S3 could be indexed as the orthorhombic phase (cell constants a =
11.20 Å, b = 11.28 Å, c = 3.83 Å; JCPDS reference code. 001-0538)
The photocatalytic splitting of water was carried out using a liquid [24]. The main XRD peaks at 15.8°, 17.7°, 22.3°, 24.9°, 29.5°, 32.5°,
photoreactor designed in our laboratory, as shown in Fig. 1 [23]. For 33.6°, 35.8°, 37.1°, 40.4°, 43.2°, 47.3°, 53.2°, 54.5°, and 60.4° were
water photo-splitting, the powdered ZnO, Sb2S3, or ZnO@Sb2S3 (0.5 g) assigned to the d200, d210, d220, d130, d211, d221, d330, d420, d231, d141,
was added to distilled water (1.0 L) in a Pyrex reactor (2.0 L capacity). d250, d530, d531, d360, and d631 planes, respectively. ZnO also had high

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Fig. 5. XPS spectra of the Sb2S3, ZnO, and [email protected] mol% Sb2S3.

crystallinity, and was formed with a hexagonal structure (cell constants phase Sb2S3, and the sets of lattice fringes of 0.279 nm (100), 0.259 nm
a = 3.24 Å, b = 3.24 Å, c = 5.17 Å; JCPDS reference code. 001-1136) (002), and 0.247 nm (101) were assigned to hexagonal phase of ZnO
with main peaks at 2θ = 31.8°, 34.3°, 36.4°, 47.5°, 57.1°, 63.2°, and [26,27]. The inset of Fig. 4B displays the SAED patterns of the pure
67.8° [25]. The positions of the ZnO peaks in the Sb2S3-photosensitized ZnO and core@shell structured ZnO@Sb2S3. The corresponding se-
ZnO particles did not differ from those of pure ZnO, and no peaks lected area electron diffraction (SAED) pattern for ZnO in the inset in
assigned to Sb2S3 were observed despite the addition of Sb2S3 to the this figure confirms the presence of a polycrystalline structure with
ZnO surface. However, a trace of Sb2S3 was visible in the samples clear special spots. Otherwise, the obvious diffraction spots within
containing 10.0 mol% Sb2S3, indicating the presence of many Sb2S3 these rings demonstrate that the ZnO@Sb2S3 is continuously poly-
particles dispersed on the ZnO surface. crystalline with good crystallinity. On the other hand, the elemental
Fig. 3A shows SEM images of the Sb2S3, ZnO, and Sb2S3-photo- mapping in Fig. 4C confirms that Zn and O elements are mostly present
sensitized ZnO particles. The pure Sb2S3 formed cubic or rectangular inside (dark color), and Sb and S elements exist mostly on the outside.
rod-like shapes, ranging in size from 1.0 to 3.0 µm in length to 0.5– Moreover, these elements are uniformly distributed. Thus, the HRTEM
1.5 µm in width. Their large size seemed to originate from the image reveals the microstructure and composition of ZnO@Sb2S3,
formation of aggregates caused by entanglement between the particles, further proving that ZnO@Sb2S3 was fabricated successfully. These
and TEM analysis (Fig. 3B) confirmed that the Sb2S3 crystals were results confirm that ZnO was present in the core and Sb2S3 formed a
approximately 300 nm long and 50 nm wide. The shape of pure ZnO shell, with a distribution of Sb2S3 nanoparticles uniformly covering the
was similar to that of Sb2S3, but its size was smaller, forming uniform top and lateral surfaces of ZnO.
1.0 × 0.5 µm particles. Moreover, the uniformity of the surface of these Fig. 5 shows the XPS spectra of Sb2S3, ZnO, and a core@shell
particles decreased depending on the loading of Sb2S3, and the size of structured [email protected] mol% Sb2S3, as a representative example. The
the particles also increased slightly at higher loadings. The reason for spectra showed stable baselines without noise and clear peaks corre-
these changes, shown in the low magnification-TEM image in Fig. 3B sponding to Zn, Sb, O, and S, confirming that each component existed
was that particles of Sb2S3 enveloped the surface of the ZnO rods as like in the samples. Fig. 5a and b show that the observed binding energies
core@shell structure, ZnO@Sb2S3 composites. Therefore, we suggest of Zn 2p3/2 and 2p1/2 in pure ZnO were 1021.8 and 1044.8 eV,
that as the Sb2S3 loading increased, the uniformity and smoothness of respectively, while the observed binding energies in 7.5 mol% Sb2S3-
the particle surface decreased. photosensitized ZnO were 1021.58 eV and 1045.58 eV. The slight
In Fig. 4, to investigate the intrinsic crystal structure of core@shell decrease in the binding energy and peak intensity of Zn 2p in the
structured [email protected] mol% Sb2S3, high-resolution TEM (HRTEM) (A), ZnO@Sb2S3 confirmed that Zn was present as ZnO at the inner surface
selected-area electron diffraction (SAED) (B), and elemental mapping of the ZnO@Sb2S3 sample. In the O1s spectrum of pure ZnO, the
image (C) are characterized. As shown in Fig. 4A-a, Sb2S3 crystals spectrum was deconvoluted to two components at binding energies of
broadly cover the ZnO crystals, and further, the lattice of each crystal is 530.3 and 531.4 eV. The first peak was attributed to O2− ions
clearly visible. One part was extracted and analyzed in detail as shown surrounded by zinc atoms in a hexagonal ZnO lattice, while the second
in Fig. 4A-b: the lattice fringes of 0.305 nm (211 diffraction plane), peak is associated with chemisorbed or dissociated oxygen, or OH
0.340 nm (111), and 0.399 nm (220) match well to orthorhombic species on the surface of ZnO nanorods [28]. Fig. 5c and d further

