Formation of Group 11 Bismuth Sulfide Nanoparticles Using Bismuth Dithioates under Mild Conditions

Article abstract of DOI:10.1002/chem.201701952

The formation of mixed-metal sulfides with the general structure AgBiS₂ and Cu₃BiS₂ by a simple two-step process utilizing bismuth dithiocarboxylates as Bi and S precursors is described. A sonochemical reaction of Bi₂O₃ with six different aryl dithioic acids: dithiobenzoic acid (BDT-H), 4-methoxydithiobenzoic acid (4-MBDT-H), 3-methyldithiobenzoic acid (3-MBDT-H), 2-mesitylenedithioic acid (2-MDT-H), 4-fluorodithiobenzoic acid (4-FBDT-H), and 2-thiophenedithioic acid (2-TDT-H) resulted in the corresponding complexes: [Bi(BDT)₃] 1, [Bi(4-MBDT)₃] 2, [{Bi(3-MBDT)₃}₂?C₇H₈] (3₂?C₇H₈), [Bi(2-MDT)₃] 4, [Bi(4-FBDT)₃] 5 and [Bi(2-TDT)₃] 6. Microwave irradiation of these bismuth(III)aryldithioate complexes with AgNO₃ or CuCl under mild reaction conditions (140 °C) resulted in the respective mixed-metal sulfides. Attempt to synthesize AuBiS₂ using similar reaction protocols were unsuccessful, resulting only in the formation of elemental Au⁰, S₈ and BiOCl.

Full text of DOI:10.1002/chem.201701952

A Journal of
Accepted Article
Title: Formation of Nanoparticle Ternary Group 11 (Cu, Ag) Bismuth
Sulfides and Au(0) utilizing Bismuth Dithioates under Mild
Conditions
Authors: Dimuthu C Senevirathna, Melissa Vivienne Werrett, Narendra
Pai, Victoria L Blair, Leone Spiccia, and Philip C Andrews
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201701952
Link to VoR: http://dx.doi.org/10.1002/chem.201701952
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Formation of Nanoparticle Ternary Group 11 (Cu, Ag) Bismuth
Sulfides and Au(0) utilizing Bismuth Dithioates under Mild
Conditions
Dimuthu C. Senevirathna,[a] Melissa V. Werrett,[a] Narendra Pai,[a] Victoria. L. Blair,[a] Leone Spiccia,[a]
and Philip C. Andrews*[a]
Abstract: The formation of mixed metal sulfides of AgBiS2 and
Cu3BiS2 via a simple two-step process utilizing bismuth dithioates as
single source Bi and S precursors is described. Sono-chemical
reaction of Bi2O3 with six different aryldithioc acids (benzodithioic,
BDT-H; 4-methoxybenzodithioic, 4-MBDT-H; 3-methylbenzodithioic,
3-MBDT-H; 2-mesitylenedithioic, 2-MDT-H; 4-fluorobenzodithioic, 4-
FBDT-H; and 2-thiophenedithioic, 2-TDT-H) resulted in the following
complexes; [Bi(BDT)3] 1, [Bi(4-MBDT)3] 2, [{Bi(3-MBDT)3}2·C7H8]
(32·C7H8), [Bi(2-MDT)3] 4, [Bi(4-FBDT)3] 5 and [Bi(2-TDT)3] 6.
Microwave irradiation of these bismuth(III)aryldithioate complexes
with AgNO3 or CuCl under mild reaction conditions (140 °C)
resulted in the respective mixed metal sulfides. Attempt to
synthesize AuBiS2 using similar reaction protocols were
unsuccessful and resulting only in the formation of elemental Au(0),
S8 and BiOCl.
