Reactive and organosoluble SnO2 nanoparticles by a surfactant-free non-hydrolytic sol-gel route

Article abstract of DOI:10.1002/ejic.201100391

Reactive SnO₂ nanoparticles have been successfully prepared by a simple non-hydrolytic sol-gel synthesis in CH₂Cl₂ t 110 °C by using SnCl₄ as a precursor and diisopropyl ether iPr ₂O) as an oxygen donor. The SnO₂ nanocrystals, with a iameter of about 4 nm, formed stable sols in organic aprotic olvents in the absence of any surfactant or coordinating gent. The lack of aggregation has been attributed to the resence of Cl and OiPr surface groups instead of OH roups. These surface groups render the nanoparticles reactive towards hydroxylated surfaces, as shown by their reaction with an oxidized silicon wafer; the nanoparticles bind niformly across the wafer to form a monolayer.

Full text of DOI:10.1002/ejic.201100391

FULL PAPER
DOI: 10.1002/ejic.201100391
Reactive and Organosoluble SnO Nanoparticles by a Surfactant-Free Non-
2
Hydrolytic Sol–Gel Route
[a]
[a]
[a]
Abdelhay Aboulaich, Bruno Boury,* and P. Hubert Mutin
Keywords: Sol–gel processes / Nanoparticles / Nanostructures / Synthetic methods / Tin
Reactive SnO
pared by a simple non-hydrolytic sol–gel synthesis in CH
at 110 °C by using SnCl as a precursor and diisopropyl ether
iPr O) as an oxygen donor. The SnO nanocrystals, with a
diameter of about 4 nm, formed stable sols in organic aprotic
solvents in the absence of any surfactant or coordinating
2
nanoparticles have been successfully pre-
agent. The lack of aggregation has been attributed to the
presence of Cl and OiPr surface groups instead of OH
groups. These surface groups render the nanoparticles reac-
tive towards hydroxylated surfaces, as shown by their reac-
tion with an oxidized silicon wafer; the nanoparticles bind
uniformly across the wafer to form a monolayer.
2
Cl
2
4
(
2
2
Introduction
We recently reported the synthesis, in the absence of any
stabilizing agent, of easily dispersible silica, silica–titania
[
40,41]
and titania nanoparticles
using another non-hydrolytic
Tin(IV) oxide is a semiconductor with a band gap of
sol–gel route (the “ether route”). Although the ether route
has proved highly successful in the synthesis of mesoporous
3.6 eV at 300 K and has been investigated for potential ap-
[
1–5]
[6–8]
plications as a sensor material,
photocatalyst,
anode
There-
[
42–44]
[
9,10]
[11–13]
mixed-oxide catalysts,
oxide nanoparticles.
it has not been used to prepare
material
as well as in photovoltaic devices.
fore there has been continuous interest in exploring syn-
This route is based on the reaction of silicon or metal
chloride precursors with stoichiometric bis(isopropyl) ether
thetic routes to SnO nanocrystals and nanostructures, in-
2
cluding flame pyrolysis,[
14,15]
[4,16]
thermal evaporation,
laser
[17]
[18–22]
(iPr O) as oxygen donor at moderate temperatures (80–
ablation of massive SnO2,
hydrothermal syntheses
2
and various sol–gel methods.[
23–32]
150 °C). It involves in the first step the “etherolysis” of the
chloride precursor leading to an isopropoxide [Equa-
tion (1)], which then condenses with the remaining chlo-
Based on non-hydrolytic (or non-aqueous) sol–gel pro-
cess,[
33,34]
Colvin et al. first reported on the synthesis of
[
33,34]
[35–37]
rides [Equation (2)].
oxide and mixed-oxide nanoparticles.
The “benzyl
alcohol” route based on the reaction of SnCl4 [or Sn-
(
OtBu) ] in benzyl alcohol appears particularly attractive
4
[
27,29,30,38,39]
(1)
for the synthesis of SnO -based nanocrystals
as
2
it leads to well-crystallized nanoparticles that can be dis-
persed in organic solvents without the use of any additional
stabilizers. Indeed, surfactants (e.g., trioctylphosphane ox-
ide, oleic acid or octylamine) are commonly used in nano-
(
2)
In this paper we report the extension of the ether route
particle syntheses to prevent aggregation and control the to the synthesis of SnO nanoparticles. Notably, we show
2
size and sometimes the shape of the particles. However, the that this route leads in very high yields to SnO nanopar-
2
adsorbed surfactant may influence the toxicity of the nano- ticles with several very original features: they can be redis-
particles and reduce accessibility to the nanoparticle surface persed in THF to form stable sols in the absence of any
as well as its reactivity, which could be detrimental to their stabilizer, their surfaces appear to be terminated by residual
applications in sensors or catalysis.[ Therefore synthetic Sn–Cl and Sn–OiPr groups (instead of Sn–OH groups),
routes to oxide nanoparticles without any stabilizer are which makes them highly reactive towards nucleophilic spe-
37]
worth exploring.
cies, and they can react with hydroxylated Si wafers to form
a monolayer of covalently bound nanoparticles.
[
a] Institut Charles Gerhardt de Montpellier, Chimie Moléculaire
et Organisation du Solide, Université Montpellier 2,
Results and Discussion
3
4095 Montpellier, France
Fax: +33-4-67143852
The nanoparticles were obtained in one step by heating
under autogenous pressure the precursor and oxygen donor
diluted in CH Cl [Equation (3)].
E-mail: bruno.boury@univ-montp2.fr
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201100391.
2
2
3644
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 3644–3649