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Fig. 6. Adsorption–desorption isotherm curves of N2 at 77 K for Sb2S3, ZnO, and ZnO@Sb2S3 catalysts.

Table 1 and 2p1/2 peaks at binding energies of 160.7 and 161.8 eV were
Atomic compositions of the external surfaces of Sb2S3, ZnO, and ZnO@Sb2S3 catalysts observed in pure Sb2S3, and these peaks were shifted to a higher
calculated from EDX data. binding energy in 7.5 mol% Sb2S3-photosensitized ZnO. Consequently,
Catalysts/ Sb atomic S Zn O (Sb2S3/ (Sb/Sb
the XPS results confirmed that the synthesized particles were ZnO with
Elements % weight Sb2S3+ZnO) × +Zn) × Sb2S3 and Sb2S3 on the surface in a core@shell configuration.
% 100 100 The performance of the catalyst is strongly related to the ability of
the reactants to adsorb on the catalyst surface. Larger surface areas
[email protected] mol 0.16 2.04 41.31 56.49 6.75 0.38
allow a greater the amount of reactant to adsorb and, consequently,
% Sb2S3 0.52 1.87 74.93 25.07 8.02 0.69
[email protected] mol 0.27 2.16 39.13 58.44 7.67 0.69 improve the catalyst's performance. Fig. 6 shows N2 adsorption–
% Sb2S3 0.86 1.92 71.20 26.02 10.10 1.19 desorption isotherm curves at 77 K for the Sb2S3, ZnO, and ZnO@
[email protected] mol 0.38 4.54 42.93 52.16 14.33 0.88 Sb2S3 samples. The radius of the pore, in which capillary condensation
% Sb2S3 1.20 3.80 73.23 21.77 16.37 1.61
occurs, can be determined as a function of the relative pressure (P/P0)
ZnO@ 0.73 8.72 51.02 39.53 25.22 1.41
10.0 mol% 2.06 6.44 76.91 14.58 25.72 2.61 using Kelvin's equation [29]. The mean pore diameter, Dp, was
Sb2S3 calculated from the relationship Dp = 4VT/S, where VT is the total
volume of the pores, and S is the BET surface area. According to the
IUPAC classification, pure ZnO displayed a Type II isotherm, corre-
confirm the presence of Sb2S3 on ZnO nanorods. The observed binding sponding to particles with no pores [30]. However, hysteresis loops
energies for Sb 3d5/2 and 3d3/2 in the Sb2S3 sample at 528.8 and were observed at higher relative pressures in ZnO@Sb2S3 samples,
538.2 eV were assigned to isolated Sb. These peaks were split into two implying a Type IV isotherm. Furthermore, the difference between the
peaks at 529.6 and 538.7 eV, which were attributed to Sb2S3. However, adsorption and desorption curves increased as the loading of Sb2S3
two peaks with very low intensity and corresponding to SbCl3 were also increased, indicating the formation of bulk mesopores between the
observed at 532.4 and 541.4 eV. Thus, it was confirmed that a small particles. The changes in the mean surface area and pore volume are
amount of chlorine, which had not yet been substituted with sulfur, listed in Table 1. In Sb2S3-photosensitized ZnO samples, the BET
remained in the Sb2S3. On the other hand, the peaks shifted to higher specific surface areas increased significantly as the loading of Sb2S3
binding energies in ZnO@Sb2S3, and the positions were attributed to a increased. However, the surface area of pure Sb2S3, which formed large
peak corresponding exactly to Sb in Sb2S3. Otherwise, broad S 2p3/2 particles, was very small: The specific surface area of regular particles is

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Fig. 7. Energy-dispersive X-ray spectroscopy curves of Sb2S3, ZnO, and [email protected] mol% Sb2S3.