particular interest as a semiconductor with a comparatively
narrow direct bandgap and absorption edge at ca 950 nm[9] that
can be modified via incorporation of another metal.[10,11]
Ternary first group metal bismuth chalcogenides are solvent
processable and with a tunable bandgap,[11] intrinsically low
lattice thermal conductivity,[3] and photoconductivity.[12] AgBiS2
and Cu3BiS3 are known to exhibit even broader absorption than
Bi2S3 and provide improved charge mobility. AgBiS2, a highly
stable, non-toxic material with its photoconductivity, absorption
coefficient (105 to 103 cm−1) and beneficial thermoelectric
properties, has been used as a sensitizer, counter electrode and
charge transfer material in solar cells.[12,13] Of the two crystalline
phases of AgBiS2; the room temperature β hexagonal phase and
the α cubic rock salt phase (formed at ca 473 K),[3,14] it is the
cubic phase which has shown appreciable photovoltaic
performance.[12] Likewise, Cu3BiS3 with its orthorhombic crystal
structure and direct band gap, as well as high absorption
coefficient of ~105 cm−1 and possibility of being a p-type
material, shape it as a prospective material for photovoltaic and
optoelectronic applications.[11]
Implementation of semiconductor metal chalcogenides in
forefront technologies such as opto-electronics, thermo-electrics,
optical recording, and catalysis, as well as for the creation of
advanced coatings, pigments and lubricants is rapidly
expanding.[1–3] From the perspective of opto-electronic
applications, cadmium and lead chalcogenides are arguably
among the most intensively studied compounds[3,4] from which
highly useful tunable properties are successfully exploited in
industry.[5] However, the pernicious toxicity of both Cd and Pb
stimulates the search for new materials with similar properties
that can be formed from abundant and non-toxic elements.
Currently, this is difficult to achieve with binary systems, but
ternary chalcogenides offer an interesting alternative with
potentially higher flexibility for the band level engineering, which
is critical for photoabsorption and photoconductive applications.
A wide range of synthesis methods exist to produce cubic
phase AgBiS2 nanomaterials. Those include vacuum fusing[3]
microwave synthesis,[14] flux technique,[15,16] solvothermal[17,18]
and ligand assisted methods.[12] A common feature of the
reported synthetic approaches is the use of an isolated
individual precursor for each element in the ternary system. High
temperature flux methods use Bi and Ag metals with sulfur
powder as the starting materials,[3,19] whereas bismuth and silver
nitrates or acetates with a variety of chalcogen precursors like
thiourea[14]
thiosemicarbazide,[18]
L-cysteine,[17]
hexamethyldislathiane[12] or Na2S[13] have been employed for the
low temperature synthesis, e.g. by using hydrothermal or
microwave irradiation. Similarly, a broad arsenal of methods to
synthesize Cu3BiS3, using individual precursors for each
component in the system, have been reported. These methods
include spray pyrolysis,[20] sputtering,[11,21,22] co-evaporation,[23,24]
solid-state synthesis,[25,26] solvothermal[27,28] and microwave
methods.[29]
Multinary chalcogenides have been increasingly investigated
and in particular,[6,7] nano size particles offer extended
possibilities to control the composition and internal structure of
the materials prior to processing, compared to the bulk. For
example, copper indium selenide has off-stoichiometric
structures in the bulk (e.g. CuIn3Se5, CuIn5Se8, Cu2In4Se7) which
leads to less deep trap states resulting in compromising its opto-
electronic properties.[8] Among metal chalcogenides with
environmentally benign elements, bismuth sulfide (Bi2S3) is of
Controlling the stoichiometry, size and impurity in
chalcogenides is an important factor, since this directly affects
the photo absorption and intrinsic defects in the material.
However, many methods used for isolating ternary
chalcogenides require high temperature or vacuum[2,13] as well
as individual precursors for each component in the system.
Reducing the number of precursors is advantageous to improve
purity, reduce defects and avoid the chance of pre-reaction
forming binary counter products.[30] Here, lies the relevance of
mitigating a modified synthesis strategy with novel dual source
precursors for producing ternary chalcogenides.
[a]
Mr. D. C. Senevirathna, Dr. M. V. Werrett, Mr. N.Pai, Dr. V. L. Blair,
Prof L. Spiccia, Prof. P. C. Andrews.
School of Chemistry
Monash University
Clayton, Melbourne, VIC 3800
Australia
phil.andrews@monash.edu
Supporting information for this article is given via a link at the end of
the document.
