Reaction of Ni2+ and SnS as a Way to Form Ni@SnS and Sn2Ni3S2 Nanocrystals: Control of Product Formation and Shape

Article abstract of DOI:10.1002/chem.201500498

Reductive diffusion of Ni²⁺ into SnS particles was shown to selectively form Sn₂Ni₃S₂, hybrid, or even core-shell Ni@SnS, Ni_1.523Sn, and Ni₃S₂, by tuning the reaction conditions at low temperatures. The mechanism of Ni²⁺ reduction and diffusion into SnS was observed in ethylene glycol, which served both as solvent and reducing agent. Tuning of reaction temperature and duration, morphology of the template SnS, and the application of ethylenediamine as supporting chelating agent, influence the formation of the final products. Their formation was controlled by carefully adjusting redox and equilibrium reactions. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy analysis (EDX). Reductive diffusion of Ni²⁺ into SnS particles is shown to selectively form Sn₂Ni₃S₂, hybrid, or even core-shell Ni@SnS, Ni_1.523Sn, and Ni₃S_2, by tuning the reaction conditions at low temperatures. Their formation is controlled by carefully adjusting redox and equilibrium reactions.

Full text of DOI:10.1002/chem.201500498

DOI: 10.1002/chem.201500498
Full Paper
&
Nanoparticles
2
+
Reaction of Ni and SnS as a Way to Form Ni@SnS and Sn Ni S
2
3 2
Nanocrystals: Control of Product Formation and Shape
[a]
[a, b]
Stefan Michael Rommel and Richard Weihrich*
Dedicated to Professor Manfred Scheer on the occasion of his 60th birthday
2
+
Abstract: Reductive diffusion of Ni into SnS particles was
plate SnS, and the application of ethylenediamine as sup-
porting chelating agent, influence the formation of the final
products. Their formation was controlled by carefully adjust-
ing redox and equilibrium reactions. The products were
characterized by X-ray diffraction (XRD), scanning electron
microscopy (SEM), and energy dispersive X-ray spectroscopy
analysis (EDX).
shown to selectively form Sn Ni S , hybrid, or even core-shell
2
3 2
Ni@SnS, Ni1.523Sn, and Ni S , by tuning the reaction condi-
3
2
2
+
tions at low temperatures. The mechanism of Ni reduction
and diffusion into SnS was observed in ethylene glycol,
which served both as solvent and reducing agent. Tuning of
reaction temperature and duration, morphology of the tem-
Introduction
as shown subsequently. Macro-sized SnS, in contrast, is known
as a stable compound that does not easily react with semicon-
ductors or metals. However, at high temperatures it reacts
with transition metals to ternary compounds with totally differ-
ent properties, like Sn Co S or Sn Ni S , in solid state reactions.
Small particles with different morphologies facilitate tuning of
interesting optical, magnetic, electrical, and chemical proper-
ties compared to their bulk counterparts. In recent years, inten-
sive research has been devoted to nano- and microcrystalline
2
3
2
2
3 2
The control of respective reactions at the nanoscale should
provide a way to understand and exploit related extended
functionality.
[
1,2]
metals and chalcogenides.
veloped for transition metal, binary oxide, and chalcogenide
Synthetic concepts are well-de-
[
3,4]
nanoparticles.
Building on these concepts, the transforma-
Bulk compounds AM S=A [M S ] were classified as multi-
3/2
2
3 2
tion to other binary or ternary compounds is desirable to en-
hance applications or functionality. However, established meth-
ods are poorly transferable for the synthesis of multimetal or
intermetallic compounds for enhanced functions, for example,
metal-ordered half antiperovskites (HAP) with layered partial
[10–13]
[M S ] structures.
These attracted attention, because the
3
2
magnetic and electronic properties can be tuned by substitu-
tion of M=Ni, Co, Rh, Pd and A=In, Tl, Pb, Sn. The properties
and supposed applications are related to intermetallic A–M
and chalcogenide-like behavior and range from small bandgap
[
5,6]
for catalysis.
To grow related ternary and multinary systems,
improved synthesis strategies have to be developed to control
formation, growth mechanisms, and shape.
[
14–16]
semiconductors and thermoelectrics
to half-metal ferro-
[16,17]
[18–21]
The concept can be exemplified for the semiconductor SnS.
At the nanoscale its electronic gap can be tuned from 1.4 to
magnets
and catalysts.
