Results in Chemistry 3 (2021) 100151

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Results in Chemistry
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Bismuth sulfide based compounds: Properties, synthesis and applications

Timothy O. Ajiboye , Damian C. Onwudiwe *
Material Science Innovation and Modelling (MaSIM) Research Focus Area, Faculty of Natural and Agricultural Sciences, North-West University, Mafikeng Campus,
Private Bag X2046, Mmabatho 2735, South Africa
Department of Chemistry, School of Physical and Chemical Sciences, Faculty of Natural and Agricultural Sciences, North-West University, Mafikeng Campus, Private Bag
X2046, Mmabatho 2735, South Africa

A R T I C L E I N F O A B S T R A C T

Keywords: Bismuth sulfide is one of the important compounds of bismuth that has garnered much attention due to its
Bismuth sulfide interesting properties and numerous applications. The structural orientation of bismuth sulfide and the char­
Properties acterization techniques have been highlighted. An in depth discussion were made on the various methods of
Synthetic methods
synthesizing bismuth sulfide including chemical, sol–gel, deposition, pyrolysis, mechanical milling, microwave,
Applications
microemulsion, Bridgman and successive ionic layer and reaction methods. Its medical applications, use in
storage and generation of hydrogen, production of energy saving devices, as sensor for gas and other bio­
molecules and as photocatalyst for the removal of pollutants from the environment were presented in details.
Finally, the future perspective for studies involving bismuth sulfide were suggested.

Introduction
Bismuth sulfide (mineral bismuthinite) is a non-toxic semiconductor
which possesses a lamellar structure joined together by weak Bi-S bonds.
It is a crystalline n-type V-VI semiconductor material that belongs to the
main group metal chalcogenides of the type AV2BVI3 (A = Sb, Bi, As; B =
S, Se, Te) [1,2]. It has a band gap energy value of 1.3 eV [3,4], which is
moderate but higher than the band gap energy of other sulfides in the
similar group [5]. This band gap energy makes it a good photocatalyst
that is active in the visible range of the solar spectrum. One of the most
widely studied structural form of bismuth sulfide is the 1D nano­
structures. The anisiotropic nature of the compound is due to the pres­
ence of Bi3+ and S2− arranged one on top of the other in infinite chains,
which are directed along the [0 0 1] axis in an orthorhombic cell struc­
ture [6]. Examples of bismuth sulfide nanostructures are stars, balls,
belts, ribbons, flowers, snowflake-like, tubes, rods and wires) [7-11]
(Fig. 1). There are quantum confinement of charge carriers that is
associated with the 1D nanostructures [5].
The coefficient of absorption of bismuth sulfide is high (about 104-
105 cm− 1), which makes it a good light absorber [12]. It has good
electrical and optoelectronic properties [12].The conduction band of
bismuth sulfide consists of Bi 6p levels, which is hybridized with 3p of S-
orbitals while the valence band is made of 3p levels of sulfur with
minimal contribution from 6p levels of bismuth [13]. They are majorly
n-type due to the large value of sulfur vacancies that enable the elec­
trical conductivity of bismuth sulfide to be tunable. The carrier mobility
and electron concentration of Bi2S3 are high, and these properties is
utilized in solar cells application. When processed into the amorphous
state, it has a low defect density and this is as a result of the presence of
the dangling bonds that results from the alteration of the ordering of the
structure [14,15]. Similar to antimony selenide and sulfides, it forms
layers and generally crystallizes as orthorhombic structure [16]. The
intrinsic resistivity(ρ) of bismuth sulfide, measured at 300 k, was 105 Ω
cm [17]. The compound has a group symmetry of Pnma, density of
6.807 g/cm3, 20 atoms per unit cell and 3.99*1026 atoms per cm3 [18].
Other reported properties at 300 K, includes intrinsic carrier concen­
tration (3 × 1018 cm− 3), carrier mobility (200 cm2/Vs), electrical con­
ductivity (ranges from 10-6 to10-7 Ω− 1 cm− 1), and hole mobility (1100
cm2/Vs) [19,20]. The refractive indices (λ) of bismuth sulfide is 589.3
nm with the values of nα, nβ and nγ being 1.315,1.900 and 1.670
respectively [19]. A study on the geometry of bismuth sulfide showed
that the bismuth atoms are found in two non-similar environments with
three in a distant and four in a near planar rectangle to make seven co-
ordinate atoms of bismuth [21].There are 32 bismuth and 48 sulfur
atoms in the super cell of bismuth sulfide and there are four different
values (2.99 , 2.75, 2.69 and 2.62 Å) of S-Bi bond lengths after optimi­
zation [22]. The supercell crystal geometry of bismuth sulfide is shown
in Fig. 2.

* Corresponding author.
E-mail address: Damian.Onwudiwe@nwu.ac.za (D.C. Onwudiwe).

https://doi.org/10.1016/j.rechem.2021.100151
Received 10 March 2021; Accepted 15 June 2021
Available online 19 June 2021
2211-7156/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
T.O. Ajiboye and D.C. Onwudiwe Results in Chemistry 3 (2021) 100151

It is possible to alter the size of bismuth sulfide crystals by electron

irradiation [24]. After refinement, the lattice parameters of bismuth
sulfide quantum dots have been given as 10.7758, 11.4228 and 4.1110 Å
respectively for the a, b and c directions. However, these values have
been reported to vary without a change in chemical composition as the
annealing temperature changes and a residual anisotropic lattice strain
relaxation has been observed [25].

Methods of synthesis of bismuth sulfide

Synthesis of bismuth sulfide usually involve the use of sulfur-

releasing precursors such as thioacetamide, thiourea, thiosulphate,
hydrogen sulfide gas, elemental sulfur and sodium sulfide [2,26-28].
Crystals of bismuth sulfide are often prepared at high temperature in a
quartz vessel containing sulfur and bismuth [29]. As a result of high
energy input required for the synthesis, in addition to the pollution
problem associated with this route, other methods of synthesis have
been explored. One of such methods is the solventless method that has
been used to prepare nanofibric, nanowires and nanorods of bismuth
sulfide [30]. Another milder method is the chemical method (hydro­
thermal and solvothermal), whereby the sulfur and bismuth sources are
allowed to react under controlled temperature [29]. Bismuth sulfide has
also been prepared from single-source precursor compounds that could
undergo thermal decomposition, thereby leaving behind their respective
metal sulfides. Examples of such precursor compounds are bismuth
complexes of xanthate [26], thiourea, alkylthiolate, thiolate and
dithiocarbonates [2,30-32]. One of the advantages of single source
precursor is that they can generate bismuth sulfide with better proper­
ties compared to the ones obtained through multiple source precursors.
The single source precursor method also allows easy manipulation of the
reaction conditions, it does not require pre reactions and the use of
poisonous gases such as hydrogen sulfide is not required [33,34]. Other
reported methods used for preparing bismuth sulfide are discussed in
details in this section.
Chemical methods
This method of producing bismuth sulfide simply involves the pre­
cipitation of the compound in a controlled manner from a homogeneous
solution. It is achieved by using the precursors of bismuth and sulfur ions
with appropriate stability constant. The reaction between the two ions is
as shown in equation 1.
Fig. 2. Bi2S3 supercell crystal structure (red balls and blue balls shows the most
stable anions and cations respectively while purple and yellow balls indicate Bi
cation and S anions respectively). Reprinted with permission from [23]. Copyright
(2013), Royal Society of Chemistry. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of
this article.)
2Bi3+ (aq) + 3S2− (aq) → Bi2S3 (s) (1)
Different chemical methods including solvothermal, ionothermal
and hydrothermal methods have been used for synthesizing bismuth
sulfide. One of the differences between these methods is the solvent used
in the reaction process. Solvothermal requires the use of different sol­
vent apart from water, while hydrothermal requires the use of water.
Ionic liquids are used as solvent for the ionothermal methods.
Hydrothermal synthesis
Hydrothermal method is a method of growing crystals in solution at
high pressure and temperature, which is usually lower than 300 ◦ C. High
temperature is required because the reactants are usually insoluble at
low temperature [35,36]. The reaction is usually carried out in a Teflon
autoclave [36]. Hydrothermal method is advantageous because it is
possible to change the crystallinity and morphological properties of the
product by altering the pH, reaction time, temperature or the mixing
ratio of the reactants [37]. It is equally cheap and energy saving [36].
Hydrothermal methods of synthesizing bismuth sulfide are usually car­
ried out at a temperature that is as low as 95 ◦ C. In some procedures, the
hydrothermal method may be assisted with constant stirring [38]. This

Fig. 1. Examples of bismuth sulfide nanostructures.

