F. Shi et al.
spectros
ACHTUNGTRENNUNG
from the reaction mixture, and it can be reused for several
runs without obvious deactivation. To the best of our knowl-
edge, several transformations were realized for the first time
by using a heterogeneous non-noble metal catalyst, that is,
selective alcohol amination with ammonia to produce pri-
mary or secondary amines, secondary aliphatic alcohol ami-
nation, diol amination, and alcohol amination with di-
CALAB 210 instrument equipped with
a
source, a hemispherical capacitor analyzer, and a 5 keV Ar+ ion gun. All
spectra were recorded by using nonmonochromatic MgKa (1253.6 eV) ra-
diation. The samples were fixed to a stainless steel sample holder by
using double-sided adhesive carbon tape. The electron binding energy
was referenced to the C1s peak at 284.8 eV. The peaks were fitted by
Gaussian–Lorentzian curves after a Shirley background subtraction. For
quantitative analysis, the peak area was divided by the element-specific
Scofield factor and the transmission function of the analyzer. The back-
ground pressure in the chamber was less than 10À7 Pa. Nitrogen adsorp-
tion–desorption isotherms were measured at 77 K by using a Micromerit-
ics 2010 instrument. The pore-size distribution was calculated from the
desorption isotherm by using the Barrett, Joyner, and Halenda (BJH)
method. The Cu, Ni, and Fe contents of the catalysts were measured by
using inductively coupled plasma atomic emission spectrometry (ICP-
AES), by using an Iris advantage Thermo Jarrel Ash device. NMR spec-
tra were measured by using a Bruker ARX 400 or ARX 100 spectrome-
ter at 400 MHz (1H) and 100 MHz (13C). All spectra were recorded in
CDCl3 or [D6]DMSO and chemical shifts (d) are reported in ppm relative
to tetramethylsilane referenced to the residual solvent peaks.
ACHTUNGTRENNUNG
Experimental Section
All solvents and chemicals were obtained commercially and were used as
received.
Typical procedure for catalyst preparation: Cu
5.1 mmol), Ni(NO3)2·6H2O (6.0 g, 20.7 mmol), Fe
5.0 mmol), and Al(NO3)3·9H2O (2.0 g, 5.3 mmol) were added to deion-
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ized water (150 mL) and agitated until complete dissolution. Then, aque-
ous Na2CO3 (50 mL, 1.7m) was added dropwise and the mixture was stir-
red for a further 2 h at RT. The reaction mixture was centrifuged and
washed with water to remove the base until the pH value of the aqueous
solution was ꢀ7. Subsequently, the solid was dried at 1208C for 4 h, cal-
cined in air at 4508C for 5 h, and reduced under a hydrogen flow for 2 h.
The solid catalyst sample was treated with aqueous NaOH (10m) to
remove the aluminum, then the solid sample was washed with EtOH (2ꢂ
20 mL) and Et2O (2ꢂ20 mL) and vacuum dried for 0.5 h. About 1.8 g of
a black solid sample, that is, moisture- and air-stable Raney-type catalyst,
was obtained and denoted as NiCuFeOx. According to the ICP-AES
measurement, the Ni, Cu, and Fe contents are 43.4, 13.4, and 12.1 wt%.
Acknowledgements
We thank the National Natural Science Foundation of China (21073208)
and the Chinese Academy of Sciences for financial support.
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The BET surface area of the obtained catalyst is 127 m2gÀ1
.
Typical procedure for the N-alkylation of amines with alcohols: Amine
(1.0 mmol), alcohol (1.0 mmol), catalyst (50 mg), and xylene (2 mL) were
added to a 40 mL pressure tube equipped with a magnetic stirrer. The
pressure tube was exchanged three times with argon and reacted under
xylene at reflux for 24 h, then cooled to RT. Acetone (ꢀ10 mL) was
added to dissolve the reaction mixture, which was filtered with Celite.
The crude reaction mixture was concentrated in vacuo and purified by
column chromatography (eluent: petroleum ether/ethyl acetate/meth-
ACHTUNGTRENNUNGanol) to give the N-alkyl amine in good yields.
Typical procedure for the N-alkylation of ammonia with alcohols:
(NH4)2CO3 (0.6 mmol; 1.2 mmol of ammonia the decomposition temper-
ature of ammonium carbonate is 588C), alcohol (1.0 mmol), catalyst
(80 mg), and xylene (2 mL) were added to a 20 mL pressure tube equip-
ped with a magnetic stirrer. The pressure tube was sealed and exchanged
three times with argon, then reacted under xylene at reflux for 24 h
before being cooled to RT. Acetone (ꢀ10 mL) was added to dissolve the
reaction mixture, which was filtered with Celite. The crude reaction mix-
ture was concentrated in vacuo and purified by column chromatography
(eluent: petroleum ether/ethyl acetate/methanol) to give the N-alkyl
amine.
Characterization of catalysts and products: XRD measurements were
conducted by using a STADI P automated transmission diffractometer
(STOE) equipped with an incident beam curved germanium monochro-
mator with CuKa1 radiation. The catalyst samples were dried in air and
pressed on a glass slide for analysis. The XRD patterns were scanned in
the 2q range of 10–808. For data interpretation, the software WinXpow
(STOE) and the database of powder diffraction file (PDF) of the Inter-
national Centre of Diffraction Data (ICDD) were used. Transmission
electron microscopy (TEM) characterization was carried out by using a
Tecnai G2 F30 S-Twin transmission electron microscope operating at
300 kV. Single-particle EDX analysis was performed by using a Tecnai
G2 F30 S-Twin Field Emission TEM in STEM mode. For TEM investiga-
tions, the catalysts were dispersed in ethanol by ultrasonication and de-
posited on carbon-coated copper grids. The X-ray photoelectron
3674
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 3665 – 3675