Known ways of synthesis pro-
vide indications that transformation of semiconductors, metals,
and intermetallics are possible, as exemplified for semi-metal
Sn Ni S . In the solid state it is obtained from the elements (Ni,
2.0 eV. This leads to promising nanoelectronic, optoelectronic,
thermoelectric, photocatalytic, solid state battery, photovoltaic,
2
3 2
[
7–9]
near infrared detector, and biomedical applications.
For in-
Sn, S), or from heazlewoodite (Ni S ) and elemental Sn, or from
3 2
[22,23]
terfaces, multilayer, or combined functions, the reactivity of
SnS nanoparticles becomes decisive. The same applies for in-
terlayer or transformation reactions to multinary compounds
SnS and Ni at 9008C.
Reaction mechanisms are not yet
known, pure samples are hardly obtained, and it is barely pos-
sible to influence the size or to selectively control the mor-
phology of particles under these conditions. However, this be-
comes possible at the nanoscale.
Subsequently, not only a solution-based route for the mor-
[
a] S. M. Rommel, Dr. R. Weihrich
Institute of Inorganic Chemistry
phology-controlled reaction of SnS to nanosized Sn Ni S at
2
3 2
University of Regensburg
Universitätsstr. 31, 93040 Regensburg (Germany)
E-mail: richard.weihrich@chemie.uni-regensburg.de
a temperature below 2008C is shown for the first time, but
also an elucidation of the reaction mechanism. A reductive dif-
2+
fusion of Ni into SnS is proposed. By varying reaction param-
[
b] Dr. R. Weihrich
eters, the formation of core-shell particles, Sn Ni S , Ni S , and
2
3
2
3 2
Departement of Chemistry
TU Munich
Lichtenbergstr. 4, 85474 Garching (Germany)
Ni1.523Sn can be controlled from a modified polyol synthesis for
[24]
isotypic Pb Ni S . This study serves as a prototype for the
2 3 2
Chem. Eur. J. 2015, 21, 9863 – 9867
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formation of similar or completely new phases by carefully ad-
justing the general method.
Results and Discussion
One-pot reaction of SnS to Sn Ni S
3 2
2
For the optimized synthesis of Sn Ni S , SnS was reacted
spherical
2
3
2
with NiCl ·6H O at 1978C for 10.5 h with ethylenediamine (en)
2
2
and NaOH in ethyleneglycol (eg) as reducing agents and sol-
vent. Essentially phase-pure spherical SnS was used as reactive
template in the synthesis. Some small reflections of the SnS
sample can be attributed to elemental Sn (Figure 1a, marked
2 3 2
Figure 2. Energy dispersive X-ray spectrum of the optimized Sn Ni S
sample.
2 3 2
Figure 3. SEM images of a,b) SnS and c,d) Sn Ni S at a magnification of 2
and 5 mm, respectively.
Figure 1.
XRD pattern of a) SnS. Almost phase-pure SnS was obtained according to
reference [25] and used as template. Elemental Sn as side phase is marked
with an asterisk, b) Sn Ni S , which was synthesized at 1978C for 10.5 h, with
2 3 2
a slow heating ramp and stops for half an hour at 50, 100, 1508C during the
heating process.
These results suggest a template-dependent growth mecha-
nism. We suppose that SnS acts as both precursor and reactive
template, which is converted into the ternary Sn Ni S . A plau-
2
3 2
sible formation mechanism of the ternary nanostructure in-
volves at least three steps [Eq. (1)–(3)]. When en is added to
2
+
with an asterisk). During the heating process, the temperature
the reaction mixture, the stable nickel complex Ni(en)
is
which is indicated by a change in
x
[28,29]
was kept constant for half an hour at 50, 100, and 1508C,
formed immediately,
before raising the temperature with a low heating ramp
color of the solution to purple. The formation of this complex
À1
2+
(about 38Cmin ).
is essential for the whole reaction, as free Ni tends to form
XRD data for Sn Ni S (Figure 1b) confirms the trigonal shan-
nickel sulfides, which is accompanied by the decomposition of
2
3 2
dite phase (space group R-3m, No. 166). No characteristic
SnS (see below). At higher temperatures of around 140–1608C,
2
+
peaks are observed for impurities, such as SnS, NiS, Ni SnS , or
the solution turns to black, as Ni(en)
x
decomposes slowly
6
2
[26]
2+
Ni Sn S , which are apparent in the phase diagram. Further
and Ni is reduced to the elemental state. This is associated
with the moderate intensity reductive characteristic of
9
2 2
evidence for the quality and the composition of the Sn Ni S
3 2
2
[20,30,31]
sample was obtained by energy dispersive X-ray spectroscopy
see Figure 2). The typical composition of 3:2:2 at.% for Ni, Sn,
en,
and also ethylene glycol itself in strong alkaline solu-
The in situ produced Ni is, in theory, highly active,
[32,33]
(
tion.
and S is observed at good agreement (3.17:2.10:2.00 at.%).