2
T.O. Ajiboye and D.C. Onwudiwe Results in Chemistry 3 (2021) 100151

method has been used to synthesize bismuth sulfide nanowires, nano­
rods and nanotubes. In this synthetic approach, Na2S and Bi(NO3)3 were
the main reagents, ethanediol was used as the solvent, while CO(NH2)2
was used for the pH adjustment [39]. Thiourea has also been used as
sulfur source to synthesize different morphologies of bismuth sulfide
nanoflowers and nanorods in a hydrothermal process. The reaction was
carried out by using thiourea and hydrated bismuth nitrate in ratio 3:2 at
180 ◦ C, with the addition of nitric acid with continuous stirring [40]. In
a bid to improving the efficiency of hydrothermal process for bismuth
sulfide fabrication, some compounds have been introduced in order to
assist the hydrothermal process. For example, tartaric acid was used to
assist hydrothermal process to synthesize nanorods of bismuth sulfides
[41]. Mercaptosuccinic acid was also used as sulfur source in the hy­
drothermal synthesis of bismuth sulfide and the procedure involved the
use of ethylenediaminetetraacetic acid disodium salt with bismuth ni­
trate [42].
Solvothermal synthesis
Solvothermal method is similar to hydrothermal as they both require
similar conditions, but organic solvents are used in place of water.
Example of such organic solvents are octadecene, decalin and toluene
[36]. Different sulfur-containing precursors have been used for synthe­
sizing bismuth sulfide through solvothermal methods. Bismuth sulfide
nanowire has been prepared by using a mixture of bismuth chloride and
cetyltrimethylammonium bromide (CTAB) used as surfactants [43]. A
change in the solvothermal reaction time was reported to affect the
morphological structure of the synthesized bismuth sulfide [43].
Nanosheets, nanorods and nanodots of bismuth sulfide were obtained by
varying the reaction conditions during solvothermal process [44]. Other
examples involving solvothermal synthesis of bismuth sulfide are shown
in Table 1. Complexes such as bismuth(III)thiosemicarbazide and bis­
muth(III) thiourea have been reported as precursors for bismuth sulfide
under solvothermal process [45]. These precursor complexes are first
prepared from the bismuth salt in the first step and this is followed by
heating the precursor complex at high temperature in the appropriate
solvent as shown in Fig. 3.
Ionothermal synthesis
Ionothermal synthesis is another chemical synthesis route, which
utilizes ionic liquids as solvents instead of water used in hydrothermal
method or organic solvents used in solvothermal method. The use of
ionic liquid is preferred because it could be used to generate particles of
smaller diameter since there is high nucleation rate [36,57]. It is also
possible to extend the hydrogen bond system, thereby results in a well-
ordered nanostructures [58]. The nucleation rate is high because the
interfacial surface tension is low when compared to the organic solvent
[36]. Examples of ionic liquids are 1-decyl-3- methylimidazolium bis
(trifluoro- methylsulfonyl) imide, 1-Hexadecyl-3-methylimidazolium-
bromide and 1- butyl-3-methylimidazolium hexafluorophosphate. This
method has also been used to fabricate bismuth sulfide. In some cases,
bismuth containing precursors such as bismuth di-n-octyl-
dithiophosphate were dissolved in these ionic solvents and then ther­
molysed. For instance, Wang et.al. [58] used ionothermal method to
fabricate both nanorods and nanoflowers of bismuth sulfide by dis­
solving bismuth di-n-octyl-dithiophosphate. Hydrated bismuth sulfide
was also used along with ionic liquid thioacetamide and distilled water
used to prepare bismuth sulfide at room temperature [59].
Sol-gel method
The use of sol–gel for synthesis purpose usually commence with the
initial solution stage, where solid particles form colloidal suspension,
followed by the gelation stage involving the formation of interconnected
network by the solid phase [36,60]. The properties of the resulting
materials could be altered by changing the additives (such as surfactants
and catalysts) used for the synthesis, using different solvent and/or
initial precursors, varying the time for gelation, changing the pH or
temperature of the reaction [60,61]. Also, different morphologies of the
products could be obtained by subjecting the precursors to be used for
sol–gel synthesis to different approaches (such as heating, electro­
spinning, deposition, and spin-coating) [36,61] as shown in Fig. 4. The
use of sol–gel as a chemical synthetic method for bismuth sulfide has
been reported [62]. In one instance, sodium sulfide was used as the
source of sulfur and trivalent bismuth was stabilized in water by using
triethanolamine and gelatine was utilized as the capping agent. The
reaction was carried out in neutral condition [62].
Deposition methods
Mass production of bismuth sulfide could be achieved via the
deposition methods. The methods are not only environmentally-friendly
but are also cheap and simple [63]. In addition, it allows the control of
the morphology of bismuth sulfide by controlling the temperature of the
substrate, gas flow rate into the process system, time of deposition,
solvent used as well as the concentration of the solution. In some cases,
deposition methods may require the use of precursor(s) [63,64].
Chemical vapour and chemical bath deposition
Crystalline bismuth sulfide could be obtained by chemical deposition
on a glass substrate at a relatively low temperature, which ranges

Table 1
Solvothermal synthesis of bismuth sulfide using different precursors and under various conditions.
Precursors Other reactants Atmosphere Temperature and time Solvent used Ref.

hexamethyldisilathiane Oleic acid, 1-octadecene and Argon atm. 90 ◦ C for 16 h and then heated up to Toluene/methanol [47]
bismuth(III) acetate 170 ◦ C
elemental S 1-octadecene Argon atm. 100 ◦ C for 20 min followed by 180 ◦ C for 1 Toluene [48]
h
Solution of sulfur/ oleylamine Oleic acid, 1-octadecene and Vacuum then 90 ◦ C in vacuum for 1 h and at 170 ◦ C in Toluene/ethanol [49]
bismuth(III) acetate argon atm. argon atmosphere.
Solution of sulfur Bismuth acetate and Oleylamine Argon atm. 130 ◦ C for 0.5 h and then kept at the same Cold toluene [50]
temperature for 0.5 h
Hexamethyldisilathiane Bismuth acetate, oleic acid, 1- – 100 ◦ C overnight, then raised to 170 ◦ C Methanol/toluene [51]
Octadecene and finally lowered to 100 ◦ C after 2 h.
Sodium diethyldithiocar-bamate Ethylene glycol(or triethanolamine – Maintained 190 ◦ C for 3 h Ethanol [52]
trihydrate for nanoflower)
elemental sulfur in oleylamine Bismuth acetate, oleic acid Argon Heated at 160 C for 1 h.
◦
Chloroform and 2-propanol [53]
octadecene
2-aminocyclopentene-1- – Room conditions 140 ◦ C for 5 h Dimethylformamide [54]
dithiocarboxylic acid
Thioacetamide Hydrated bismuth nitrate, tin Room conditions 180 ◦ C for 12 h. Deionized water and [55]
chloride and indium chloride absolute ethanol
Thiourea Hydrated bismuth nitrate Room conditions 100 ◦ C for 20 h Propanol [56]

