S. Zhao et al. / Applied Catalysis A: General 453 (2013) 188–194
189
2
. Experimental
of K-Ln(PW11)2 (Ln = Y, La, Ce, Nd, Sm, Eu, Gd, Tb, Er and Yb)
should be K11[Y(PW11O39) ]·14H O, K11[La(PW11O39) ]·13H O,
2
2
2
2
2
.1. Chemical materials
K11[Ce(PW11O39) ]·14H O,
K
11
[Nd(PW11O39) ]·16H O,
K [Sm
11
2
2
2
2
(
PW11O39) ]·16H O,
K
[Eu(PW11O39) ]·16H O,
K
11[Gd(PW11
2
2
K
11
2
2
K
cis-Cyclooctene (95%), cis-2-hexen-1-ol (94%), cis-2-nonen-1-
O39) ]·21H O,
11[Tb(PW11O39) ]·26H O,
11[Er(PW11O39) ]·
2
2
2
2
2
ol (95%), trans-2-hexen-1-ol (97%), trans-2-hepten-1-ol (96%),
trans-2-octen-1-ol (97%), trans-2-decen-1-ol (95%), 1-octen-3-
ol (98%), geraniol (97%), thioanisole (98%), dibenzothiophene
23H O and K11[Yb(PW11O39) ]·19H O.
2
2
2
2.4. Synthesis of DA-La(PW11)2, DDA-La(PW11)2,
(
(
DBT, 98%), diphenyl sulfide (DPS, 98%), dimethyl sulfoxide-d6
DMSO-d ) (99.5%), 30% H O aqueous solution and all solvents
TDA-La(PW11)2, HDA-La(PW11)2 and ODA-La(PW11)2
6
2
2
were purchased from Alfa Aesa. Decyltrimethylammonium bro-
mide (DA-Br, 99%), dodecyltrimethylammonium bromide (DDA-Br,
In a typical synthesis of DA-La(PW11)2, an aqueous solution
of (2.0 g, 0.31 mmol) K-La(PW11)2 was dropped into a chloroform
solution of (1.1 g, 3.75 mmol) DA-Br. A white precipitate formed
after the addition of the whole K-La(PW11)2 aqueous solution and
then the product was separated after a further 1 h of stirring. The
9
8%), tetradecyltrimethylammonium bromide (TDA-Br, 98%),
hexadecyltrimethylammonium bromide (HDA-Br, 99%), octade-
cyltrimethylammonium bromide (ODA-Br, 98%), cyclododecene
(
98%) and dicyclopentadiene (99%) were obtained from TCI. Ana-
product was washed twice with H O and dried in air [9]. DDA-
2
lytical yttrium (III) chloride hexahydrate (YCl ·6H O), lanthanum
La(PW11)2, TDA-La(PW11)2, HDA-La(PW11)2 and ODA-La(PW11)2
were prepared with a similar procedure. In the H NMR spectra,
the singlet peak at 2.5 ppm and 3.3 ppm is assigned to be DMSO-d6,
3
2
1
(
III) chloride heptahydrate (LaCl ·7H O), cerium (III) chloride hep-
3
2
tahydrate (CeCl ·7H O), neodymium (III) chloride hexahydrate
3
2
(
NdCl ·6H O), samarium (III) chloride hexahydrate (SmCl ·6H O),
and the water in DMSO-d , respectively.
3
2
3
2
6
1
europium (III) chloride hexahydrate (EuCl ·6H O), gadolinium (III)
For DA-La(PW11)2, H NMR (400 MHz, DMSO-d , ppm): ı = 0.868
3
2
6
chloride hexahydrate (GdCl ·6H O), terbium (III) chloride hexahy-
(3H, br), 1.263 (14H, m), 1.678 (2H, br), 3.159 (3H, m), 3.400 (2H,
3
2
3
1
drate (TbCl ·6H O), erbium (III) chloride hexahydrate (ErCl ·6H O),
br). P NMR (400 MHz, DMSO-d , 85% H PO , ppm): ı = −12.8 (2P,
3
2
3
2
6
3
4
−
1
ytterbium (III) chloride hexahydrate (YbCl ·6H O), potassium
s). FT-IR (KBr, cm ): ꢁ = 3462, 2955, 2922, 2851, 1635, 1488, 1471,
1376, 1098, 1048, 944, 883, 833, 783, 722, 594, 510. Elemental anal-
ysis (%) Found: C 21.48, H 4.17, N 1.87, La 1.55, W 51.34; Cacld. for
[(n-C10H21)(CH ) N]11La(PW11O39) ·7H O: C 21.95, H 4.43, N 1.97,
3
2
acetate (CH COOK), acetic acid (CH COOH) and phosphotungstic
3
3
acid (H PW12O40·xH O) were obtained from Energy Chemical in
3
2
shanghai. All the chemicals and solvents were used without further
purification.
3
3
2
2
La 1.78, W 51.70.
For DDA-La(PW11)2, 1H NMR (400 MHz, DMSO-d6, ppm):
ı = 0.863 (3H, br), 1.256 (18H, m), 1.678 (2H, br), 3.202 (3H, m),
2.2. Measurements
3
.382 (2H, br). 31P NMR (400 MHz, DMSO-d , 85% H PO , ppm):
6 3 4
−
1
Powder X-ray diffraction (XRD) patterns were recorded on a
ı = −12.8 (2P, s). FT-IR (KBr, cm ): ꢁ = 3461, 2955, 2922, 2851,
1636, 1488, 1471, 1376, 1099, 1049, 943, 883, 834, 784, 720, 594,
509. Elemental analysis (%) Found: C 24.83, H 5.03, N 1.86, La 1.90,
W 50.05; Cacld. for [(n-C12H25)(CH ) N]11La(PW11O39) ·7H O: C
Rigaku XRD-6000 diffractometer under the following conditions:
0 kV, 30 mA, Cu K␣ radiation (ꢀ = 0.154 nm). Fourier transform
4
infrared (FT-IR) spectra were recorded on a Bruker Vector 22
infrared spectrometer using KBr pellet method. Scanning electron
microscopy (SEM) images and energy dispersive X-ray (EDX) ana-
lytical data were obtained using a Zeiss Supra 55 SEM equipped
3
3
2
2
24.37, H 4.81, N 1.89, La 1.71, W 49.73.