2
Reactive and Organosoluble SnO Nanoparticles
(
3)
Information on the progress of the reaction was obtained
1
by H NMR analysis of the reaction mixture before and
after heating at 110 °C (Figure 1; the sample prepared by
1
heating at 110 °C is referred to as 110-SnO ). The H NMR
2
2
Figure 2. TEM image of the 110-SnO nanoparticles after disper-
sion and dilution in THF (left) and the corresponding particle size
distribution (right) determined by analysis of more than 200 par-
spectrum recorded after heating shows the complete disap-
pearance of the signals arising from iPr O (septuplet at δ =
2
3
.69 ppm and doublet at δ = 1.15 ppm) and the presence of ticles.
a septuplet at δ = 4.26 ppm and a doublet at δ = 1.55 ppm,
which indicates the formation of a large amount (Ͼ95%)
of the expected byproduct, iPrCl. A small signal at δ =
1.76 ppm (doublet of triplets) shows the presence of propyl-
ene, whereas the resonances at δ = 1.25 and δ ≈ 0.9 ppm
suggests the presence of propylene oligomers. These com-
pounds likely arise from the thermal decomposition of
iPrCl, leading to propylene and HCl, followed by the poly-
merization of propylene. Both reactions could be catalysed
by Sn species. The yield (based on the weight of SnO after
2
calcination in air) was very high (88%).
2
Figure 3. Schematic representation of a nanoparticle in 110-SnO .
At this point there is no control during the synthesis of
the amount of residual chlorine and isopropoxide groups.
As a stoichiometric amount of ether was used and as the
etherolysis step appeared to be complete, the amount of re-
sidual chlorine and alkoxide groups should be similar.
However, in principle it should be possible to favour the
formation of either chloride or isopropoxide surface groups
by using either an excess of SnCl or an excess of iPr O.
1
Figure 1. H NMR spectra of the starting solution of mixed reagent
4
2
before heating (bottom) and of the crude mixture after reaction at
10°C (top).
Another possibility would be a post-modification of the
nanoparticles, for instance, with an alcohol, which would
1
The TEM image of the 110-SnO powder redispersed in substitute the chloride and isopropoxide groups.
2
THF evaporated on a grid (Figure 2) shows the presence of
The absence of residual OH groups and the presence of
well-dispersed nanoparticles with rounded shapes; the OiPr were confirmed by FTIR spectroscopy (Figure 4). The
nanoparticles exhibit a narrow size dispersity and an bands characteristic of OiPr groups (C–H vibrations at
average diameter of about 4 nm. The absence of aggregation 1364, 1455 and 2978 cm–1 and C–O vibrations at 1041 cm )
of the nanoparticles is ascribed to the chemistry involved disappear upon calcination at 500 °C (sample denoted as
–1
[
40,41]
in this process.
Indeed, in the absence of secondary 500-SnO ). The 110-SnO powder reacts readily with water
2 2
reactions, the non-hydrolytic process used here leads to and the spectrum of a sample exposed to ambient humidity
–1
chloride and isopropoxide surface groups [Equations (2) is dominated by very broad bands at around 3000 cm and
–1
and (3), Figure 3] instead of the Sn–OH groups usually a band at 1614 cm , which indicate the presence of hydro-
present at the surface of oxide particles. The presence of gen-bonded OH groups and adsorbed water.
residual Sn–Cl groups in the 110-SnO sample (9.5 wt.-%
The dispersibility of the nanoparticles in aprotic organic
2
Cl) was confirmed by the acid–base titration of an aqueous solvents such as THF can be ascribed to the presence of
suspension of the powder, whereas the carbon content surface Cl and OiPr groups, which make the nanoparticles
(8.9 wt.-%) is consistent with the presence of residual Sn– organophilic. The stability of the sols (in the absence of
OiPr groups. The average formula derived from the C and water) has to be related to the very low rate of Cl/OiPr
Cl content is SnO1.5(OiPr)0.4(Cl)0.6. This average formula is condensation [Equation (2)] at room temperature.
in good agreement with the weight loss (32%) determined
Conversely, the presence of Sn–Cl and Sn–OiPr functions
by TGA in air for 110-SnO (see Figure S1), assuming con- and the absence of any stabilizing agent at the surface
2
version to SnO2.
render these “naked” nanoparticles highly reactive towards
Eur. J. Inorg. Chem. 2011, 3644–3649
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3645

A. Aboulaich, B. Boury, P. H. Mutin
FULL PAPER
2
Figure 6. AFM image of a monolayer of 110-SnO nanoparticles
deposited on an oxidized Si wafer (left) and the corresponding
height distribution (right).
2
Figure 4. Transmission FTIR spectra of (a) dried 110-SnO ,
(
b) 500-SnO
2 2
and (c) dried 110-SnO nanoparticles after exposure
to ambient humidity for 60 min.
nucleophiles such as water, alcohols or silanols. This reac-
tivity allows SnO nanoparticles to be anchored to hydrox-
2
ylated surfaces, as depicted in Figure 5. The nanoparticles
will bind to the surface by condensation of the surface hy-
droxy groups with residual Sn–Cl and Sn–OiPr groups.
Moreover, in the absence of water and at room temperature,
the nanoparticles do not bind to each other by Sn–Cl/Sn–
OiPr condensation, thus the reaction should stop after the
formation of a single monolayer of nanoparticles.
Figure 7. AFM image of the surface of a silicon wafer after dipping
for 2 h in a CH
2 2 2
Cl /EtOH/110-SnO sol (left) and corresponding
height profile (right) across the surface.
The powder XRD pattern of dried 110-SnO (Figure 8)
2
shows the presence of poorly crystalline SnO . The particu-
2
larly broad reflection at around 27° suggests the presence
of an amorphous phase, possibly adsorbed organic com-
pounds. This broad component disappears after treatment
Figure 5. Deposition of a monolayer of SnO
2
nanoparticles by di-
rect contact between reactive SnO
ated surface.
2
nanoparticles and an hydroxyl-
in air at 300 °C (300-SnO ), whereas the other reflections
2
were not significantly affected. As expected, heat treatment
This was demonstrated by immersing an oxidized silicon at 400 (400-SnO ) and 500 °C (500-SnO ) led to the growth
2
2
wafer for 2 hours in a sol of 110-SnO nanoparticles in of SnO crystals, as shown by the decrease of the peak
2
2
THF (0.7 wt.-% in SnO ). After washing the wafer in an widths. All the peaks could be indexed to the standard cas-
2
ultrasonic bath an AFM image was recorded that shows siterite SnO2 phase (JCPDS Card No. 41-1445). The
the presence of a dense nanoparticle layer on the surface average crystallite size [estimated from the widths of the
(Figure 6). The corresponding height distribution shows a (110) and (101) reflections using Scherrer’s equation] in-
sharp peak, ascribed to holes between nanoparticles, and a creases from about 3 to 14 nm (Table 1) between 300 and
broader peak (shoulder) in the 3–8 nm range, consistent 500 °C.
with the formation of a monolayer of nanoparticles.
Interestingly, the deposit can be tuned by changing the the decrease in the specific surface area from 180 m g for
deposition solvent. Indeed, when the same procedure was dried 110-SnO to 70 m g for 500-SnO (Table 1). The
The growth of the SnO crystallites is also evidenced by
2
2
–1
2
–1
2
2
performed in an ethanol/THF mixture (volume ratio 1:1), average diameters estimated from the specific surface areas
the number of particles anchored at the wafer surface dras- are similar to those determined from the XRD patterns,
tically decreased (Figure 7). This indicates that the reactiv- which indicates that the nanoparticles are monocrystalline
ity of the particles with the wafer surface decreased, most and non-porous.
likely due to the reaction of the nanoparticles and/or wafer
The TEM images (Figure 9) of dried 110-SnO show the
2
surface groups with EtOH. However, the height of the par- presence of small spherical aggregates of around 15 nm
ticles dispersed on the wafer surface ranged between 5 and built of primary nanoparticles (≈4 nm). After calcination at
8
nm, which suggests some aggregation of the nanopar- 500 °C, spherical aggregates with diameters of around
ticles, possibly due to the presence of traces of water in the 300 nm formed by the self-assembly of primary nanopar-
ethanol used. ticles (≈15 nm). A similar morphology has previously been
3646
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 3644–3649

2
Reactive and Organosoluble SnO Nanoparticles
[
45]
yet been elucidated. The very broad feature between 400
and 700 cm–1 has been ascribed to surface modes and is
very sensitive to the specific surface area and the level of
[
46]
crystallinity of the particles.
2
Figure 8. XRD patterns of dried 110-SnO before and after calci-
nation for 2 h at 300, 400 and 500 °C in dry air.
Table 1. Average diameters of the nanoparticles estimated by poros-
imetry (BET method) and XRD.
Samples
BET
S [m g ], D [nm]
XRD
D [nm]
2
–1
[a]
Dried 110-SnO
2
180, 4.8
180, 4.8
90, 9.7
–
2
Figure 10. Raman spectra of the SnO samples.
3
4
5
00-SnO
00-SnO
00-SnO
2
2
2
3.1
8.4
13.9
Indeed, in our case, the intensity of this band decreased
with the specific area. Interestingly, a clear correlation has
70, 12.4
[
a] Calculated from the specific surface area S by using the expres- been reported between the intensity of the surface modes
sion D = 6000/(dS), with d representing the cassiterite density (6.9).
[45]
and the response of SnO gas sensors to CO.
2
reported for mesoporous titania–vanadia catalysts prepared
by the same non-hydrolytic sol–gel route.[
42]
Conclusions
The Raman spectra of the different samples are displayed
–
1
The results reported herein show that organo-soluble and
reactive SnO nanoparticles with low size polydispersity can
in Figure 10. All the spectra show the A (630 cm ) and
1
g
–
1
B2g (770 cm ) modes typical of the tetragonal structure of
2
be obtained by the reaction of SnCl with a stoichiometric
amount of iPr O in CH Cl at 110 °C. The nanoparticles
cassiterite. In addition, the spectra of 110-SnO , 300-SnO2
4
2
and 400-SnO display a very broad feature between 400 and
2
2
2
2
–
1
–1
can be easily dispersed in THF, leading to a stable sol of
well-dispersed nanoparticles (≈4 nm). These nanoparticles
appear to be terminated by chloro and isopropoxy groups,
which accounts for their original properties: their organ-
ophilic character, the absence of aggregation at room tem-
perature in the absence of water and their reactivity towards
nucleophiles. This unique surface chemistry and the absence
of non-hydrolytic condensation at room temperature allow
the self-limiting anchoring of nanoparticles to hydroxylated
surfaces. The low synthesis temperature, the excellent yield
and the high surface area of the nanoparticles are ad-
ditional valuable points. This simple synthetic route should
be applicable to other metal oxides, provided that the chlo-
ride precursors are soluble in aprotic organic solvents such
as dichloromethane or chloroform.
7
00 cm and several bands in the 200–400 cm region.
These 200–400 cm bands have previously been reported
–
1
for several nanostructured SnO , but their origin has not
2
Experimental Section
Materials: Tin tetrachloride (99.99% Aldrich) was used without
further purification. Bis(isopropyl) ether (iPr
tetrahydrofuran (THF; 99% VWR) were purified by distillation
over sodium wire under N and CH Cl by distillation over P
2
O; 99% Acros) and
Figure 9. SEM images of (a,b) dried 110-SnO
2
and (c,d) 500-SnO
2
.
2
2
2
2 5
O .
Eur. J. Inorg. Chem. 2011, 3644–3649
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3647

A. Aboulaich, B. Boury, P. H. Mutin
FULL PAPER
Synthesis of SnO
out under argon using standard Schlenk techniques and a glovebox
MBRAUN, H O Ͻ 0.1 ppm, O Ͻ 0.1 ppm). The water content
in iPr O and CH Cl (determined by Karl-Fischer titration) was
lower than 10 ppm. In a typical experiment, SnCl (1.33 g,
.11 mmol), iPr O (1.045 g, 10.22 mmol) and CH Cl (31 mL) were
successively introduced under argon into a 70 mL Pyrex tube that
was sealed after freezing the mixture in liquid nitrogen. The tube
was heated at 110 °C for 60 h, then cooled to room temperature
and opened in a glovebox. The white suspension was transferred
to a centrifugation tube, which was closed, and the precipitate iso-
lated by centrifugation (10 min, 20000 rpm). The white precipitate
2
Nanoparticles: All manipulations were carried
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Acknowledgments
[
We wish to thank Prof. Thierry Toupance from ISM Bordeaux 1
for fruitful discussions on the synthesis and characterization of the
[
SnO
2
nanoparticles.
Wark, M. Niederberger, Chem. Mater. 2006, 18, 2848.
3648
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 3644–3649

2
Reactive and Organosoluble SnO Nanoparticles
[
[
[
[
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