3
T.O. Ajiboye and D.C. Onwudiwe
Fig. 3. Solvothermal synthesis of Bi2S3. Reprinted with permission from [46].Copyright (2017), John Wiley and Sons.
between 250 and 380 ◦ C. At a temperature lower than 250 ◦ C (such as
95–250 ◦ C), thin films are formed [65]. Chemical bath deposition
method has also been used for synthesizing bismuth sulfide and this
involved the deposition of thioacetamide, ethylenediamine tetraacetic
acid and bismuth nitrate unto a glass substrate coated with tin oxide and
fluorine. Unlike chemical vapour deposition, that was carried out at a
relatively high temperature, deposition temperature of chemical bath is
usually lower than 100 ◦ C [7]. Although, they both require glass sub­
strate for the deposition. One of the studies in which bismuth sulfide thin
films was produced through chemical bath deposition involved the use
of thioacetamide (as sulfur source), ethylenediamine tetraacetic acid
(EDTA) (as the complexing agent), and bismuth nitrate (as the bismuth
source) [66]. Chemical bath deposition method was also used to incor­
porate bismuth sulfide into titanium oxide nanotubes [67]. It has also
been used to fabricate InBiS3-In2S3-Bi2S3, a ternary composite [68].
Another useful form of deposition are the vacuum and non-vacuum
based deposition. Out of these two, vacuum method is important for
preparing Bi2S3 film with high quality and properties, which are
required for the applications of films [69].
Electrochemical deposition
Electrochemical deposition method has also been used to prepare
bismuth sulfide [70]. This method was used to fabricate nanocomposite
of bismuth sulfide and titanium oxide nano-arrays [71]. It was also used
to deposit bismuth sulfide quantum dots by using sodium citrate, sodium
thiosulphate and bismuth nitrate. The reference electrode used was
calomel electrode, platinum sheet was used as the counter electrode,
while the bismuth sulfide quantum dots was used as the working elec­
trode. The system was composed of three electrodes [72]. A special type
of electrochemical deposition is galvanostatic co-deposition (Fig. 5a),
whereby bismuth sulfide films were complexed with bismuth selenides
and was deposited on the glass substrate. The galvanostatic co-
deposition method is a cheap and simple method [73].This method
was also used to deposit bismuth sulfide on cadmium sulfide function­
alized with tin oxide and fluorine. The co-deposition was achieved by
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Results in Chemistry 3 (2021) 100151
using triethanol amine and bismuth nitrate as the cationic precursor
with current density of 0.3 mA cm− 2 [74]. Another electrochemical
deposition technique is pulse plating whereby bismuth sulfides are
deposited on fluorine-tin-oxide (FTO) glass substrates (Fig. 5b). The
clean FTO is used as anode during the electroplating process [75].
Atomic layer deposition
The ability to limit the mechanism of growth, generation of products
that is not only uniform but pin hole-free and good coatings on other
semiconductors made atomic layer deposition to be one of the desired
methods for fabricating bismuth sulfide [76]. Mahuli et al. [77] used
quartz crystal-built hot-wall reactor to obtain pure form of poly­
crystalline bismuth sulfide from hydrogen sulfide and bismuth(III) bis
(2,2,6,6-tetramethylheptane-3,5-dionate). This was carried out at the
atomic layer deposition temperature close to 250 ◦ C. Bismuth sulfide
and antimony sulfide quantum dots were also deposited on titanium
oxide nanorods by using atomic layer deposition method [78].
Evaporation deposition
Deposition of polycrystalline thin film of bismuth sulfide from a
single source has been achieved at low vapour phase temperature. This
was accomplished by using the mixture of elemental sulfur and bismuth,
but has also been prepared by using precipitates of bismuth sulfide
[79,80]. The use of bismuth sulfide precipitate for evaporation deposi­
tion is advantageous because it leads to highly polycrystalline bismuth
sulfide thin film. The deposition process is achieved at comparatively
lower substrate temperature and lower vacuum pressure. Hence, the
deposition will not require further annealing [79,81].
Physical deposition
The physical deposition technique is also used to deposit thin film on
substrates. One of the common physical deposition methods is the
pulsed layer deposition, which allows direct contacts of the atoms of the
nanoparticles and the substrates [82]. It is advantageous because it is
relatively cheap, fast and simple with better reproducibility when
T.O. Ajiboye and D.C. Onwudiwe
Fig. 4. Sol-gel method of synthesis of bismuth-based nanoparticles and the different morphologies obtained. Reproduced from [36]. Royal Society of Chemistry
(2020). Open Access under Creative Common.
compared to the chemical techniques [82]. The use of physical deposi­
tion method for fabricating bismuth sulfide has been reported [83].
Hot wall deposition
This method involves the use of substrates placed along with poly­
crystalline bismuth sulfide inside quartz tubes having a cylindrical
shape. Three-zone temperature is then used to heat the tube to a tem­
perature that was slightly lower than the melting point of bismuth sul­
fide (usually 470 ◦ C). Bismuth sulfide was deposited on the substrates
that was inside the quartz tube [84]. The deposition of bismuth sulfide
wires was achieved through hot wall deposition on silicon. It was
discovered that silicon was one of the suitable substrate for bismuth
sulfide nanowires at high temperature, since the presence of silicon
prevented the formation of undesirable substituted products [84].
Spin coating deposition
Spin coating deposition involves the preparation of thin film of bis­
muth sulfide by using rotating spin coater. Bismuth sulfide has been
prepared via this method by using a solution of chloroform and bismuth
complex introduced into the spin coater under atmospheric pressure for
less than a minute. This was subsequently followed by air-drying on hot
plate at 70 ◦ C for 5 min. After this procedure, it was introduced into
argon-gas containing reaction tube before final annealing to obtain
bismuth sulfide thin films [64]. In some cases, the crystals were obtained
by blowing nitrogen gas. Optimization of the time for blowing the gas or
air and the rate of spinning are necessary to get bismuth sulfide with
uniform morphology [85]. The process involved in spin-coating has
been summarized and presented in Fig. 6.
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Results in Chemistry 3 (2021) 100151
Thermal evaporation
This method of synthesizing bismuth sulfide involves the subjection
of the sulfur-releasing and bismuth-containing compounds in the solvent
matrix to a temperature that is usually more than 100 ◦ C in an autoclave
[86,87]. In a typically process, dilute acetic acid was used as the solvent
for dissolving Bi(NO3)3⋅5H2O and C2H5NS. Both PVP and H2NCONH2
were introduced into the solution before it was heated for 24 h at 160 ◦ C
inside the Teflon-lined autoclave [86]. Bismuth sulfide powder was also
used to deposit pure bismuth sulfide powder as thin film at a tempera­
ture as high as 600 ◦ C [15]. Kachari and Rahman reported the synthesis
of bismuth sulfide using two different tantalum boats which were used
to co-evaporate sulfur and bismuth at room temperature [69]. The
thermal co-evaporation has also been carried out by using tungsten boat
as the source instead of using tantalum and alumina boats and this was
followed by inter-diffusion of bismuth and sulfur during the heat
treatment in the quartz tube [88,89].
Sputtering
Sputtering technique involves the use of vacuum pump, a source of
radiofrequency and a chamber for deposition. Inert gas (usually argon)
are released at lower pressure into the target, which is usually on top of
the substrate. The radiofrequency generates plasma, which ionizes the
inert gas and the ionized gas bombards the target to release atoms [90].
There are different sputtering set-ups, but the common one is cylindrical
in shape and made from stainless steel with pumping, degassing and
heating components. It works by depositing bismuth sulfide via direct
current [91]. Bismuth sulfide and SnS have been used as targets for the
T.O. Ajiboye and D.C. Onwudiwe Results in Chemistry 3 (2021) 100151

Fig. 5. (a): Galvanostatic co-deposition. Reprinted from [74]. Copyright (2016), with permission from Elsevier. (b) Schematic representation of the synthesis of Bi2S3 by
pulse-plating method. Reproduced from [75]. Royal Society of Chemistry (2020). Open access under Creative Common.

Fig. 6. Schemes representation of the different stages (a-e) in spin-coating deposition proess. Reproduced with permission from [85]. Copyright (2019), John Wiley
and Sons.

sputter, which led to their deposition. The deposition was carried out
after these binary sulfides were prepared via uniaxial hot pressing. The
thickness of the deposition was varied by changing the temperature of
the substrate and sputter parameters [92].
Pyrolysis
It is a method that generally requires a compressor, nebulizer (or
atomizer) and a component for releasing the reactants (such as spray
gun). Sulfur and bismuth precursors were used for the synthesis of bis­
muth sulfide by pyrolysis and the two precursors were mixed thoroughly