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As we have recently reported, aryldithioic acids (ArCS2H)
react efficiently with crude bismuthinite (Bi2S3) to form
bismuth(III) aryldithioates, [Bi(S2CAr)3] in high yield and high
purity.[31] We have since discovered that crude bismite (Bi2O3)
can be substituted for bismuthinite in this process reducing the
reaction time from 4 h to 1 h. Crystalline Bi2S3 nanorods can
then be easily generated from [Bi(S2CAr)3], upon mild solution
decomposition.[31,32]
The method described herein uses microwave irradiation to
produce finely dispersed nano-sized mixed metal sulfides (and
Au). Full synthetic details are provided in the Supporting
Information (SI). As
a
representative example, the
heterogeneous sono-chemical reaction of bismite (Bi2O3) with 3-
methylbenzenedithioic acid (3-MBDT-H) in toluene gave the
corresponding bismuth(III) arenedithioate, crystallized as [{Bi(3-
MBDT)3}2·C7H8] (32·C7H8), as a red-orange solid after one hour.
Complete conversion could be observed visually through full
consumption of the crude yellow Bi2O3. The resulting solid is
easily isolated by filtration and subsequently purified by
recrystallization from hot toluene. Each complex ([Bi(BDT)3] 1,
[Bi(4-MBDT)3] 2, [{Bi(3-MBDT)3}2·C7H8] (32·C7H8), [Bi(2-MDT)3]
4, [Bi(4-FBDT)3] 5, [Bi(2-TDT)3] 6) was therefore isolated as an
air-stable red (1-3, 5-6) or yellow (4) crystalline solid (yield 75-
85%). Elemental analysis, FTIR, 1H and 13C NMR and mass
spectrometry confirmed the composition of the crystalline solids.
This data is provided in further detail in the Supporting
Information.
Building on this process we can now report the highly
efficient synthesis of nanoparticles of AgBiS2 and Cu3BiS3 from
the reaction/decomposition of [Bi(S2CAr)3], formed from a range
of aryldithioc acids (Figure 1), in the presence of AgNO3 or CuCl
respectively. However, an analogous reaction with HAuCl4 did
not generate AuBiS2, but resulted in deposition of elemental gold
via the gold(I) dithioate complex [Au(S2CAr)]. This is
summarized in Scheme 1.
The solid state structures of [Bi(4-MBDT)3] 2, [{Bi(3-
MBDT)3}2·C7H8] (32·C7H8) and [Bi(2-MDT)3] 4, were determined
by single crystal X-ray diffraction from crystals grown in either
toluene (3) or DMSO (2 and 4). As an illustrative example, the
crystal structure of [{Bi(3-MBDT)3}2·C7H8] (32·C7H8) is shown in
Figure 2, with 2 and 4 given in the SI along with a summary of all
the crystallographic data.
Figure 1. Structures and abbreviations of the aryldithioic acids used in the
synthesis of bismuth(III) dithioate complexes 1 - 6.
Figure 2. Molecular structure of [{Bi(3-MBDT)3}2·C7H8] (32·C7H8). Thermal
ellipsoids are given at 50% probability. Hydrogen atoms have been omitted for
clarity. Selected bond lengths (Å) and angles (°): Bi(1)-S(1), 2.7319(8); Bi(1)-
S(2), 2.8496(8); Bi(1)-S(3), 2.7544(8); Bi(1)-S(4), 2.9134(8); Bi(1)-S(5),
2.5731(7); Bi(1)-S(6), 2.9209(8); S(1)-Bi(1)-S(2); 63.34(2); S(3)-Bi(1)-S(4),
62.50(2); S(5)-Bi(1)-S(6), 64.29(2).
Scheme 1. Synthesis pathway for mixed metal sulfide nanoparticles, as well
as gold. The bismuth dithioate ([Bi(S2CAr)3]) is formed from the reaction of
Bi2O3/Bi2S3 with an aryldithioic acid. The mixed metal sulfide is subsequently
produced from the reaction/decomposition of [Bi(S2CAr)3] with a group eleven
salt. In the case where HAuCl4 is used, the mixed metal sulfide AuBiS2, is not
isolated and instead gold is finally recovered.