Fig. 8. UV–visible spectroscopy curves (A) and Tauc plots (B) of Sb2S3, ZnO, and ZnO@Sb2S3.

typically related to the particle size, with smaller particles having a be large, affecting the apparent atomic ratios in the EDX data. The
greater surface area [31]. amount of Sb2S3 present on the surface increased proportionally to the
The atomic composition of the external surface of the catalysts was amount added to the catalyst, suggesting that these values are reliable.
analyzed by EDX, as shown in Fig. 7, revealing the presence of Sb and S
in pure Sb2S3, and Zn and O in the pure ZnO. The composition of the 3.2. Spectroscopic properties of ZnO, Sb2S3, and ZnO@Sb2S3
samples was found to have Sb:S and Zn:O atomic ratios of 39.2:60.7
and 42.0:57.9, respectively, which are close to the ideal stoichiometric Fig. 8 exhibits the UV–vis spectra of Sb2S3, ZnO, and ZnO@Sb2S3
mole fractions of pure Sb2S3 and ZnO. Each component was found to
samples. The absorption by hexagonally symmetric ZnO normally
be homogeneously dispersed in the EDX the mapping images of Sb, S, appears at ~ 400 nm in pure ZnO, and the absorption bands in the
Zn, and O. The atomic ratios in Table 1 represent the real amounts on
spectra for ZnO@Sb2S3 were similar to that of pure ZnO. The band gap
the external surface of the ZnO@Sb2S3 samples. The stoichiometric
in a semiconductor material is closely related to the range of
atomic ratios of these samples were not constant because of the varying
wavelengths it absorbs, and longer wavelengths of light are absorbed
loadings of Sb2S3 and because EDX only investigates the surface
as the band gap decreases. Consequently, photocatalytic materials with
composition of samples. The catalysts used in this study had core@
a narrow band gap can readily be used in conjunction with visible light,
shell-type structures, in which ZnO was used as a core and Sb2S3 was
but a smaller band gap could reduce the photoactivity by increasing the
the shell. Therefore, the amount of Sb2S3 on the surface is expected to
recombination rate between electrons and holes. The absorptions

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Fig. 9. CV curves of pure Sb2S3 and ZnO particles (A) and peak/onset energy values (B).

Fig. 10. PL spectra (A) and photocurrent responses (B) of Sb2S3, ZnO, and ZnO@Sb2S3 catalysts.

maxima in ZnO@Sb2S3 were slightly shifted to a shorter wavelength Ag+ = + 0.42 eV) was used as an internal standard, and − 4.8 eV was
compared to those of pure ZnO, although the broadened tail may fixed as an energy level in the vacuum set. The energy levels of the
indicate a sulfur component. The band gaps, obtained by extrapolation HOMO and LUMO can be calculated using the following formula:
to the meeting point of the tangents from pure ZnO and [email protected] mol HOMO (or LUMO) (eV) ＝ − 4.8 − (Eonset − E1/2(Ferrocene)). Here, Eonset
% Sb2S3, were 3.09 and 3.18 eV, respectively. Sb2S3, which has a band is the starting point of the redox potential wave and is used more than
gap of 1.56 eV, absorbed across the entire visible region and acted the peak potential values. The onset potentials for reduction, measured
similarly to sulfur in the red color range. against an Ag/AgCl reference electrode, in ZnO and Sb2S3 were − 0.28
The utility of the CV results of pure Sb2S3 and ZnO particles, shown and + 0.22 V, respectively. The LUMO energy levels were, therefore,
in Fig. 9A is highly dependent on the analytical conditions being calculated to be − 4.1 and − 4.6 eV, respectively. The results of the CV
studied since samples must be redox active within the experimental investigations support the UV–vis spectra, shown in Fig. 9A. The band
potential window. It is desirable for samples to display a reversible gap of Sb2S3 was smaller than that of pure ZnO, and its valence and
wave, which indicates a reversible reaction and displays a hysteresis of conduction bands were at energy levels than those of ZnO. This result
absolute potential between the reduction and oxidation peaks. When implies that, in ZnO@Sb2S3, electrons were excited from the valence
such reversible peaks are observed, thermodynamic information, in the band of Sb2S3 to the conduction band of ZnO. Thus, the electrons can
form of the half-cell potential (E°1/2) can be determined [32]. only recombine with the holes slowly, allowing the holes in the valence
Reversible curves were found for pure Sb2S3 and ZnO, assigned to band to persist for a longer time than in pure Sb2S3 or ZnO.
the Sb(III) → Sb(0) and Zn(II) → Zn(0) redox processes, respectively. Consequently, the photocatalytic activity of the ZnO@Sb2S3 is en-
The CV tests confirm the energy of the HOMO (conduction band) and hanced.
LUMO (valence band) of the solid particles [33]. Ferrocene (E1/2 vs. Ag/ Fig. 10 A shows the PL spectra of the prepared Sb2S3, ZnO, and ZnO@

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Fig. 11. Evolutions of H2 and O2 (A) over Sb2S3, ZnO, and ZnO@Sb2S3 catalysts and a proposed mechanism (B) for water photo-splitting in this photosystem.