6
T.O. Ajiboye and D.C. Onwudiwe
using magnetic stirrer to obtain homogenous solution. It also requires
the use of clean substrate that are preheated to a certain substrate
temperature [93]. Examples of pyrolysis methods are spray pyrolysis,
microprocessor-based spray pyrolysis, improved spray pyrolysis, corona
spray pyrolysis, electrostatic spray pyrolysis and ultrasonic spray py­
rolysis. All these are atomization techniques and could be used to control
both the distribution and size of the droplets over the hot substrate [27].
Spray pyrolysis
Preparation of bismuth sulfide by spray pyrolysis method involves
the spraying of solution containing both bismuth and sulfur onto a
heated substrate. As soon as the sprayed solution comes in contact with
the heated surface, the precursors decompose to form product crystal­
lites or single crystallite of bismuth sulfide. A pyrolytic break down
occurs as a result of the heat, which is then followed by the recombi­
nation of bismuth and sulfide. Any volatile by-product formed during
this process will escape as a result of the high temperature of the heated
surface [90]. This method has attracted attention because it is simple,
does not require vacuum, cheap, fast and could be adopted for com­
mercial purposes [94]. The set-up for spray pyrolysis requires a pre­
cursor solvent, oxidizer dispersion gas, flame source, thermocouple,
section for thermophoretic sampling with subsequent transmission
electron microscope analysis(TS-TEM), Phase-Doppler anemometry
(PDA) and camera coupled with optical emission spectroscopy (OES)/
laser sheet (LS). The schematic diagram showing the connection and
arrangement of these parts are shown in Fig. 7. In some cases, there are
modification of the spray pyrolysis and one of such is the use of ultra­
sonic spray pyrolysis for preparing bismuth sulfide. This technique was
used to prepare nanocrystalline bismuth sulfide from thiourea and bis­
muth nitrate at a relatively low temperature [27].
Corona spray pyrolysis
Ordinary spray pyrolysis usually suffers from low efficiency of
deposition (the ratio of atoms sprayed is far more than the ratio that is
deposited) resulting in poor atom economy. Corona spray pyrolysis was
designed to overcome this challenge. The method has been used to
prepare bismuth sulfide and was found to also improve the optical and
Fig. 7. Schematic set-up of flame spray pyrolysis. Reproduced from [95]. John Wiley and Sons (2019). Open access under Creative Common.
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Results in Chemistry 3 (2021) 100151
electrical properties of the bismuth sulfide produced. This techniques
require the use of aerosol-loaded corona discharge and there is electric
field between the substrate [96].
Ultrasonic spray pyrolysis
Just like the other form of spray pyrolysis, the ultrasonic spray py­
rolysis requires four major steps: the generation of precursor solution
drops; evaporative reduction of the size of the drop; precursor conver­
sion and formation of solid particles [97,98]. The demerit of ultrasonic
spray pyrolysis is low throughput, but it is a method of choice compared
to other form of pyrolysis. This is due to the generation of products with
narrow particle size distribution and decreasing the size of the drop is
possible by raising the ultrasonic frequency [97,99]. Mahmoud et al.,
used spray pyrolysis to prepare bismuth sulfide thin films and the tem­
perature of the substrates as well as molarity of the solution used were
found to affect the optical, electrical and structural properties of the
bismuth sulfide obtained [27,100]. Asynchronous-pulse modified form
of ultrasonic spray pyrolysis has also been used to prepare rod-like and
nanocrystalline thin-films Bi2S3 by using thiourea and bismuth nitrate as
sulfur and bismuth precursors respectively [27].
Solution pyrolysis
This method of preparing bismuth sulfide involves the preparation of
bismuth complex, e.g bismuth dithiocarbamate, followed by spreading
of the prepared complex on a glass substrate and introduction of
appropriate solvent (usually chloroform or p-xylene, depending on the
substituents on the dithiocarbamate).The mixture is usually heated to
100 ◦ C for 1 h, followed by cooling to room temperature and after which
the heating was carried out for 1 h in the temperature range 250 to
350 ◦ C [101].
Mechanical milling
This is one of the easiest method of preparing bismuth sulfide
nanocrystals, and could be used with other methods to improve the
properties of bismuth sulfide produced. It involves the high speed
rotation of steel ball with the reactants under inert atmosphere. The size
T.O. Ajiboye and D.C. Onwudiwe
of the particle size obtained at the end of the milling largely depend on
the size of the steel ball used. Large steel ball will lead to generation of
bismuth sulfide with smaller size [90]. In some cases, surfactants are
used to assist the milling process and the product obtained depends on
the factors listed [102] in Fig. 8.
Bismuth sulfide has been prepared by mixing sulfur powder with
bismuth in ratio of 3:2 respectively. These reactants were introduced
into a vial made from steel and stainless-steel balls whose weight were
about 20 folds more than the weight of the reactant mixture were added.
The vial was subjected to mechanical milling at high energy and 600
rpm for half of a day after it has been placed in glove box filled with
argon, to yield bismuth sulfide powder [103]. The combination of
electric discharge and mechanical milling as a method for synthesizing
bismuth sulfide has also been reported by Calka et al. [104]. It requires
the mixing of sulfur and bismuth in a stoichiometric amount under an
inert atmosphere. This was followed by vibrational ball milling with
electric discharge assistance. The electric discharge initiates chemical
reactivity between electrodes in the set-up while the vibration causes the
mixing of the contents.
Microwave-assisted method
This method is not only fast and simple, but it is highly efficient for
synthesizing bismuth sulfide nanoparticle in solution [3]. It has been
used to prepare bismuth sulfide nanowhisker by reacting bismuth nitrate
and thiourea in the system containing poly (N-vinyl-2-pyrrolidone) [3].
The formation of bismuth sulfide has also been achieved under micro­
wave by using thioacetamide and bismuth nitrate according to the
following reaction (Equations (2)-(4)) [40]:
Bi(NO3)3 + H2O → BiONO3 + 2HNO3 (2)
CH3CSNH2 + H2O → CH3CONH2 + H2S (3)
3H2S + 2BiONO3 → Bi2S3 + 2HNO3 + 2H2O (4)
Propylene glycol and ethylene glycol played important role in the
synthesis of bismuth sulfide nanorods. Apart from the role of solvent,
they assist in stabilizing and complexing the nanoparticles at the sur­
faces [29].The bismuth sulfide was also capped by these polyols through
Fig. 8. Factors affecting product obtained through surfactants-assisted mechanical milling.
8
Results in Chemistry 3 (2021) 100151
the hydrogen bond formed by their hydroxyl group. Also, the formation
of bismuth sulfide nanorod under microwave could be attributed to soft
template role played by these polyols [40]. The microwave method is
efficient, simple and fast. Compared to other conventional methods,
microwave synthesis generates pure, fast, small-sized particles with
narrow size distribution [40]. In addition to the use of dual precursors
under microwave synthesis, the decomposition of single source precur­
sor (containing both bismuth and sulfur) has been reported for the
synthesis of bismuth sulfide nanorods. Onwudiwe reported a simple
microwave irradiation of bismuth dithiocarbamate complex in ethylene
glycol and dimethyl formamide solvents, which resulted into bismuth
sulfide nanorods of different dimensions [105].
Rapid polyol process
The use of polyol as an independent method for fabricating different
morphologies of bismuth sulfide has been reported apart from its use to
assist microwave method. For instance, nanorods of bismuth sulfide was
fabricated by this method using ethylene glycol as the polyol with
thiourea and bismuth nitrate as the sulfur and bismuth sources respec­
tively. The reaction involved the formation of bismuth-thiourea com­
plexes in the first stage, then followed with a high temperature
decomposition of the complex [106]. Polyol process is a novel efficient,
simple and fast method compared to some other synthetic methods
[106].
Sonochemical method
The use of ultrasound is now a powerful tool in synthetic chemistry
and it has been used to fabricate novel materials that possess unique
features. Sonochemical techniques produces materials with higher sur­
face area and reduced particle size compared to some other synthetic
methods [107]. In Sonochemical method, solutions are subjected to
powerful ultrasound radiation leading to the collapse of the bubbles in
the solution via acoustic field. During this process, high pressure and
high temperature are generated inside these bubbles [107,108]. This
method has been adopted to synthesize various bismuth sulfide nano­
structures [109]. For example, Wang et al. [109] used sonochemical
T.O. Ajiboye and D.C. Onwudiwe
method to prepare bismuth sulfide nanorods by using sodium thiosul­
fate, bismuth nitrate and different complexing agents. Some of the
complexing agents used are sodium tartrate, triethanolamine, thio­
acetamide and ethylenediamine tetraacetic acid. The length and diam­
eter of the resulting bismuth sulfide nanorods were found to vary with
the type of complexing agent used in the synthesis process. One of the
merits of sonochemical method are the high purities, narrow size dis­
tributions and uniform shapes of the materials synthesized through this
method. In addition, it allows the reaction conditions and the reaction
rates to be varied [107-109].
Microemulsion method
This method involves the use of colloidal nanoparticles of oil in water
or water in oil, where surfactant films are used as stabilizer. The stable
dispersion that is formed could be used as nano-reactors to prepare
bismuth sulfide. The properties of the bismuth sulfide to be formed could
be changed by controlling the parameters used to form this nanoreactors
[110]. The droplet size of the surfactants, film flexibility of the surfac­
tants, relative amount of the reactants used as well as the concentration
of these reactants determine the size of the nanoparticles that is
obtainable through microemulsion method [110-113]. The bismuth
sulfide used to coat PEGylated chitosan in a study by Wang et al., was
fabricated by using microemulsion method [114]. Bismuth sulfide
nanorods and nanospheres have also been prepared by microemulsion
method in a water–oil colloidal solution made with water, n-pentanol,
Triton X-100 and cyclohexane as the medium of reaction [115]. Apart
from the fact that the particles obtained via this microemulsion method
are in the nano range, the bismuth sulfide obtained are usually crys­
talline [115].
Successive ionic layer adsorption and reaction method (SILAR)
Two beakers are required for the two reaction solutions used in the
SILAR method. One of the beakers contains the solution of one of the
anions, while the second beaker contains the solution of one of the
cations [116]. The method is usually employed when bismuth sulfide is
Fig. 9. Synthesis of Bi2S3 through improved SILAR method. Reprinted with permission from [119]. Copyright (2017), Elsevier.
9
Results in Chemistry 3 (2021) 100151
to be deposited on a material. The material is first dipped into the so­
lution containing bismuth ions for a while; it is then properly washed
and dried after which it is dipped into the solution containing the sulfide
ions to complete the SILAR cycle [116,117]. The number of SILAR cycles
determines the amount of bismuth sulfide that would be deposited on
the material. Compared to chemical deposition method, SILAR method
is cheap and simple and could be used with other synthetic methods such
as ultrasound method [116,117]. This method (assisted by ultrasound)
was used to deposit bismuth sulfide on titanium oxide that was used for
various photocatalytic applications [117]. It has also been used at room
temperature to deposit bismuth sulfide nanoparticles on fluorine-
decorated SnO2 glass substrate [118]. Wang et al. [119] modified the
SILAR method by using methoxyethanol as solvent instead of acetone
having low solubility and used it for synthesizing Bi2S3. In this synthesis,
Na2S methanol solution was used with bismuth nitrate in 2-methoxye­
thanol solution and then deposited on a glass substrate before anneal­
ing in Ar at 200 ◦ C. The entire processes were carried out for 30
complete SILAR cycles and the synthesized bismuth sulfide showed an
improved photocurrent density. The process of this improved SILAR
synthesis has been summarized in Fig. 9.
Bridgman method
The growth of bismuth sulfide crystals could also be achieved by
using Bridgman method (also called Bridgman–Stackbarger technique).
This method relies on the relative movement of the furnace and the
crucible as well as temperature gradient between the set-up [120]. The
temperature gradient of the Bridgman furnace is measured by using
thermocouple. Example of Bridgman crystal growth set-up is shown in
Fig. 10. Shaban et al. [121] used the modified Bridgman method to
synthesize bismuth sulfide. The synthesis was achieved in the charged
ampoule that was placed inside a tube furnace that has three zones with
the temperature at the middle set to 1048 K. This temperature was
chosen because it corresponds to the temperature of crystallization of
bismuth sulfide. The gradual solidification of bismuth sulfide was ach­
ieved when it reached the third zone. Modified Bridgman–Stackbarger
technique has also been used for synthesizing bismuth sulfide. In the
T.O. Ajiboye and D.C. Onwudiwe
Fig. 10. Bridgman method of crystal growth (a)melting and solidification chambers (b)lateral thermocouple with solidification mold. Reprinted with permission
from [122]. Published by Springer Nature, Copyright (2010).
modified method, the charged ampoule was made to move with slow
motion by reducing the speed of the motor and the starting materials
were directly heated [121].
Advantages and disadvantages of the different synthetic methods
of Bi2S3
Each of the methods discussed have their advantages and disad­
vantages, and these have been summarized in Table 2. Some of these
methods could lead to the generation of other secondary crystalline
phases as impurities. Example of such secondary phases are bismuth
oxide, crystalline sulfur and crystalline bismuth. The amount of this
secondary crystalline phase impurities formed could be minimized by
optimizing the reaction conditions such as the time and temperature of
reaction [123]. When SILAR method is used, the solubility of the salts
used for the preparation is very important because if bismuth salt is not
totally soluble, it could reduce the amount of bismuth cation in the
system thereby reducing the yield of Bi2S3.The insoluble bismuth salt
could also be a source of impurities for the obtained product. To mini­
mize this, glycerol and methanol are usually used as solvent for bismuth
sulfide due to the presence of –OH through which bismuth could form
metal complex in these solvents [124].
Characterization of bismuth sulfide
Gravimetric and volumetric methods of chemical analysis could be
used to determine the chemical composition of bismuth sulfide [106].
The optical and morphological properties of bismuth sulfide could be
obtained from other analytical tools. One of the analytical tools that is
used for characterizing bismuth sulfide is powdered x-ray diffraction
(XRD) (Fig. 11a). The powdered XRD technique is a vital analytical
measurement that offers information on the crystallinity and structure of
bismuth sulfide. The crystal structure and composition of Bi2S3 are
usually analyzed through powdered XRD diffraction with Cu-Kα radia­
tion and and cobalt based X–ray source [137]. Generally, the intensity
and the integrity of the crystalline peaks obtained in the XRD pattern
improves with increase in the time of irradiation and calcination
[3,138,139]. Typically, all the peaks are usually indexed as ortho­
rhombic phase and the prominent peaks are obtained at scattering an­
gles (2θ) of approximately 32◦ , 28.5◦ and 25◦ . These three peaks are
respectively indexed to (2 2 1), (2 1 1) and (1 3 0) planes [139].
Depending on the synthesis route adopted, impurity peaks such as
10
Results in Chemistry 3 (2021) 100151
bismuth oxide or bismuth metal are usually found in the XRD pattern.
The broadness of the peaks is used to determine the extent of size
reduction and if within the nanometer scale. The diffraction pattern of
pure Bi2S3 tallies with diffraction data of Bi2S3 (JCPDS No. 170320) with
Pbnm space group [140]. If not in its pure phase, the peak at 26.7◦ may
sometimes be observed in the pattern, which is attributed to the pres­
ence of BiS2 [141].
Energy Dispersive X-Ray Spectroscopy (EDX) is used to confirm the
chemical composition of bismuth sulfide. A correct EDX spectra for
bismuth sulfide shows the ratio of bismuth-to-sulfur as 2:3, which is the
stoichiometric ratio of the two elements [142]. In some cases, the EDX
spectrum may show the ratio of some other elements that were not part
of the composition of the prepared sample as shown in Fig. 11b. For
example, elements such as the atmospheric oxygen, carbon and copper
sometimes appear in the EDX spectrum, and they emanate from the test
grid used for the measurement [142].
To properly understand the crystal orientation and identify the lat­
tice defects of bismuth sulfide, Raman spectroscopy (Fig. 11c) is the
technique of interest [8]. It is also useful in investigating the concen­
tration of dopants that may be introduced into Bi2S3 [8]. In a typical
Raman spectrum of Bi2S3, there are five vibrational peaks around 965,
606, 422, 306 and 260 cm− 1; and these are the Raman band used for
identifying crystalline form of Bi2S3 [5,41]. These vibrational peaks are
from different wavelength of laser excitation. It has also been discovered
that both bulk Bi2S3 and nanosheet Bi2S3 have similar signals [143]. The
Raman peaks of bismuth sulfide nanoflowers and nanorods reported by
Yu and Cao also displayed similar peak but the peak intensity of the
nanoflower are often higher[8].The nanorod of Bi2S3 usually absorb
around 262 nm in the UV–vis absorption spectrum which shows that its
band gap is 2.74 eV [144]. X-ray photoelectron spectroscopy (XPS) is
used to determine the chemical composition, oxidation states and
quality of the sample [145]. The binding energy of bismuth sulfide are
224.9–235.6 eV, 158.0–171.6 eV and 163.2–166.2 eV for S (2s), Bi (4f7/
2) and Bi (4f5/2) respectively [138,142,146].The peaks for Bi (4f7/2) and
Bi (4f5/2) are strong and the ratio of sulfur-to-bismuth is approximately
3:2 as shown in Fig. 11(d-f) [146]. In some cases, 284.8 eV for C 1 s as
well as 531 eV for O 1 s could be observed, and could be as a result of the
adsorption of molecules of gases (such as O2, CO2 or H2O) by the powder
samples from the atmosphere [147].
The analysis of nitrogen adsorption–desorption isotherms is a tech­
nique generally used to determine the pore-network dimensions, struc­
ture and surface area of powdered materials. The estimation of the pore-
T.O. Ajiboye and D.C. Onwudiwe Results in Chemistry 3 (2021) 100151