Susequent formation of AgBiS2 and Cu3BiS3 nanoparticles
was achieved in two simple steps. Firstly, the crystalline
[Bi(S2CAr)3] complexes 1 - 6 were isolated and dissolved in
DMSO with oleic acid or 1-dodecanethiol as the surfactant. Next,
a stoichiometric amount of AgNO3 or CuCl was added and the
solution exposed to microwave iradiation at 140 °C for 40
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minutes. The solution darkened and a black precipitate formed.
The resultant black precipitate was washed several times with
ethanol, collected by centrifugation and prepared for analysis.
Heating a DMSO suspension of the red-brick precipitate of
[Au(3-MBDT)] (7) to 140 °C for 40 minutes under microwave
irradiation produced a single piece of Au(0) (0.191 g, yield 97%)
confirming our earlier observation that Au(III) from HAuCl4 can
be easily reduced to Au(0) in two simple steps.
When this method was repeated with HAuCl4, as a gold
source, a different outcome was observed. After combining
[Bi(S2CAr)3] and oleic acid in DMSO, HAuCl4 was added and a
suspension of a red-brick color precipitate immediately formed.
Upon microwave irradiation (140 °C, 40 min) this transformed
into a pale yellow solution with concomitant deposition of Au(0)
metal (as confirmed by energy dispersive X-ray spectroscopy
(EDX), Figure S12). The pale yellow solution was kept, and
upon slow evaporation, yielded crystals of elemental sulfur
alongside bismuth(III) oxychloride (BiOCl) as confirmed by
scanning electron microscopy (SEM), EDX and single crystal X-
ray diffraction (Figures S13 and S14). This unusual result
suggests Au(III) is reduced to Au(0) while S2- present from the
decomposition of either or both [Bi(S2CAr)3] and [Au(S2CAr)],
oxidizes to S(0).
The formation and isolation of AgBiS2 and Cu3BiS3
nanoparticles was confirmed using transmission electron
microscopy (TEM), selective area electron diffraction (SAED)
and EDX. EDX microanalysis was used to confirm the presence
and relative ratios of each element in AgBiS2 and Cu3BiS3
nanoparticles (Figures S15 and S16) which proved to be
consistent with AgBiS2 and Cu3BiS3. As shown in Figure 4 (top)
the Cu3BiS3 particles appear rounded (possibly spherical) with
diameters ranging from 60-80 nm. The AgBiS2 particles (Figure
4, bottom) are generally larger (80-90 nm) and appear less
speherical but still rounded at the edges. Lattice fringes can be
clearly observed in the high resolution TEM (HR-TEM) images
(Figure 4, right) of both the Cu3BiS3 and AgBiS2.
This redox process was further investigated. First, the red-
brick precipitate formed from the combination of HAuCl4 with
[Bi(S2CAr)3] (in DMSO) was identified as [Au(3-MBDT)] (7), in
which gold has reduced to the Au(I) oxidation state. A similar
result occurs when using Au(I) directly, as AuCl. Compound 7 is
insoluble in all NMR solvents so elemental analysis and FTIR
was used to confirm the composition. However, compound 7
was soluble in acetone in the presence of PPh3 and upon slow
evaporation, crystals of [Au(3-MBDT)(PPh3)2] (8) were obtained,
as determined by single crystal X-ray diffraction. The solid-state
structure is shown in Figure 3 and a summary of crystallographic
details provided in the SI.
In both samples, the particles isolated appear to be
aggregated however, clear SAED patterns were obtained for
both AgBiS2 and Cu3BiS3 (Figures S17 and S18). The AgBiS2
SAED pattern could be indexed to the cubic phase of AgBiS2
̅
(Fm3m, a=b=c= 5.648
Å
).[34–36] The SAED pattern collected from
the Cu3BiS3 sample shows individual bright spots, indicative of a
crystalline material. Although no obvious ring patterns were
observed, various d-spacings could be calculated from the bright
spots, which match well with the orthorhombic phase of Cu3BiS3
(P212121, a=7.723, b=10.395 and c=6.716 Å).[35,37]
Figure 3. Molecular structure of [Au(3-MBDT)(PPh3)2] (8). Thermal ellipsoids
are given at 50% probability. Hydrogen atoms have been omitted for clarity.