The refined lattice constants for the measured sample are
a=5.455(3) Š and c=13.188(3) Š, which is in accordance with
the previously reported data (a=5.4606(2) Š and c=
and it can be incorporated immediately in the present SnS
[34]
under retention of its shape.
Ni þ x en Ð ½NiðenÞxŠ2þ
2
þ
ð1Þ
ð2aÞ
ð2bÞ
ð3Þ
[
18]
1
3.188(1) Š). An average crystallite size of 21.8 nm was esti-
[
27]
mated by the Scherrer equation, based on XRD line widths
calculated at the highest peak, hkl 246). Figure 3a–d shows
SEM images of SnS nanospheres and as-prepared Sn Ni S at
HOCH
2
CH
2
OH ! CH
3
CHO þ H
O
2
(
2
þ
þ 2 Hþ
2 Ni þ 2 CH
CHO ! 2 Niin situ þ CH
COCOCH
3 3
2
3 2
3
different magnifications. It is obvious that the products adopt
the same spherical shape as the precursor SnS.
2
SnS þ 3 Niin situ ! Sn Ni S
2
3 2
Chem. Eur. J. 2015, 21, 9863 – 9867
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Interesting results were obtained when the proposed mech-
anism was studied using different temperatures, morphology
of the SnS template, and reducing agents. Therefore, a series
of related experiments was designed.
Role of ethylene glycol and ethylenediamine
The solvent medium and reducing agent ethylene glycol has
often been used for reduction of metal ions and also as an in-
[
32,33]
hibitor for coagulation.
The present studies confirm that
NiCl ·6 H O can be reduced to the elemental state by just re-
2
2
fluxing in ethylene glycol and NaOH, with or without the addi-
tion of ethylenediamine [Eq. (4)]. Nevertheless, without ethyle-
nediamine, larger and agglomerated Ni particles are obtained,
[
33,35,36]
which is in accordance with the literature.
Furthermore,
Figure 4. a) Reaction products of a synthesis with a rapid heating ramp.
b) Reaction products of a synthesis where all starting materials were injected
into the refluxing solution.
the formation of a certain amount of nickel sulfides is observed
when en is not added to the solution. In the present case,
[37]
[38]
2À
NiS and Ni3S2 are then formed, with S released from SnS.
[
39]
2À
Intermetallic Ni1.523Sn
is also found, which is assumed to
centration of S in solution is due to the dissolution equilibri-
2
+
2+
2À
result from a co-reduction of Sn and Ni [Eq. (5a)–(7b)].
um of SnS and increases at high temperature. When S is con-
sumed by the formation of NiS, it is recovered by dissolving
SnS in accordance with the concept of Le Chatelier [Eq. (5a,b)].
By extending the reaction time and keeping the rapid heating
ramp constant, SnS disappears, but the amount of Sn Ni S
3 2
2
þ
À
Red :
Ni þ 2 e ! Ni
ð4Þ
ð5aÞ
ð5bÞ
ð6aÞ
ð6bÞ
ð7aÞ
ð7bÞ
Sol: eq: : SnS Ð Sn þ þ S2À
2
2
does not increase. Instead, the quantity of Ni S rises, which is
3
2
Sol: eq: : Ni þ S2À Ð NiS
2
þ
2+
an indicator of progressive reduction of Ni , which is present
in NiS [Eq. (6a,b)]. At long reaction times Ni1.523Sn appears,
3 Ni þ 2 S2À þ 2 e ! Ni S
2
þ
À
Red :
Red :
Red :
3
2
2+
2+
which is either the product of a co-reduction of Ni and Sn
2
+
À
2À
or a further reductive interdiffusion process of Sn on Ni par-
ticles [Eq. (7a,b)].