Table 2 Table 2 (continued )

Advantages and disadvantages of Bi2S3 synthetic methods. Synthesis Advantages Disadvantages Ref.
Synthesis Advantages Disadvantages Ref. method
method
polar metals in the
SILAR It can be used for large Its performance is [118,125] system.
scale preparation; influenced by Microwave Short time of reaction; Expensive; Not [136]
cheap; requires low precursor solution Higher yield; easy to suitable for
temperature and its chosen handle and reproduced. monitoring reaction
procedure is simple; progress; Not easy to
thickness control is scale up.
possible
Chemical Large quality crystals High cost of the [126]
(hydrothermal, could be obtained equipments network structure of Bi2S3 is based on the physical adsorp­
solvothermal required; high tion–desorption analyses, and also reveals some key parameters such as
and percentage of
the amount of the pores, their size distribution, and also the perme­
ionothermal) impurities compared
to other methods ability of the nanometric powders [148,149]. Jiao et al [150]. reported
such as sputtering. the nitrogen adsorption–desorption isotherm of bismuth sulfide which
Sol-gel Simple, economical and Contraction usually [126,127] showed type IV isotherm. The isotherm was with the loop of hysteresis,
efficient method to occur during which showed that it possessed a mesoporous structure (relative pres­
produce high quality processing; Organic
coverage; It can be solvent used may be
sure within 0.6–1.0). In addition, the BET surface area (8.2 m2g− 1) and
carried out at a low toxic; It takes longer the pore size (10.0 nm) of the bismuth sulfide were also derived from the
sintering temperature time. isotherm.
of 200–600 ◦ C The morphology, crystallographic and structure of bismuth sulfide
Deposition Easier and simple to Low yield is gotten; [128]
could be further explored by transmission electron microscopy (TEM)
form thin films. it is an expensive
method analysis. Scanning electron microscopy (SEM) offers information on the
Thermal It has minimal effect on Contamination from [129] external morphology of the Bi2S3. Example of SEM image obtained from
evaporation the physical properties released gases; Bi2S3 is shown in Fig. 12b. High resolution scanning electron microscopy
of the product; deposition may be (HR-SEM) has been used to explore the morphological behavior of Bi2S3
thickness of the film is uneven
controllable;
nanopowder with change in temperature. The study established that as
comparatively cheap the temperature of reaction increased, the particle size of bismuth sul­
and simple. fide also increased. Energy dispersive spectroscopy (EDAX) could be
Sputtering Economical; less Nature of the sputter [128] used to confirm the presence of S and Bi atoms [151].
impurities compared to influence the
Electrochemical Impedance Spectroscopy (EIS) is used to charac­
chemical method properties of the
product obtained. terize bismuth sulfide in order to determine its efficiency of separation,
Mechanical Useful for large scale It may lead to [128,130] ion diffusion resistance and charge transfer ability. The charge transfers
milling production; improved grinding of resistance obtained from EIS value for pure Bi2S3 electrode is 258 Ω
product could be microstructures; [152]. The photoluminescence studies (PL) is used to study the electron-
gotten. steel ball may
contaminate;
hole recombination fate in the nanostructure of bismuth sulfide [142].
elongated milling PL of Bi2S3 showed one sharp peak around 340 nm (3.64 eV) and
time required; another broad peak around 661 nm (1.87 eV). While the sharp peak is
Consumption of high ascribed to the band edge emission, the broad peak is as a result of the
energy
surface defects [153]. The presence of Bi2S3 in materials could also be
Pyrolysis Relatively simple and High cost of [128]
cheap; Control of pyrolysis reactors confirmed by studying the spectra obtained from EDXRF as shown in
particle size is possible. Fig. 12a. The peaks at 15.25, 13.02, 10.84 and 9.42 keV are assigned Bi
Brigdman Simple to operate; The crystal being in [131,132] Lγ1, Bi Lβ1, Bi Lα1 and Bi Ll respectively. There are four peaks that
Several crystals could contact with the wall overlapped around 2.4 keV. These peaks are Bi Mα2 and Bi Mα1 at 2.42
be obtained in a single of the crucible can
cycle of crystal growth; experience
keV, S Kβ at 2.46 keV and the last one is S Kα at 2.31 keV [154]. To
Since low temperature mechanical stress; understand how the sulfur and bismuth are distributed in Bi2S3,
is used, obtained high level of elemental mapping images could be used along with the SEM images as
crystals are crack-free. impurity. shown in Fig. 12c-d.
Microemulsion Microemulsion High volume of [126,133]
The thermal stability of Bi2S3 could be studied using thermogravi­
formation can be surface-active agent
reversed; energy is needed; metric analysis, which is a technique used to determine the changes in
contribution is not the weight of materials as its temperature increased. The decomposition
required during of Bi2S3 usually occur at a temperature ranging from 480 to 800 ◦ C with
synthesis; usually the mass loss of around 7% as shown in Fig. 13 [155].
produce
The material used for the preparation of Bi2S3 and method of prep­
thermodynamically
stable product. aration could influence the pattern of decomposition obtained. In the
Sonochemical Minimal number of It usually give low [126,134] TGA/DTG/DTA pattern obtained by Patil et al. [156] from the bismuth
reaction steps; It does yield compared to sulphide synthesized via single diffusion method, two stages of decom­
not require the use of other methods
position were identified. The weight loss up to 37 ◦ C was not significant
additional additives;
Shorter reaction time. which simply implies that bismuth sulfide was thermally stable up to
Rapid Polyol Simple metal salts may Polyol has restricted [135] this temperature. However, beyond 37 ◦ C, bismuth sulfide became un­
be used; cost effective. reducing power; stable to thermal energy. The first stage of decomposition in the range
polar polyol may not 37 to 102 ◦ C corresponded to 12.130% weight loss and it was attributed
sufficiently stabilize
to the loss of H2O and SO2. The second stage was between 102 and
947 ◦ C. In this stage, about 14.984% weight loss was obtained instead of
the calculated 18.934%. The lower value of weight loss could be due to