Sb2S3. PL measurements are often used to investigate the separation 3.3. Photocatalytic hydrogen production performances of ZnO, Sb2S3,
efficiency of the photogenerated electron/hole pairs of semiconductor and ZnO@Sb2S3
particles. In general, there is a strong relationship between the PL
intensity and photoactivity: the lower the PL intensity, the higher the Fig. 11A-a summarizes the H2 and O2 evolution from water photo-
photocatalytic activity [34]. The light-emitting wavelengths of different splitting over the Sb2S3, ZnO, and ZnO@Sb2S3 catalysts in a batch-type
materials are different and, for comparison, the samples were all excited liquid photo system. The figure shows that, even after 10 h, almost no
at the same wavelength of 275 nm in this study; the emission peaks were hydrogen was generated by the pure ZnO and Sb2S3 catalysts, while a
located at a maximum of 468 nm. The PL intensity of the ZnO was much significant amount of H2 gas was collected for the ZnO@Sb2S3
higher than the ZnO@Sb2S3, possibly because of the new oxygen catalysts. The amount of H2 produced over the [email protected] mol% Sb2S3
vacancies produced in the latter. The pure Sb2S3 showed the lowest PL reached 77.5 μmol without catalytic deactivation. These results are
intensity, and the PL intensity increased with increasing ZnO. The typical encouraging. Recent publications have mostly investigated hydrogen
real-time photocurrent responses of Sb2S3, ZnO, and ZnO@Sb2S3 samples production by decomposing light alcohols, such as methanol, rather
to a light source being switched on and off are depicted in Fig. 10B. In than by decomposing water [36,37] because of the high energy (at least
general, a response is generated when photogenerated electron-hole pairs 1.23 eV) required to decompose water. Therefore, it is very difficult to
are separated, and the effect of illumination is seen as an increase in decompose water to obtain hydrogen stably using a general photo-
current, which might result from photo-carrier generation as well as catalyst such as TiO2. Thus, many researchers have used light alcohol
carrier mobility enhancement [35]. When the light was turned on, the as a raw material for hydrogen production, and we have produced
photoreduction current rapidly increased, and then reached a steady state hydrogen by photocatalytic decomposition of methanol in many of our
after a few seconds. Then, when the light was turned off, the photocurrent studies [38,39]. However, in this study, we confirmed that hydrogen
decreased instantaneously to almost zero. Under illumination, the pure could be stably obtained by decomposing water when a suitable
ZnO exhibited the highest photocurrent up to the 4th cycle, which is amount of Sb2S3 is loaded on a ZnO catalyst. In conclusion, this study
typical of extrinsic semiconductors. However, the response decreased suggests that, if a suitable sulfur compound with good optical activity is
rapidly over time, indicating deactivation of the catalyst. On the other coated on a ZnO catalyst, it is possible to produce hydrogen readily
hand, the current density of Sb2S3 was very low but remained constant from water decomposition. The amount of H2 produced by the ZnO@
throughout the cycles. The photocurrent of the ZnO@Sb2S3 composites 10.0 mol% Sb2S3 was rather low, despite the higher Sb2S3 loading. This
was initially smaller than that in ZnO and decreased as the amount of result likely occurred because too many electrons were excited to the
Sb2S3 increased. However, their sensitivity remained constant as the on- conduction band of ZnO at high Sb2S3 loadings, leading to the capacity
off cycle progressed, but the ZnO response decreased. The signal for of the conduction band of ZnO being reached and the electrons instead
[email protected] mol% Sb2S3 was the highest after the fifth on-off cycle, residing in the conduction band of Sb2S3. Eventually, these electrons
suggesting that the separation of electrons and holes was accelerated in relax again and recombine with holes, which leads to the inactivation of
[email protected] mol% Sb2S3. Eventually, this effect had a positive effect on the the catalyst. Therefore, an optimal loading of Sb2S3 exists. On the other
activity of the catalyst. hand, quantitatively, the amount of oxygen is half the amount of

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