3 NiS þ 2 e ! Ni S þ S
3 Ni þ 2 Sn þ þ 4 e ! Ni Sn
3
2
2
À
3
2
Co-Red : 2 Sn þ 3 Ni2þ þ 10 e ! Ni Sn
2þ
À
Role of the SnS source
3
2
In addition to the importance of the reaction temperature and
heating ramp we found that the tin sulfide source plays an im-
portant role in this modified polyol process. Two kinds of SnS
sources (SnSspherical, SnSbulk) were tested for the preparation of
Sn Ni S . As shown before, it is possible to synthesize the
Red=reduction, Sol. eq.=solution equilibrium, and Co-Red=
co-reduction.
2
3 2
Effect of heating ramp, temperature, and reaction time on
products
phase-pure shandite phase, when using spherical SnS under
optimized conditions. Whereas, when SnSbulk (prepared by
a solid-state method) is used, only small amounts of the target
shandite phase are observed. Prominent side phases Ni S , and
2
+
The temperature-dependent stability of the [Ni(en)x] complex
explains the challenging reproducibility and sensitivity of the
reaction using different heating ramps and temperatures. With
the initially described slow heating ramp, the formation of
3
2
Ni1.523Sn, plus a small unknown phase, are also apparent. Differ-
ent heating ramps and reaction times did not increase the
amount of Sn Ni S . One can conclude that the morphology of
2
+
Sn Ni S from SnS and Ni in eg with en starts at a tempera-
2
3
2
2
3 2
2
+
ture below 1668C. In this temperature region the Ni(en)
the applied SnS precursor plays a key role in the synthesis of
Sn Ni S . As diffusion in nanoparticles is much faster than in
x
2
+
complex starts to decompose and Ni is slowly released to
the reaction solution and rapidly reduced. The Ni formed in
situ should then be incorporated immediately into SnS to form
2
3 2
[40]
the bulk materials, this can possibly lead to facilitated chemi-
cal transformation of the particles. The spherical shape of the
precursor makes it extremely susceptible to its surroundings
and Ni can diffuse into the lattice more easily.
2
+
Sn Ni S . At a low Ni concentration, reduction is thus pre-
2
3 2
ferred. By using a rapid-heating ramp, NiS, Ni S , and unreacted
3
2
SnS are found as products in the XRD patterns (see Figure 4a).
2
+
Clearly, Ni(en)x and SnS decompose too quickly under these
conditions. The formation of NiS is then related to high con-
Hydrazine as reducing agent (Ni-coated SnS)
2
+
centration of uncomplexed Ni .This clearly demonstrates the
role of the solubility product of NiS, which is reached when
When ethylenediamine is replaced by hydrazine as the addi-
tional reducing agent and the temperature is lowered to 708C,
only a small amount of Sn Ni S is formed, and the main prod-
2
+
Ni is not hidden in the en–complex. Furthermore, the con-
2
3 2
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ucts were Ni and SnS according to the X-ray diffraction data
Figure 5). Figure 5a shows the pristine SnS, whereas Figure 5b
described before, and refluxed at 1978C for 10.5 h; by using
Ni3S2,bulk and SnCl ·2H O as starting materials, the reaction
(
2
2
shows the products after reaction with the addition of hydra-
stopped at Ni S , with a small NiS side phase. NiCl ·6H O,
3 2 2 2
SnCl ·2H O, and Na S/S also resulted in Ni S and NiS, with the
2
2
2
3 2
addition of Ni1.523Sn, when Na S was applied. These results alto-
2
gether underline that one challenging point of the synthesis is
the integrity of SnS. After dissolution of SnS it is not possible
to get to the Sn Ni S phase. With careful adjustments, the
2
3 2
method should be applicable to other M+AX systems too, in-
[41]
cluding compounds with varying M content like PtSnS or
[42]
Pd InSe.
5
Conclusion
Nanocrystalline Sn Ni S could be directly prepared for the first
2
3 2
time under ethylene glycol reflux at a temperature as low as
50–1978C. It was evident that the supporting chelating and
1
reducing agent ethylenediamine, the reaction temperature,
and the morphology of the precursor play an important role in
the synthesis. A reductive diffusion-based mechanism with SnS
as reactive template was discussed. After rapid reduction of
Figure 5. a) Pristine SnS. b) Product after reaction with hydrazine to Ni@SnS
core-shell particles. c) Reaction of Ni@SnS to Sn Ni S in a solid state reaction
2 3 2
at 7008C (5 days).