11
T.O. Ajiboye and D.C. Onwudiwe Results in Chemistry 3 (2021) 100151

Fig. 11. (a) Typical XRD pattern; (b) EDX spectrum; (c) Raman spectrum; (d–f) XPS spectrum of Bi2S3 . Reprinted with permission from [142]. Copyright (2017),
published by Elsevier.

Fig. 12. (a) EDXRF spectrum of Bi2S3 nanoparticles, (b) SEM image of nano-Bi2S3, and (c and d) elemental mapping of Bi2S3 nanoparticles. Reproduced with
permission from [154]. Copyright (1986), Royal Society of Chemistry.

incomplete decomposition of bismuth sulfide. At the end of the
decomposition at 947 ◦ C, about 68.93% residual weight was left and this
residue was found to be bismuth oxide. The DTA curve of bismuth sul­
fide showed two endothermic peaks at 82 ◦ C and 302 ◦ C, without
exothermic peak which indicated the loss of water and sulfur dioxide at
these two stages. Also, the DTG curve showed one exothermic peak at
73 ◦ C and an endothermic peak at 183 ◦ C. The exothermic peak of the
DTG indicated the loss of water and two molecules of SO2 while the
endothermic peak was as a result of loss of four molecules of SO2 [156].
Different studies have used all these characterization techniques to
confirm the formation of bismuth sulfide made via different methods of
synthesis. Few examples of the recent investigations involving bismuth

12
T.O. Ajiboye and D.C. Onwudiwe Results in Chemistry 3 (2021) 100151

Fig. 13. TGA/DSC of Bi2S3. Reproduced with permission from [155]. Copyright (2021), published by Elsevier.

sulfide, method used for their synthesis, applications, various charac­
terization used to confirm the formation of Bi2S3 and the type of mi­
crostructures from those investigations are shown in Table 3.
Applications of bismuth sulfide
Bismuth sulfide has been used as materials in different applications
such as photocatalyst, sensors, imaging, optoelectronic device, ther­
moelectric device, chemotherapy, electrochemical hydrogen storage, X-
ray computed tomography, thermoelectrics, photovoltaic and so on
[3,171]. Bismuth sulfide has a high figure of merit value (ZT) and Peltier
effect, hence, they are used as cooling material [172]. Some of these
applications are discussed in this section.
Medical applications
Bismuth sulfide nanoparticles have been used in various medical
applications due to their cost effectiveness, ability to function without
leaving any residue in the organisms, long time of residence, low cost
and high coefficient of X-ray attenuation [173,174]. In addition, they
are flexible for use in medicine and they are usually required at a lower
dose. One of the medical applications of bismuth sulfide is their use as
CT contrast agents (Fig. 14) [173]. Bismuth sulfide is a preferred ma­
terial for this application because the attenuation coefficient of bismuth
is the largest among the common materials that has been used for this
application [174]. It has also been used to simultaneously spot cancer
cells and destroy the cells at the same time. For instance, Liu et al. [173]
used the bismuth sulfide nanorods to simultaneously monitor the tumor
cells via imaging and then destroyed the tumor cells based on the photo-
thermal and tomographic techniques. Similarly, heterojunction system
of bismuth sulfide and bismuth vanadate was used synergistically for
photo-thermal therapy, radiodynamic therapy, radiotherapy, photo­
acoustic imaging and computed tomography [175].
Bismuth sulfide nanoparticles conjugated with immunoactive poly­
mer have been used for treating tumor cells. Although, bismuth sulfide
nanoparticles could initiate the tumor destruction, but the inclusion of
the immunoactive polymer boosted its accumulation in the cancerous
cells, which resulted to faster destruction of the cells [176]. Bismuth
sulfide has also been used to carry chemotherapy drug (curcumin). This
is beneficial since bismuth sulfide does not only function in the
enhancement of therapeutic radiation (radiotherapy), but also assist in
chemotherapeutic destruction [177]. Other examples of studies
involving the medical applications of bismuth sulfide are summarized in
Table 4.

Table 3
Examples of recent synthesis, characterization and application of Bi2S3 and its composites.
Method of synthesis Characterizationtechniques Applications Type of Ref.
microstructure

SILAR method EDS,SEM Photovoltaic material Quantum dots [124]

Spray pyrolysis XRD, EDS,SEM – Spherical [157]
Hydrothermal XRD,XPS,FTIR, TEM, Elemental mapping,SAED Supercapacitor Leaf-like [158]
Hydrothermal XRD, XPS, SEM, TEM, EDX p-Nitrophenol removal from Nanoflowers [159]
water
Hydrothermal SEM, XRD, XPS and UV–Vis Tetracycline removal from Nanorod [160]
water
Hydrothermal XRD, FT-IR, SEM, EDS and mapping, TEM, HRTEM, Brunauer-Emmett-Teller (BET), Cephalexin removal from Nanorod [161]
UV–vis diffuse reflectance spectroscopy (UV-DRS) and PL spectra wastewater
Hydrothermal XRD, FTIR, SEM, EDX, BET, TEM, PL, and UV–vis DRS analyses Antibiotic degradation Flower-like [162]
Solvothermal SEM, TEM,HRTEM and XRD Sodium-ion batteries Nanosphere [152]
Solvothermal XRD, FT-IR, BET, FESEM and TEM Capturing of radioiodine gas Flower-like [163]
Facile reflux SEM, EDAX, UV–Vis Spectroscopy and FT-IR. XRD Degradation of methylene Nanorod [164]
blue
Refluxcondensation XRD, SEM, and TEM Methylene blue removal Rice grain-like [165]
Electro-deposition XRD, SEM, UV–vis and PL Tetrabromobisphenol – [166]
degradation
one-pot solvothermal BET, XPS, XRD, SEM, and TEM Divalent lead detection Flower-like [167]
solvothermal- XRD, XPS, SEM, PL and EIS Tetracycline degradation Sea urchin-like [168]
hydrothermal
Ball milling XRD, EDS and FESEM Thermoelectric application – [169]
Dip-coating XRD, SEM and FTIR Photodiode Nanowires [170]
(Deposition)

13
T.O. Ajiboye and D.C. Onwudiwe Results in Chemistry 3 (2021) 100151

Fig. 14. Application of bismuth sulfide in CT- imaging. Reproduced from [36]. Royal Society of Chemistry open Access (2020).

Table 4
Medical applications of bismuth sulfide composites.
Bismuth sulfide-containing material Fabrication method Application Performance Ref.

Nanobone of Au@Bi2S3 nanobones – Liver cancer therapy Ablation of HEpG2 which is the cancer of the [178]
liver.
MnS@Bi2S3 Two step reactions Radiation therapy photoacoustic tumor imaging and treatment [179]
PEGylated chitosan coated with Bi2S3 Reverse- Cancer therapy Destroyed HepG2 cells in the presence of laser [114]
microemulsion radiation.
Nano-urchins of PEGylated bismuth sulfide Hydrothermal Drug delivery(Doxorubicin) and photothermal High drug loading capacity [180]
process therapy
bis-N-nitroso compounds and Bi2S3 – Cancer therapy Kills cancer cells than when pure Bi2S3 was used [181]
nanocomposite
Bi2S3/FeS2 Biomimetic one-pot Imaging and cancer cells killing High photothermal efficiency [182]

Energy-storage devices
The development of materials that lack toxic elements (such as lead
and cadmium) for solar cells devices led to the use of bismuth sulfide in
energy storage devices [51]. Raut et al. [183] fabricated bismuth sulfide
thin-films used as electrochemical capacitor by using a cheap and simple
technique that rely on adsorption processes. The bismuth sulfide thin-
films exhibited high value of specific capacitance when high concen­
tration was used, which was an indication that ionic conductivity of this
material increased with concentration. This allows the redox build-up on
the surface of electrode as reported in previous studies on the properties
of other supercapacitors [184]. Compared to the bismuth sulfide
microflowers fabricated via hydrothermal method, thin-film bismuth
sulfide displayed better specific capacitance as super capacitor [185].
Flower-like bismuth sulfide with good charge and discharge capacity, as
well as better coulombic efficiency has been used as anode material. Its
performance was found to be better compared to when the anode ma­
terial was bulk bismuth sulfide [58]. Other applications of bismuth

Table 5
Applications of bismuth sulfide in energy saving devices.
Bi2S3-containing compounds Synthetic methods Application Performance Ref.

