Inorganic Chemistry
ARTICLE
were first dried with thionylchloride, washed with toluene, dried in vacuum,
Transmission Electron Microscopy. For TEM investigations
the sample was suspended in ethanol and dropped onto a carbon coated
copper grid. The images were obtained using a Philips EM420 instru-
ment with an acceleration voltage of 120 kV.
For HRTEM investigations the sample was also suspended in ethanol
and sprayed onto a carbon coated copper grid using the sonifier
described in ref 44. The TEM work was carried out with a Tecnai F30
S-TWIN transmission electron microscope equipped with a field emis-
sion gun working at 300 kV. High-resolution (HR-) TEM and electron
diffraction patterns were acquired with a CCD camera (14-bit GATAN
794MSC).
and stored in a glovebox under N atmosphere. Tetrahydrofuran was dried
2
with CaCl
onhydride Li[Et
and SbCl (ABCR, 99.99%) were used as obtained, and SbCl was stored in
2
and Na/K and freshly distilled before use. Lithium triethylbor-
3
BH] (Aldrich, 1 M in THF, referred to as “superhydride”)
3
3
a glovebox. Zn particles were synthesized by the reaction of ZnCl with
2
2
equiv of the 1 M solution of superhydride in THF at ∼65 °C. The
particles were washed several times with THF, dried in a vacuum, and
stored in a glovebox. Sb particles, Ni particles, and Cu particles were
3 2
produced by reducing SbCl , NiCl , and CuCl with 3, 2, and 1 equiv of the
1
M superhydride solution at room temperature, respectively. The black
particles were repeatedly redispersed in THF and decanted from the
solution, dried in a vacuum, and kept in a glovebox.
Synthesis of Binary Antimonide Nanoparticles. Trioctyla-
mine and tetraethyleneglycol (Aldrich, 98%) were degassed and stored
under Ar before use.
’
ASSOCIATED CONTENT
Supporting Information. (1) H NMR data of Sb,
1
S
b
1
measured under Ar; (2) H NMR data of Sb, measured under
ambient air; time-dependent and temperature-dependent
(ex situ) X-ray diffraction plots of (3) formation of NiSb and
CoSb. In a typical synthesis, nanoparticles of the nominal composition
CoSb were prepared by heating of Sb-nanoparticles (1 mmol) and
Co (CO) (0.5 mmol) in tetraethyleneglycol (ultrasound bath for 10
2
8
(4) formation of Cu Sb; (5) X-ray diffraction, Rietveld refine-
2
min) with a heating rate of about 5 K/min. The reaction mixture was
heated to ca. 280 °C. For intermediate products, 2 mL of the solution
was extracted by syringe at approximately 150, 200, 250, and 280 °C.
After the solution was cooled to room temperature, the resulting black
product was collected by centrifugation (9000 rpm), washed with
ethanol, and dried under a steady Ar flow.
ments, and corresponding difference plots of the final ZnSb
product. This material is available free of charge via the Internet
at http://pubs.acs.org.
’
AUTHOR INFORMATION
NiSb. In a typical synthesis, nanoparticles of the nominal composition
NiSb were prepared by heating of Sb-nanoparticles (1 mmol) and Ni-
nanoparticles (1 mmol) in tetraethyleneglycol (ultrasound bath for
Corresponding Author
*Phone: +49 6131 392-5135. Fax: +49 6131 392-5605. E-mail:
tremel@uni-mainz.de.
10 min) with a heating rate of about 5 K/min. The reaction mixture was
heated to ca. 170 °C and held there 210 min. For intermediate products,
’
ACKNOWLEDGMENT
2
1
mL of the solution was extracted by syringe at approximately 70, 80,
40, and 170 °C. After the solution was cooled to room temperature, the
resulting black product was collected by centrifugation (9000 rpm),
washed with ethanol, and dried under a steady Ar flow.
This research was supported by the DFG priority program
SPP1386 Nanostructured Thermoelectrics. C.S.B. and G.K. are
recipients of a fellowship from MATCOR, the Graduate School
of Excellence of the State of Rhineland-Palatinate.
Cu
tion Cu
and Cu-nanoparticles (2 mmol) in tricotylamine (ultrasound bath for
0 min) with a heating rate of about 5 K/min. The reaction mixture was
2
Sb. In a typical synthesis, nanoparticles of the nominal composi-
2
Sb were prepared by heating of Sb-nanoparticles (1 mmol)
’
REFERENCES
1
(
(
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1
963, 35, 1–&.
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0 and 100 °C. After the solution was cooled to room temperature, the
(
resulting black product was collected by centrifugation (9000 rpm) and
washed with ethanol. Afterward, the black powder was washed two times
(
with 1 M HCl in saturated NH Cl solution to remove possible Cu
4
residues. The powder was then again washed with ethanol and dried
under a steady Ar flow.
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(
(
3
00 °C at a rate of ca. 15 K/min in a polar, strongly coordinating solvent
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product was then washed with ethanol and dried with streaming Ar to a
dry powder.
(
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2
(
(
5
X-ray Powder Diffraction. X-ray powder diffraction data were
collected with a Bruker-AXS D8-Discover diffractometer in reflection
geometry equipped with a HiStar detector using graphite monochromatized
Cu KR radiation. Samples were glued on top of glass and (111) silicon
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vinylacetate). Rietveld refinements were performed with TOPAS Academic
(
(
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41
v4.1 applying the fundamental parameter approach.
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dx.doi.org/10.1021/ic200074z |Inorg. Chem. 2011, 50, 6938–6943