Selected bond lengths (Å) and angles (°): Au(1)-S(1), 2.8347(6); Au(1)-S(2),
2.5712(6); Au(1)-P(1), 2.3402(6); Au(1)-P(2), 2.3024(6); S(1)-Au(1)-S(2);
65.453(17).
Figure 4. TEM images of the Cu3BiS3 (top) and AgBiS2 (bottom) isolated from
the microwave reaction of [{Bi(3-MBDT)3}2·C7H8] (32·C7H8) with CuCl or
AgNO3. High resolution TEM images (right) show the clear lattice fringes
observed in each sample.
The complex contains one Au(I) atom which is coordinated
by two sulfur atoms from the 3-MBTD ligand in a bidentate
fashion, and PPh3 ligands giving an overall distorted tetrahedron
geometry around the Au(I) center. It is isostructural with
[Au(BDT)(PPh3)2][33] and [Au(S2C-p-tolyl)(PPh3)2].[33]
Bulk analysis, in the form of powder X-ray diffraciton
(PXRD) was used to further confirm the purity of the
samples analysed by TEM. Figures 5, 6 and 7 show the
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PXRD
patterns of synthesized AgBiS2 and Cu3BiS3
nanoparticles as well as Au; formed from the microwave
irradiation of [{Bi(3-MBDT)3}2·C7H8] (32·C7H8) with AgNO3,
CuCl and HAuCl4 respectively. The experimental patterns
(black) match well with their corresponding standard PXRD
patterns (red). This bulk analysis supports the TEM, SAED
and EDX analysis of the mixed metal sulfide nanoparticles.
The observed diffraction peaks suggest that these materials
are pure AgBiS2, Cu3BiS3 and Au, containing no traces of
side products or monometallic sulfides. The black solids
isolated from the reactions of the remaining complexes (1,
2, 4-6) with either AgNO3 or CuCl show comparable PXRD
patterns with AgBiS2 (Figures S19 – S23) and Cu3BiS3
(Figures S24 – S28).
Figure 7. Comparison of the powder X-ray diffraction pattern of standard
metallic Au (red)[39] and synthesised Au from [{Bi(3-MBDT)3}2·C7H8]
(32·C7H8) (black).
We have discovered a novel method for the formation of
nanoparticles of the ternary group 11 bismuth sulfides, AgBiS2
and Cu3BiS3 under mild conditions using bismuth dithioates as
reactive single-source precursors of Bi and S. The attempted
synthesis of the gold analogue using a similar method
resulted only in reduction of Au from +III (in HAuCl4) to +I
(as the gold dithioate), and ultimately to agglomerated
Au(0) on gentle heating.
Figure 5. Comparison of the powder X-ray diffraction pattern of standard
AgBiS2 (red)[34] and synthesised AgBiS2 nanoroparticles from [{Bi(3-
Acknowledgements
MBDT)3}2·C7H8] (32·C7H8) (black).
The authors thank Monash University and the Australian
Research Council (DP140102093 and LE110100223) for
financial support and acknowledge use of the facilities and the
assistance of Dr. Tim Williams at the Monash Centre for Electron
Microscopy. The authors acknowledge that part of this research
was undertaken on the MX1 beamline at the Australian
Synchrotron, Victoria, Australia.
Keywords: bismuth • nanoparticles • mixed metal sulfides •
dithioate ligands • microwave
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Entry for the Table of Contents (Please choose one layout)
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The formation of mixed metal sulfides
of AgBiS2 and Cu3BiS2 via a simple
two-step process utilizing bismuth
dithioates as single source Bi and S
precursors is described. Microwave
irradiation of bismuth(III)aryldithioate
complexes with AgNO3 or CuCl under
mild reaction conditions (140 °C)
resulted in the respective mixed metal
sulfides.
Dimuthu C. Senevirathna,[a] Melissa V.
Werrett,[a] Narendra Pai,[a] Victoria. L.
Blair,[a] Leone Spiccia,[a] and Philip C.
Andrews
Page No. – Page No.
Formation of Nanoparticle Ternary
Group 11 (Cu, Ag) Bismuth Sulfides
and Au(0) utilizing Bismuth Dithioates
under Mild Conditions
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Author(s), Corresponding Author(s)*
((Insert TOC Graphic here))
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Title
Text for Table of Contents
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