Bi2S3-Bi2Se3 Galvanostatic co-deposition Solar cell Better photocurrent output [73]

Nano-tube arrays Bi2S3/TiO2 Electrodeposition and Photoelectrode − 0.8 A⋅cm− 2 in 1 h 30 min. [71]
anodization
Bi2S3 Thermal evaporation photovoltaic power conversion efficiency of 0.75% [15]
Ribbon Bi2S3 Thermal evaporation Solar cell 13% device efficiency [14]
1D TiO2 /Bi2S3 quantum dots Pulsed laser deposition Solar cell 3.06% energy conversion efficiency [82]
conjugate films Bi2S3/CdS Electro-deposition Liquid-junction solar cell 0.93% Photoconversion efficiency [74]
Bi2S3 Refluxing process Sodium-ion battery 69.7% retention after 40 cycles withcharge capacity of [186]
461 mAh g− 1
Composite of Bi2S3/Reduced One-pot hydrothermal route Sodium-ion battery Charge capacity of 1073.1 mAh g− 1 with good cycling [187]
Graphene Oxide performance
Bi2S3/PbS Chemical deposition Solar cells Under solar radiation, current density of40 mA/cm2 was [188]
achieved.
Nanorods of Bi2S3 – Photovoltaic In the presence of light, it displayedSignificant negative [189]
shift (− 34 mV).
LaO1− xFx/Bismuth sulfide – Supercapacitor Good performance [190]
Bi2S3/C Mechanical milling Lithium-ion battery After 100 cycles,490 mAh g− 1 which is 85% of the first [103]
cycle charge capacity
Bi2S3 – Thermoelectric material At 900 K, maximum value of 0.21 was obtained as the [22]
figure of merit(ZT)
Nanowire array of Bi2S3 Hydrothermal Schottky Diode Relative conductivities of 1.9 10-4 S cm− 1. [42]
Architectures of Bi2S3 One-pot hydrothermal Supercapacitor electrodes and Current densities up to 10 mA cm− 2 discharge efficiency [185]
Schottky diode
Nanowire of Bi2S3/Ag2S Standard Schlenk technique Solar cells 2.5% power conversion efficiency [191]
Bi2MoO6/ Bi2S3 Hydrothermal Electrode Good photoelectrochemical capacity [192]
Bi2S3 modified glassy carbon Electrochemical Electrode Good anti-interference and reproducibility [193]
electrode
SnO2/ Bi2S3 SILAR Solar cell Conversion efficiency of 0.27% [194]
Bi2S3/Ag2S/ZnO SILAR Photoelectrode photoconversion efficiency of 12.63% [195]
Bi2S3/ZnS/ZnO SILAR Photoanode 220 μA/cm2 at 0.2 V photocurrent density [196]
Composite of Bi2S3-PPy yolk-shell Bio-inspired material Rechargeable batteries Efficient lithium storage cyclability [197]

14
T.O. Ajiboye and D.C. Onwudiwe Results in Chemistry 3 (2021) 100151

sulfide and their composites as energy storage devices are summarized
in Table 5.
Removal of pollutants
The negative environmental impact of the discharge of organic and
inorganic waste into the environment by industries such as rubber,
printing, textile, plastic, leather, and mining has necessitated the
removal of these pollutants from the environment [198]. Bismuth sul­
fide based compounds are among the materials that have been used for
remediating the environment from these pollutants. Rhodamine B has
been removed from water by using bismuth sulfide and copper sulfide
composite as photocatalyst under visible lights [199]. Methyl orange has
been photocatalytically degraded by bismuth sulfide-containing photo­
catalyst (Bi2S3/ZnO) under visible light. The presence of bismuth sulfide
in the composite resulted into the removal of more than 80% of methyl
orange [200]. Bi2Sn2O7/ Bi2S3 is another composite of bismuth sulfide
that was used to degrade dye (Rhodamine B). Apart from the removal of
dyes from the environmental samples, bismuth sulfide has also been
used for the removal of toxic metals from the environment. For instance,
the use of bismuth sulfide as efficient photocatalyst for removing hex­
avalent chromium from water through photocatalytic reduction process
has been reported [142]. Bismuth sulfide has been used for the simul­
taneous removal of organic and inorganic pollutants [201]. Examples of
investigations involving the use bismuth compounds in environmental
remediation are shown in Table 6. In all the investigations, the amount
of pollutants removed was more than 50%, which showed that they are
good adsorbents and/or photocatalysts.
Sensing applications
Sensing devices have been fabricated by using various bismuth sul­
fide nanostructures and one of such sensing devices is laser detector. The
desirable properties of bismuth sulfide that made it good for fabricating
laser detector are its non-toxic nature, large surface area, chemical
stability, high crystallinity and light absorptivity ability in the visible
and near infra-red region of the solar spectrum [52,224,225]. Bismuth
sulfide microflowers and substrate made from printing paper were used
to successfully fabricate sensitive laser detector [224]. Apart from the
microflower, bismuth sulfide nanorods have also been used to fabricate
laser detector and the performance of the nanorods was found to be
better than that of the microflower. The better performance of bismuth
sulfide nanorod are shown in the higher linear range, better photo-
sensitivity and linear current features compared to the microflower
[52]. Despite the fact that the bismuth sulfide nanorods performed
better than the nanoflowers [52], its performance as sensing material
was lower when it was decorated with gold nanoparticles [53]. Oleate
ligands-capped crystalline bismuth sulfide nanorods was also used as
sensing device with response in the millisecond range [48]. The use of
composite made from bismuth sulfide and bismuth oxychloride was also
reported as fast and sensitive photodetector [226]. Nanocomposite
made from bismuth sulfide and graphene oxide was reported for elec­
trochemical detection of hexanitrodiphenylamine. The bismuth sulfide
used in the composite was made via thermolysis of bismuth tris-(hex­
adecyldithiocarbamate) [227]. Various biological species has also been
detected by bismuth sulfide-containing sensors. Cancer antigen, carci­
noembryonic antigen and A-fetoprotein were jointly detected by using
gold-coated bismuth sulfide. Hydrogen peroxide in the biological sam­
ple was detected by amperometric method which has bismuth sulfide as

Table 6
Pollutants removal by bismuth sulfide-containing compounds.
Bi2S3 composites Fabrication method Removal techniques Pollutants removed Conditions Ref.

Ternary composites of 1D-Bi2S3@2D- – Photocatalysis Degradation of tetracycline Visible light [202]

GO/3D-BiOI
Bi2S3@MoS2 Hydrothermal Adsorption and Methylene blue and Rhodamine B Visible light [203]
photocatalysis
Bi2S3/ nanowire arrays TiO2 Electrochemical deposition Photocatalysis Cr (VI) and methyl orange Light [204]
/graphene quantum dots Irradiation
Nanorods of Fe2O3/Bi2S3 Hydrothermal synthesis photocatalysis phenol and methylene blue Visible light [205]
Nanoflower Bi2O3/Bi2S3 Hydrothermal method Photocatalysis RhB and Cr(VI) Visible light [198]
Bi2S3/Bi2WO6 Hydrothermal method Photocatalysis Ofloxacin degradation Visible light [206]
Composite of Zn0.5Cd0.5S/Bi2S3 Facile method Photocatalysis Rhodamine B degradation Visible light [207]
SnO2/Bi2S3/BiOCl–Bi24O31Cl10 Hydrothermal then thermolysis Photocatalysis Rhodamine B Degradation Visible light [208]
MoS2 Nanosheet-Coated Bi2S3 Hydrothermal Photocatalysis Cr(VI) reduction Visible light [209]
Hollow Bi2S3 nanospheres Hydrothermal Photocatalysis Cr(VI) reduction Visible light [210]
Bi2S3/BiOI Ion exchange method photocatalysis Methyl orange removal Visible light [211]
Bi2S3/BiVO4 microspheres Limited chemical conversion route photocatalysis Rhodamine B Visible light [212]
Powder of CuS/Bi2S3 Hydrothermal Photocatalysis Rhodamine B Visible light [199]
Nanostructures of Bi2S3 Solvothermal Photocatalysis Rhodamine B, methylene blue Visible light [44]
and methyl orange
Nanorods and nanosheets of Bi2S3 on Hydrothermal Photocatalysis Rhodamine B removal Visible light [213]
Bi2O3
Bi2S3/Bi2Sn2O7 Hydrothermal Photocatalysis Rhodamine B removal Visible light [145]
Bi2O2CO3/Bi2S3 Ion exchange Photocatalysis Rhodamine B removal Visible light [214]
Bi2S3/ZnIn2S4 Microwave-assisted Photocatalysis Methylene blue Visible light [215]
Bi2MoO6 /Bi2S3 In situ anion exchange Photocatalysis Cr(VI)removal Visible light [216]
Bi2S3/SnIn4S8 Solvothermal Photocatalysis Removal of Rhodamine B (and Visible light [55]
bacteria)
bismuth sulfide@polyacrylonitrile Ultrasonication Adsorption Iodine removal – [217]
CuWO4/Bi2S3/ZIF67 Hydrothermal Photocatalysis Degradation of Cephalexin and LED [218]
Metronidazole antibiotics illumination
BiNbO4/Bi2S3 Combination of ion exchange technique, heat- Adsorption and Rhodamine B removal Visible light [219]
treatment and precipitation photocatalysis
Hollow microspheres Bi2S3 Polyol process Adsorption Adsorption of silver ions – [220]
Composite of CuWO4/Bi2S3 Hydrothermal Photocatalysis Removal of cephalexin Visible light [221]
graphene aerogel Bi2S3-BiVO4 Hydrothermal Photocatalysis and Bisphenol A and Cr(VI) Visible light [222]
adsorption
Nanocomposite of KIT-5/Bi2S3-Fe3O4 – Photocatalysis Removal of parathion pesticides Visible light [223]
Bi2S3 nanostructure microwave irradiation photocatalysis Reduction of Cr(VI) Visible light [10]

15
T.O. Ajiboye and D.C. Onwudiwe
the active material [54]. Bismuth sulfide nanoparticles has also been
used as gas sensor [225]. For instance, methanol vapor was detected by
using a sensor fabricated from bismuth sulfide nanoparticles [225].
Sensors fabricated from bismuth sulfide nanowire have been used for the
detection of hydrogen. The sensor has sensitivity of 22%, but its per­
formance improved when it was doped with palladium nanoparticles
[228]. In addition, microbes have also been detected by using bismuth
sulfide-based sensors. Nanocomposite of bismuth sulfide nanorods and
nanogold was reported for the detection of Escherichia coli O157:H7
[229].
Water splitting, hydrogen and oxygen generation
Photoelectrochemical catalysis for the generation of oxygen and
hydrogen from water has attracted some research attention lately. The
process is based on the ability of some materials to trap energy from the
sun and simultaneously use same to split water into hydrogen and ox­
ygen, and this has been used in the generation of chemical fuel [230].
The hydrogen generation rate of bismuth sulfide has been improved
through a better charge transfer process obtained by the compositing
bismuth sulfide with molybdenium disulfide as solar-light active pho­
tocatalyst. When the ratio of bismuth-to-molybdenium was 1:1, about
61.4 μmol/h of hydrogen was liberated [231]. Heterostructures made
from zinc oxide and bismuth sulfide has also been used under visible
light to generate hydrogen from water. The performance of this photo­
catalyst increased due to the presence of bismuth sulfide in the com­
posite [200]. Similarly, the quantity of hydrogen obtained spiked when
bismuth sulfide was introduced into the nanotube of titanium oxide
under visible light. About 13 folds increment in the generation rate of
hydrogen was observed compared to when pure titanium oxide nano­
tube was used [67]. Bi2S3 nanorods decorated on MoS2/WS2 nanosheets
has also been used to generate hydrogen via water splitting [230]. A
complex of bismuth sulfide and TiO2 was used for photo-splitting of
water in methanol to liberate hydrogen gas [232]. A high photocatalytic
performance was obtained due to electrons and holes recombination as a
result of the formation of the composite. This enhanced hydrogen evo­
lution was also observed when composite of Bi2S3/g-C3N4 was used as
photocatalyst in water splitting [233].
Electrochemical hydrogen storage, fuel production and reduction of CO2
Hydrogen could be used as energy source to power automobiles,
however, the efficient storage of hydrogen is challenging due to the
absence of good hydrogen-storage materials. A good storage material
should have capacity to store large volume of hydrogen over a wide
range of temperature [234]. The problem of hydrogen storage could be
solved by using bismuth sulfide nanocrystals. Bismuth sulfide nano­
structures has been reported to possess sites of hydrogen adsorption
[58]. The hydrogen penetrates the interlayers of the bismuth sulfide
crystals after it has been adsorbed on its interstitial pores. Bismuth
sulfide synthesized via the assistance of biomolecules also displayed a
significant capacity for storing hydrogen generated electrochemically.
The ability of bismuth sulfide to store hydrogen has been reported to be
influenced by properties such as morphology, pore density and particle
size [146]. Both bismuth sulfide nanorods and nanoflowers have also
been found to be effective for hydrogen storage [58]. Bismuth sulfide-
containing compounds have been reported to generate useful products
from carbondioxide. For example, CO and H2 were obtained in the
presence of visible light by using composite made from Bi2S3 and CdS as
the photocatalysts. In the synthesis of this active photocatalysts, tetra(4-
carboxyphenyl)porphyrin iron(III) chloride was used as the photosen­
sitizer, which boosted the amount of CO and H2 obtained by 8.2 folds
and 1.7 folds respectively [235].
16
Results in Chemistry 3 (2021) 100151
Thermoelectric and other device applications
The Figure of merit (ZT), which is a dimensionless parameter used to
determine if a particular material will be useful as thermoelectric device
[236], has confirmed that Bi2S3 is a good thermoelectric material [22].
The high ZT value of Bi2S3 is as a result of its low thermal conductivity
and high Seebeck coefficient. However, further improvement of its ZT
value by reducing the value of electrical resistivity is being investigated
[237]. Although, the thermoelectric property of Bi2S3 crystal is depen­
dent on the planar direction on the crystal. The higher ZT value could be
achieved along the ac plane [22]. Bi2S3 produced through ball milling
was used as thermoelectric material and it was observed that optimi­
zation of the process of ball milling increased the power factor to 233
µW K− 2 m− 1 at 573 K. When the mechanical alloying was assisted by
spark plasma sintering, the sulfur content of Bi2S3 was modified leading
to the generation of sulfur vacancy. The presence of sulfur vacancy led to
the reduction of electrical resistivity from 10− 2 to 10− 4 Ω m. As a result,
the power factor jumped from 91 to 254 µW K− 2 m− 1 [238]. The ther­
moelectric properties of Bi2S3 has also been improved by compositing it
with other materials. For instance, bismuth was used to form a com­
posite with Bi2S3 and the nanocomposite performed 5 fold better than
pristine Bi2S3 as thermoelectric material [239]. Bismuth sulfide has also
been introduced into bulk digenite (Cu1.8S) to obtain thermoelectric
material with low toxicity, low cost and better performance [240].
Apart from its usage as thermoelectric device, Bi2S3 has been used for
other device structures. For instance, it has been used in developing laser
detector which has fast response and high flexibility. Laser detector
made from bismuth sulfide microflower was deposited on paper
measured laser signal that was as weak as 3.3 mW/cm2 at 450 nm. The
sensitivity of the device was improved as indicated by the change in the
values of current intensity, irradiation power density and photocurrent
as shown by Fig. 15 (a-f) [224]. Bi2S3 nanoparticles is also good as
supercapacitor because it has retentivity of about 79% even after 1000
cycles coupled with specific capacitance 470 Fg-1at current density 0.5
Ag− 1 [241]. The sulfur source used for the synthesis of bismuth sulfide
influence the maximum energy density and maximum specific capaci­
tance of Bi2S3 when it is used as electrode and in storing charge. The
Bi2S3 made by using thiourea as sulfur source displayed better ability to
store charge than the one made from sodium sulfide due to stronger
π-interaction between organic and inorganic species [242]. Composite
of Bi2S3 has also been used in developing memory device that possess a
long retention time and high dynamic random access memory [243].
Conclusion and recommendations
The synthesis of bismuth sulfide is desirable due to its non-toxicity
and low cost. These properties are also responsible for its numerous
applications in areas such as environmental remediation, fabrication of
electronic devices, photodetectors and medical applications. The high
demand for bismuth sulfide has spurred the search and exploration of
different synthesis routes. The different methods of synthesis of bismuth
sulfide has been critically examined. However, there are other methods
such as sulfurization, solventless synthesis, close-space vapour transport
and molecular beam epitaxy that were not discussed. Hyphenated
techniques of the common methods of preparing bismuth sulfide could
be considered, where the advantages of each of these techniques are
hybridized for improved properties. Numerous bismuth compounds
have been used as catalysts in effecting organic reactions such as ring
opening of cyclopropanes, Wagner–Meerwein rearrangements,
Hantzsch aromatization, Fries rearrangement, Baylis–Hillman reaction,
ring opening of epoxides etc. Bismuth sulfide has not been used as
catalyst for most of these reactions apart from its usage as catalyst in the
ring opening of epoxides and Suzuki-Miyaura cross-coupling reactions.
Hence, the use of bismuth sulfide as catalyst for some of these organic
reactions is worthy of investigation. In addition, its medical usage as
artificial enzyme and wound healing process has not been properly
T.O. Ajiboye and D.C. Onwudiwe
Fig. 15. (a) Flexible laser detector schematic illustration with photograph of the device as inset, (b) I-V curves of the laser detector measured under light and in the
dark with 30 V bias at 650 nm laser beam, (c) curve obtained when 450 nm laser beam was used, (d) curve obtained when 780 nm laser beam was used, (e) Linear fit
curves of photocurrent with 650 nm laser beam with different intensities, (f) I–V curves illuminated at different laser wavelength when the light intensity was
maintained at 23 mW/cm2. Reprinted with permission from [224]. Copyright (2021), published by Elsevier.
studied, and this is an area that could be recommended for further study.
CRediT authorship contribution statement
Timothy O. Ajiboye: Conceptualization, Writing-original draft
preparation. Damian C. Onwudiwe: Conceptualization, Writing - re­
view & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
Authors acknowledges funding of support from National Research
Foundation (NRF), South Africa and North-West University, South
Africa.
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