1
For TDA-La(PW11)2,
H NMR (400 MHz, DMSO-d6, ppm):
ı = 0.861 (3H, br), 1.250 (22H, m), 1.678 (2H, br), 3.202 (3H, m),
with an EDX detector. Transmission electron microscopy (TEM)
3.383 (3H, br). 31P NMR (400 MHz, DMSO-d , 85% H PO , ppm):
6
3
4
1
−1
micrographs were recorded using a Hitachi H-800 instrument.
H
ı = −12.8 (2P, s). FT-IR (KBr, cm ): ꢁ = 3447, 2955, 2922, 2851,
1636, 1488, 1471, 1376, 1099, 1050, 944, 882, 834, 784, 721, 594,
510. Elemental analysis (%) Found: C 27.06, H 5.41, N 1.79, La 2.02,
W 48.08; Cacld. for (n-C14H29)(CH ) N]11La(PW11O39) ·7H O: C
3
1
1
NMR and P NMR spectra were recorded on a Bruker NMR ( H,
3
1
4
00 MHz; P, 109 MHz) spectrometer. Chemical shifts (ı) were
reported in ppm downfield from external SiMe and 85% H PO for
4
3
4
3
3
2
2
1
31
H and P NMR spectra, respectively. The elemental analysis has
26.62, H 5.16, N 1.83, La 1.65, W 47.92.
1
been carried out on an EAI CE-440 elemental analyzer. The water
drop static contact angle was measured using an OCA 20 from Data-
Physics Instruments GmbH, using the sessile drop and tilting plate
measuring method. The products of the catalytic reactions were
analyzed by Agilent 7820A gas chromatography (GC) system using
a 30 m 5% phenylmethyl silicone capillary column with an ID of
For HDA-La(PW11)2, H NMR (400 MHz, DMSO-d , ppm):
6
ı = 0.862 (3H, br), 1.248 (26H, m), 1.675 (2H, br), 3.134 (3H, m),
3.399 (2H, br). 31P NMR (400 MHz, DMSO-d , 85% H PO , ppm):
6
3
4
−
1
ı = −12.8(2P, s). FT-IR(KBr, cm ): ꢁ = 3503, 2955, 2922, 2851, 1636,
1488, 1471, 1376, 1098, 1050, 945, 883, 834, 784, 721, 594, 514. Ele-
mental analysis (%) Found: C 29.78, H 5.86, N 1.79, La 1.88, W 45.81;
Cacld. for [(n-C16H33)(CH ) N]11La(PW11O39) ·12H O: C 29.40, H
0.32 mm and 0.25 m coating (HP-5). Yields were determined by
3
3
2
2
GC analysis based on H O . Assignments of corresponding products
5.54, N 1.74, La 1.57, W 45.75.
2
2
were analyzed by 1H NMR.
For ODA-La(PW11)2,
1
H NMR (400 MHz, DMSO-d6, ppm):
ı = 0.863 (2H, br), 1.246 (30H, m), 1.246 (30H, m), 1.678 (2H,
2
.3. Synthesis of K11[Ln(PW11O39)2] (K-Ln(PW11)2, Ln = Y, La, Ce,
br), 3.069 (3H, m), 3.401 (2H, br). 31P NMR (400 MHz, DMSO-d ,
6
−
1
Nd, Sm, Eu, Gd, Tb, Er and Yb)
85% H PO , ppm): ı = −12.9 (2P, s). FT-IR (KBr, cm ): ꢁ = 3524,
3
4
2
955, 2922, 2851, 1636, 1488, 1471, 1376, 1097, 1049, 946,
(
10.0 g, 3.47 mmol) H PW12O40·xH O in 20 ml H O was
883, 834, 784, 721, 594, 515. Elemental analysis (%) Found:
C 31.60, H 6.20, N 1.71, La 1.64, W 44.58; Cacld. for [(n-
C18H37)(CH ) N]11La(PW11O39) ·11H O: C 31.38, H 5.82, N 1.69,
3
2
2
treated successively with the warm concentrated solutions of
(
0.6 g, 1.85 mmol) LnCl ·xH O (Ln = Y, La, Ce, Nd, Sm, Eu, Gd,
3
2
3
3
2
2
Tb, Er and Yb; x = 6 or 7) and (8.0 g, 0.08 mol) CH COOK (pH
La 1.52, W 44.30.
3
was adjusted to 7.0 with CH COOH). The mixture was stirred at
3
◦
9
0 C until a clear solution was obtained. The clear solution was
2.5. Procedure for catalytic oxidation with H O
2 2
◦
cooled to room temperature and then put in refrigerator (∼4 C)
overnight. The obtained precipitate was filtered and recrystal-
lized twice [8]. From the TGA and ICP analysis, the formulas
In a typical experiment, 1 mmol substrate, 30% H O2 aque-
2
ous solution, 0.25 mol% DA-La(PW11)2 and 0.2 ml acetonitrile