2
+
Ni with hydrazine at 708C, Ni does not diffuse into SnS, but
core-shell-particles are formed. However, they can be trans-
ferred to the ternary Sn Ni S by solid-state reactions at T>
2
+
zine. The reduction of Ni seems to be too fast to form
Sn Ni S under these conditions, so that elemental Ni is formed
2
3 2
2
3
2
2+
2À
5
008C. At high concentrations of uncomplexed Ni and S ,
on SnS (marked with an asterisk). No consecutive reactions are
observed in solution, especially for SnS, which does not dis-
solve. The washed and dried product reacts to Sn Ni S in
the binary sulfides NiS and Ni S are formed and SnS is dis-
3
2
solved. Additionally, under the present reductive conditions
2
3
2
2+
Sn forms the intermetallic Ni1.523Sn after a long reaction time.
a solid state reaction at T=500–7008C (Figure 5c, small side
The present study shows that binary compounds can indeed
be transformed to ternaries with different functions. Thereby,
core-shell particles can be designed based on the rate of re-
duction. The discussed method leads to ways to obtain related
compounds and functionalized materials.
phases of Ni S and Ni1.523Sn are marked with # and +, respec-
3
2
tively). We conclude on the formation of core-shell particles
Ni@SnS.
The whole system presented is determined by equilibrium
and redox reactions [Eq. (4)–(7b)], which have been summar-
ized in Scheme 1. As shown above, the concentration of free
2
+
0
Ni is particularly crucial for the competing reduction to Ni
or the formation of NiS.
Experimental Section
Synthesis
Preparation of spherical SnS (SnSspherical) particles: SnS starting
material was prepared by a modified solvothermal route described
in reference [25]. Sn powder and excess thiourea were added to
a glass ampoule that had been filled with the solvent mixture
(water/ethylenediamine=1:1) up to 80% of the total volume. The
ampoule was sealed and maintained at 1808C for 12 h. After cool-
ing down to room temperature the products were washed thor-
oughly with distilled water and ethanol and dried at 758C.
2
+
Scheme 1. Equilibrium and redox reactions in the SnS, [Ni(en)] system.
Preparation of spherical Sn Ni S : The particles were prepared
2
3 2
from a stoichiometric mixture of NiCl ·6H O (0.1676 g, 0.71 mmol)
and SnSspherical (0.0709 g, 0.47 mmol) in a 250 mL round-bottom
flask. SnSspherical was added to the flask, which was then filled with
2
2
Discussion of the mechanism of formation for Sn Ni S
3 2
2
To exclude any other mechanisms of formation for the Sn Ni S
3 2
2
7
0–100 mL ethylene glycol (eg) and magnetically stirred. After half
phase, like a dissolution–precipitation process, which proceeds
over chemical intermediates like Ni3S2 or NiS, the following
tests were conducted. In one approach all starting materials
were injected into refluxing ethylene glycol, which resulted in
NiS, Ni S , and Ni1.523Sn (Figure 4b). Further experiments were
an hour, NiCl ·6H O was added under continuous stirring. Lastly,
2
2
ethylenediamine (en, 4.75 mL) and NaOH (0.5126 g, 12.8 mmol)
were introduced to the reaction mixture. Following further stirring
for half an hour, the flask was heated to 166–1978C at different
heating ramps. After refluxing for 0.5 h–10.5 h, the mixture was
naturally cooled to room temperature. The products were filtered
3
2
all conducted at the optimized slow-heating ramp for Sn Ni S ,
2
3 2
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Preparation of Ni-coated SnS particle and transformation to
Sn Ni S : The synthesis of Ni@SnS follows the same procedure as
2
3 2
described for spherical Sn Ni S , with the exception that ethylene-
2
3
2
diamine is replaced by hydrazine. The mixture is kept at 60–708C
for 3 h under stirring. After cooling to room temperature, the prod-
ucts were filtered and washed several times with distilled water
and alcohol and dried at 758C overnight.
[
[
Analysis
The structure of the products was characterized by X-ray powder
diffraction, using a Huber G670 diffractometer equipped with an
imaging plate with monochromatic CuKa1 radiation (l=1.54060 Š,
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ating voltage of 15 kV. Morphologies of the as-prepared samples
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Digital Scanning Microscope DSM 950.
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Acknowledgements
The work was supported by the Deutsche Forschungsgemein-
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Published online on June 1, 2015
Chem. Eur. J. 2015, 21, 9863 – 9867
www.chemeurj.org
9867
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim