Superhydrophobic, chiral, and mesoporous TsDPEN copolymer coordinated to ruthenium species as an efficient catalyst for asymmetric transfer hydrogenation

Article abstract of DOI:10.1016/j.nantod.2013.07.002

Homogeneous chiral catalysts usually show higher catalytic activities than corresponding heterogeneous chiral catalysts, because of their easy interaction between catalytically active sites with reactant molecules. We demonstrate here superhydrophobic, chiral, and mesoporous catalysts (TsDPEN-Ru) synthesized from copolymerization of N-p-styrenesulfonyl-1,2-diphenylethylenediamine (V-TsDPEN) with divinylbenzene and loading of Ru species exhibiting much higher activities in asymmetric transfer hydrogenation (ATH) of ketones in aqueous solution than corresponding homogeneous chiral catalyst. This phenomenon is strongly related to the unique features of high enrichment for the reactants in superhydrophobic TsDPEN-Ru catalysts due to their good wettability, as well as easy transfer of product from the catalyst into water phase. These features open a door for design and developing a wide variety of chiral catalysts for asymmetric catalysis.

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RAPID COMMUNICATION
Superhydrophobic, chiral, and mesoporous
TsDPEN copolymer coordinated to
ruthenium species as an efficient catalyst
for asymmetric transfer hydrogenation
Qi Suna, Yinying Jina, Longfeng Zhub, Liang Wanga,
Xiangju Menga,∗, Feng-Shou Xiaoa,∗∗
a Department of Chemistry, Zhejiang University, Hangzhou 310028, PR China
b State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun
130012, PR China
Received 3 February 2013; received in revised form 19 June 2013; accepted 1 July 2013
Summary
Homogeneous chiral catalysts usually show higher catalytic activities than
KEYWORDS
corresponding heterogeneous chiral catalysts, because of their easy interaction between
catalytically active sites with reactant molecules. We demonstrate here superhydrophobic,
chiral, and mesoporous catalysts (TsDPEN-Ru) synthesized from copolymerization of N-p-
styrenesulfonyl-1,2-diphenylethylenediamine (V-TsDPEN) with divinylbenzene and loading of
Ru species exhibiting much higher activities in asymmetric transfer hydrogenation (ATH) of
ketones in aqueous solution than corresponding homogeneous chiral catalyst. This phenomenon
is strongly related to the unique features of high enrichment for the reactants in superhydropho-
bic TsDPEN-Ru catalysts due to their good wettability, as well as easy transfer of product from
the catalyst into water phase. These features open a door for design and developing a wide
variety of chiral catalysts for asymmetric catalysis.
Superhydrophobicity;
Chirality;
Mesoporous polymer;
TsDPEN ligand;
Asymmetric transfer
hydrogenation
© 2013 Published by Elsevier Ltd.
Introduction
Homogeneous chiral catalysts play an important role for
the synthesis of pharmaceuticals and fine chemicals, but
their poor recyclabilities strongly influence their wide appli-
cations [1]. Therefore, the development of heterogeneous
chiral catalysts has attracted much attention [2], but their
performance is normally lower than those of corresponding
homogeneous chrial catalysts due to the lower degree of
∗
∗∗
Corresponding author.
Corresponding author. Tel.: +86 571 88273282;
fax: +86 571 88273698.
E-mail addresses: mengxj@zju.edu.cn (X. Meng),
fsxiao@zju.edu.cn (F.-S. Xiao).
1748-0132/$ — see front matter © 2013 Published by Elsevier Ltd.
http://dx.doi.org/10.1016/j.nantod.2013.07.002
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Q. Sun et al.
exposure or poorer wettability of active sites to reactants
[3].
from the catalyst into water phase due to the superhy-
drophobicity of catalyst.
As a typical homogeneous chiral catalyst, ruthenium-N-
(p-toluenesulfonyl)-1,2-diphenylethylenediamine (TsDPEN-
Ru, Noyori-Ikariya catalyst) has been extensively investi-
gated [4]. However, this chiral catalyst immobilized onto
insoluble supports shows relatively low yield in asymmet-
ric transfer hydrogenation (ATH) of ketones because of
poor wettability of the chiral catalyst to the ketones [5].
To increase the wettability, phase transfer catalysts are
introduced into the H2O—oil—solid system [6].
Recently, it has been reported that the hydrophobic-
ity of porous catalysts has good wettability to reactant
molecules, which is very helpful for the enrichment of
organic reactants, significantly enhancing the catalytic per-
formance [7]. In this work, we have successfully synthesized
superhydrophobic, chiral, and mesoporous, TsDPEN copoly-
mer (PCP-TsDPEN) from the copolymerization for the first
time. After coordination with ruthernium species, the het-
erogeneous superhydrophobic PCP-TsDPEN-Ru catalyst has
significantly enhanced catalytic performance together with
easy and excellent recyclability in ATH of ketones compared
with the corresponding homogeneous chiral catalyst. This
phenomenon is strongly related to the unique features of
good enrichment of the reactants and easy product transfer
Results and discussion
PCP-TsDPEN-Ru sample was synthesized from copolymer-
ization of N-p-styrenesulfonyl-1,2-diphenylethylenediamine
(V-TsDPEN) with divinylbenzene (DVB) under solvother-
mal conditions (Scheme 1), followed by coordination of
[RuCl2(p-cymene)]2. The V-TsDPEN was synthesized from
1,2-diphenylethylenediamine and p-styrenesulfonyl chlo-
ride. In the synthesis of PCP-TsDPEN, various mass ratios
(x) of V-TsDPEN to divinylbenzene have been used, yield-
ing various porous PCP-x-TsDPEN samples (Table S1). All the
samples exhibit high surface area, large pore volume, and
uniform mesopore sizes (Figs. S1 and S2 and Tables S1 and
S2). IR spectroscopy (Fig. S3) shows that PCP-1/8-TsDPEN
gives additional bands at ca. 1095, 1160 and 1345 cm−1
,
compared with pure PDVB sample. These bands are charac-
teristic of C N and O S O bonds, in good agreement with
the presence of V-TsDPEN [8]. Moreover, the intensities of
these bands increase with the ratios of V-TsDPEN to DVB (Fig.
S4). These results indicate the successful incorporation of
V-TsDPEN in the samples.
+
O
S
HN
NH2
H2N
NH2
O
S
O
O
Cl
*
*
*
*
*
*
RuCl2(p-cymene)
O
S
O
O
S
O
*
*
HN
N
Cl
Ru
H2N
N
H
PCP-TsDPEN-Ru
PCP-TsDPEN
Scheme 1 The route for synthesizing PCP-TsDPEN-Ru catalyst.
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Superhydrophobic, chiral, and mesoporous TsDPEN copolymer
3
type-IV sorption isotherms with
a
hysteresis loop at
0.45—0.95, which indicates the presence of mesoporosity in
the samples. Correspondingly, PCP-TsDPEN and PCP-TsDPEN-
Ru give the pore size distributions at ca. 12.6 and 11.8 nm,
BET surface areas at 528 and 481 m2/g, and pore volumes
at 0.59 and 0.55 cm3/g respectively (Tables S1 and S2).
Fig. 1B and Fig. 1C show scanning electron microscope
(SEM) and transmission electron microscope (TEM) images of
PCP-TsDPEN and PCP-TsDPEN-Ru samples, giving direct evi-
dence of abundant mesoporosity, in good agreement with
those of the sample N2 sorption isotherms. Fig. 2 shows
elemental mapping for C, O, S, N, and Ru in the PCP-
TsDPEN-Ru, exhibiting very uniform elemental distribution.
These results suggest that the PCP-TsDPEN-Ru is a copolymer,
rather than a mixture of polydivinylbenzene and polyme-
rized V-TsDPEN.
Fig. 3 shows contact angles of water, 1-phenyl-ethanol,
and acetophenone on the sample surface. When a water
droplet was contacted with the surface of PCP-TsDPEN,
the contact angle (CA) was about 151◦ (Fig. 3A), indicat-
ing that the sample is superhydrophobic. When a water
droplet was contacted with the surface of PCP-TsDPEN-
Ru, the contact angle was still about 150◦ (Fig. 3B). This
result indicates that the introduction of Ru species in the
sample does not influence the sample superhydrophobic-
ity. When a 1-phenyl-ethanol droplet was contacted with
the surface of PCP-TsDPEN-Ru, the angle was 16◦ (Fig. 3C).
In contrast, when an acetophenone droplet was contacted
with the PCP-TsDPEN-Ru, the acetophenone was momen-
tarily into the sample, giving the swelling surface (Fig. 3D).
These results indicate that the wettability of acetophenone
into PCP-TsDPEN-Ru is much better than that of 1-phenyl-
ethanol. TG curve of PCP-TsDPEN shows that no weight loss
occurs below 300 ◦C (Fig. S6), indicating its good thermal
stability.
To determine the chirality of PCP-TsDPEN sample, the
enantiomers of 1,2-diphenylethylenediamine were used as
starting materials. As a result, both PCP-(S)-TsDPEN and PCP-
(R)-TsDPEN were obtained. Fig. 4 shows CD spectra (circular
dichroism spectra) of PCP-(S)-TsDPEN and PCP-(R)-TsDPEN
samples. As expected, both show mirror signals at ca. 245,
275 and 365 nm, although there is a peak shift. In fact, the
peak shift also can be observed at monomer of V-TsDPEN
(Fig. S7). In addition, UV—visible spectroscopy shows that
PCP-(R)-TsDPEN sample has similar adsorption peaks at ca.
245, 290 and 350 nm (Fig. S8), suggesting that the mirror
CD peaks associated PCP-(R)-TsDPEN and PCP-(S)-TsDPEN are
not artificial [9].
Figure 1 (A) N2 sorption isotherms of (a) PCP-TsDPEN and (b)
PCP-TsDPEN-Ru samples. (b) Isotherms in A have been offset by
200 cm3/g. Inset: pore size distributions; SEM images of (B) PCP-
TsDPEN and (C) PCP-TsDPEN-Ru samples. Inset: corresponding
TEM images of the samples.
Based on the results of N2 sorption isotherm, SEM and
TEM images, elemental mapping, IR, contacting angles of
water, as well as CD spectra, it can be concluded that the
superhydrophobic, chiral, and mesoporous TsDPEN copoly-
mers have been successfully synthesized. After loading Ru
species, the Ru species could be coordinated with nitrogen
atoms in TsDPEN ligands in the samples.
To evaluate the catalytic performance of the superhy-
drophobic, chrial, and mesoporous PCP-TsDPEN-Ru, ATH of
acetophenone as a model was chosen, and the catalytic
results are presented in Table 1. Notably, PCP-TsDPEN-Ru
catalyst shows a full conversion with 94.0% ee in 1.5 h at
40 ◦C (entry 1, Table 1). This activity is even higher than
that of TsDPEN-Ru species in the nanocages containing phase
Particularly, after coordination of ruthenium species, the
band attributed to C N band of PCP-1/8-TsDPEN-Ru slightly
shifts to lower wavenumber, while the bands associated with
O S O bond almost do not change. These results suggest
that the ruthenium species should coordinate with nitrogen
atoms rather than sulfur atoms. The measurements of water
on the surface of the samples show that the contact angles
are higher than 150◦ when x is less than 1/8, indicating their
superhydrophobicity (Fig. S5).
As typical samples, PCP-1/8-TsDPEN, and PCP-1/8-
TsDPEN-Ru (abbreviation: PCP-TsDPEN and PCP-TsDPEN-Ru)
are carefully investigated. Fig. 1A shows N2 isotherms of
PCP-TsDPEN and PCP-TsDPEN-Ru samples, exhibiting typical
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Q. Sun et al.
Figure 2 (A) SEM image of PCP-TsDPEN-Ru; (B), (C), (D), (E), and (F) elemental mapping for C, O, S, N, and Ru in the yellow
rectangle of PCP-TsDPEN-Ru, respectively. The bars in the samples are 60 ␮m.
transfer catalyst, one of the best hetergeneous catalysts in
ATH reactions [6c]. This result suggests that the superhy-
drophobic and mesoporous PCP-TsDPEN-Ru catalyst is very
active. When the reaction temperature is increased to 70 ◦C,
the full conversion takes for only 0.5 h (entry 2, Table 1). The
reaction can be also performed at room temperature, but
required longer reaction time 8 h (entry 3, Table 1). Interest-
ingly, even if the S/C ratio is increased to 500, the conversion
of acetophenone could still reach 98% with 93.1% ee (entry
4, Table 1).
Figure 3 (A) Contact angle of water on the surface of PCP-TsDPEN; (B), (C), and (D) contact angles of water, 1-phenyl-ethanol,
and acetophenone on the surface of PCP-TsDPEN-Ru, respectively.
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Superhydrophobic, chiral, and mesoporous TsDPEN copolymer
5
Table 1 Asymmetric transfer hydrogenation of ketones catalyzed by PCP-TsDPEN-Rua.
Entry
R1
R2
Time (h)
Conv. [%]b
Sel. [%]b
ee [%]b
1
2c
3d
4e
5f
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3CH2
CH3
CH3
CH3
CH3
CH3
CH3
CH3
H
H
H
H
H
H
H
H
1.5
0.5
8
>99.5
>99.5
>99.5
98
81
52
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
94.0
90.1
94.3
93.1
95.1
93.1
94.2
92.9
92.8
95.2
98.4
94. 8
94. 3
93. 2
93.7
94.2
9
1.5
1.5
1.5
1.5
1.5
2
2
3
1.5
2.5
1.5
1.5
6g
7h
8i
>99.5
94
9
H
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
>99.5
5.1
10
11j
12
13
14
15k
16l
a
p-CH3O
m-CH3O
p-CH3
p-Cl
p-Br
H
H
Reactions were carried out under N2 atmosphere at 40◦C, using 0.5 mmol of ketones, 2.5 mmol of HCOONa, and a S/C ratio of 100 in
5 mL degassed water.
b
Determined by GC on a Supelco ␥-DEX 225 capillary column.
c
Reaction at 70 ◦C.
d
Reaction at RT.
e
Acetophenone (2.5 mmol), HCOONa (12.5 mmol), water (20 mL) and a S/C ratio of 500.
TsDPEN-Ru as catalyst.
Using 3 mL of H2O and 3 mL of DMF as solvent.
Reused.
Recycles for 14 times.
Determined by GC on a Agilent CycloSil-B.
PCP-(1/8)-(S)-TsDPEN-Ru was used as catalyst.
PS-TsDPEN-Ru without nanoporosity was used as catalyst.
f
g
h
i
j
k
l
To understand the high activities in this work, the
dependences of acetophenone conversion on reaction
time over heterogeneous PCP-TsDPEN-Ru and homogeneous
TsDPEN-Ru catalysts are compared, as shown in Fig. 5A.
Notably, when the reaction time is less than 30 min, both
catalysts exhibit similar reaction rate. However, when the
reaction time is over 40 min, PCP-TsDPEN-Ru catalyst shows
much higher reaction rate than TsDPEN-Ru catalyst. The
PCP-TsDPEN-Ru catalyst gives the conversion at 97% for
70 min, while TsDPEN-Ru catalyst shows the conversion
at only 81% for 90 min (entry 5, Table 1). To explain this
phenomenon, the percentage of the reactant (acetophe-
none) and product (1-phenyl-ethanol) in the catalyst and
water has been measured, and the results (Fig. 5B) show
that the heterogeneous catalyst of PCP-TsDPEN-Ru has a
strong ability for enrichment of reactant in the catalyst and
transfer of product from the catalyst to water phase. This
phenomenon is obviously related to the superhydropho-
bicity of the catalyst. The adsorption of acetophenone on
the superhydrophobic catalyst is much easier than that
of 1-phenyl-ethanol, in good agreement with that the
wettability of acetophenone into PCP-TsDPEN-Ru is much
better than that of 1-phenyl-ethanol (Fig. 3C and D). In this
case, when the reaction time is over 40 min, about 60% ace-
tophenone is converted, but the residual reactant (>80%) is
still enriched in the catalyst, and a large amount of product
(>90%) are transferred from the catalyst to the water phase
(Fig. 5B). This feature leads to very high activity in ATH
over PCP-TsDPEN-Ru catalyst. The phenomena of reactant
enrichment in the catalysts such as carbon nanotube [7b,c],
amphiphilic polymer-based catalyst [7d,e], and superhy-
drophobic catalysts [7a], have been reported, which plays
an important role for enhancing catalytic activities.
Very interestingly, when the mixed solvent of water and
DMF is used, the conversion is very low at only 52% (entry
6, Table 1). This result is well interpreted by the absence
of the product transfer from the catalyst to water solution.
Notably, catalyst recyclability is very important for practical
applications. As observed in Table 1 (entries 7 and 8) and
Table S3, even recycling for 14 times, the conversion and
ee value still remained at 94 and 92.9%, respectively. The
leaching of the catalyst is not detected by ICP-MS analysis.
These results indicate that the PCP-TsDPEN-Ru is a very effi-
cient and recyclable catalyst in ATH reactions using water
as solvent.
Encouraged by superior performance in ATH of ace-
tophenone, other ketones have been intensively expended.
Table
1 also presents the catalytic data in ATH of
electron-rich and electron-deficient aromatic ketones over
the mesoporous superhydrophobic PCP-TsDPEN-Ru catalyst
(entries 9—14). The results show that various ketones are
efficiently converted into chiral alcohols with high ee val-
ues (92.8—98.4%) using HCOONa as the reductant and water
as the solvent. The substitution position of the ketones has
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5
A
800
b
b
a
0
282
600
369
0
20 40 60 80 100 120
Pore Diameter (nm)
-5
249
b
400
200
a
-10
a
a
-15
-20
0
0.0
0.2
0.4
0.6
0.8
1.0
250
300
350
400
)
0
Wavelength (nm)
Relative Pressure (P/P
Figure 4 CD spectra of (a) PCP-(R)-TsDPEN and (b) PCP-(S)-TsDPEN.
Figure 5 (A) ATH catalytic kinetics over PCP-TsDPEN-Ru and TsDPEN-Ru catalysts; (B) percentage of ATH reactant and product in
PCP-TsDPEN-Ru catalyst and water at various reaction time. Reaction conditions: acetophenone (0.5 mmol), HCOONa (2.5 mmol),
H2O (5 mL), S/C = 100, N2, 40 ◦C.
no significant influence on the reaction time for obtaining
high conversion (entries 9—14, Table 1). The solid reac-
tant of 4-bromoacetophenone (melting point 48—53 ◦C) can
be also reduced to corresponding chiral alcohol (entry
14, Table 1) with high activity and ee value, although a
longer time is needed, compared with liquid reactant of 4-
chloroacetophenone (entry 13, Table 1). Notably, when the
substrate with hydrophilic hydroxyl group (o-acetylphenol)
was used, the heterogeneous PCP-TsDPEN-Ru gives similar
activity to the homogeneous TsDPEN-Ru, which indicates
that the PCP-TsDPEN-Ru is favorable for the hydrophobic
substrates (Table S3).
been successfully synthesized from a copolymerization of
divinylbenzene with V-TsDPEN ligands. After coordination
of Ru species, the PCP-TsDPEN-Ru catalysts show superior
performance in ATH reactions using water as green solvent.
The enrichment of the reactant in the catalyst and the
product transfer from the catalyst to the water phase in
the reaction system would be responsible for the superior
catalytic performance. This feature should be potentially
important for designing and preparing novel catalysts for
organic synthesis in the future.
Experimental
Conclusion
Catalysts preparation
In summary, TsDPEN-functionalized copolymers (PCP-
TsDPEN) with the features of superhydrophobicity, high
surface area, large pore volume, abundant mesoporo-
sity, good thermal stability, and obvious chirality have
Synthesis of p-styrenesulfonyl chloride
p-styrenesulfonyl chloride was synthesized according to
the literature [10]. As a typical run, 15 g of sodium p-
styrenesulfonate was dissolved in 80 mL of anhydrous DMF
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Superhydrophobic, chiral, and mesoporous TsDPEN copolymer
7
(dried over CaH2) under N2 and cooled to 0 ◦C, followed
by addition of 30 mL of SOCl2. After stirred at 0 ◦C for
30 min, the mixture was stirred at room temperature for
another hour, and then poured into ice. The resulting aque-
ous layer was extracted with diethyl ether. Finally, the
collected organic phase was combined, dried over MgSO4
and evaporated to obtain a light yellow liquid, which was
p-styrenesulfonyl chloride.
before a certain amount of [RuCl2(p-cymene)]2 and CH2Cl2
was added. The mixture was stirred at 40 ◦C under N2 for
2 h, filtered off and washed with excess of CH2Cl2 in order
to remove physical adsorbed Ru species. The catalyst was
dried at room temperature under vacuum.
Characterization
Nitrogen sorption isotherms at the temperature of liquid
nitrogen were measured using Micromeritics ASAP 3020M
and Tristar system. The samples were outgassed for 10 h
at 100 ◦C before the measurements. ICP analysis was mea-
sured with a Perkin-Elmer plasma 40 emission spectrometer.
1H NMR spectra were recorded on a Bruker Avance-400
(400 MHz) spectrometer. Chemical shifts are expressed in
ppm downfield from TMS at ı = 0 ppm, and J values are given
in Hz. Diffuse reflectance ultraviolet—visible (UV—vis) spec-
tra were measured with spectrometer of PE Lambda 20, and
BaSO4 was an internal standard sample. CD spectra were
performed on MOS-450. XPS spectra were performed on a
Thermo ESCALAB 250 with Al K␣ irradiation at ꢀ = 90◦ for X-
ray sources, and the binding energies were calibrated using
the C1s peak at 284.9 eV. FTIR spectra were performed on IFS
Synthesis of (1R,
2R)-N-p-styrenesulfonyl-1,2-diphenylethylenediamine
(1R, 2R)-N-p-styrenesulfonyl-1,2-diphenylethylenediamine
was synthesized as follows: 1 g of (1R, 2R)-1,2-
diphenylethylenediamine (4.71 mmol) was dissolved in
20 mL of CH2Cl2 in the presence of excessive of triethyl-
amine and cooled to 0 ◦C, followed by the slow addition of
5 mL of CH2Cl2 solution containing 1 g of p-styrenesulfonyl
chloride (4.78 mmol), and stirred at room temperature
overnight. The solution was washed with 5% NaOH aqueous
solution, dried with MgSO4, and evaporated under vacuum
to remove the solvent. The obtained solid was dissolved
in diethyl ether, followed by the addition of 1 mL of
concentrated HCl (37 wt%). The formed white precipitated
was filtrated, treated with 5% NaOH aqueous, and then
extracted with CH2Cl2 for 3 times. The combined organic
phase was washed thoroughly with brine and dried over
with MgSO4. The solvent was removed under vacuum and
1.28 g of light yellow solid (72% yield) was obtained, which
66 V (Bruker) IR spectrometer in the range 400—4000 cm−1
.
Scanning electron microscope (SEM) images were performed
using a Hitachi SU 1510. Transmission electron microscope
(TEM) images were performed using Hitachi HT-7700. Con-
tact angles of water and organic compunds were measured
on a contact angle measuring system SL200KB (USA KNO
Industry Co.), equipped with a CCD camera. The static con-
tact angles were measured in sessile drop mode.
1
was denoted as V-TsDPEN [11]. H NMR (400 MHz, DMSO-d6,
298 K, TMS): ı 6.64—7.38 (m, 14H), 6.64—6.67 (m, 1H), 5.87
(d, 1H, J = 16.8 Hz), 5.35 (d, 1H, J = 11.2 Hz), 4.33 (d, 1H,
J = 7.2 Hz), 3.95 (d, 1H, J = 6.6 Hz) ppm.
(1S, 2S)-N-p-styrenesulfonyl-1,2-diphenylethylenedia-
mine was synthesized as the same method except that (1S,
2S)-1,2-diphenylethylenediamine was used.
Catalytic tests
In the asymmetric transfer hydrogenation of aromatic
ketones, all reactions were carried out under a nitrogen
atmosphere by using standard Schlenk-type techniques.
As a typical run, a desired amount of PCP-TsDPEN-Ru,
HCOONa·2H2O (2.5 mmol) and ketones (0.5 mmol, S/C = 100)
were added into degassed water (5 mL) in a Schlenk tube
and the mixture was stirred at 40 ◦C for a desired time.
After the reaction, the mixture was extracted with ethyl
acetate and catalyst was taken out from the system by cen-
trifugation and the liquid was passed through a short column
before analyzed by gas chromatography (GC-1690 Kexiao Co.
equipped with a flame ionization detector and a Supelco ␥-
DEX 225 capillary column). Dodecane was added as internal
standard.
Synthesis of PCP-TsDPEN with various amount of
V-TsDPEN (PCP-x-TsDPEN)
PCP-x-TsDPEN (x stands for the mass ratios of V-TsDPEN to
divinylbenzene) was synthesized via solvothermal synthe-
sis according to the literature [12]. As a typical run, 2 g
of divinylbenzene and 0.25 g of V-TsDPEN were dissolved in
20 mL of DMF, followed by addition of 0.05 g of azobisisobu-
tyronitrile (AIBN). After stirring for 3 h at room temperature,
the mixture was transferred into an autoclave at 100 ◦C for
24 h. After extraction of solvent with ethanol, a light yel-
low solid product was obtained, which was designated as
PCP-1/8-TsDPEN.
The recyclability of PCP-TsDPEN-Ru was studied using
acetophenone as substrate. For recycling the catalyst, the
catalyst was separated by centrifugation, washed with
water (5 mL × 5 mL), then another portion of acetophenone
(0.5 mmol), HCOONa·2H2O (2.5 mmol) and degassed H2O
(5 mL) were added. The reactions were conducted at 40 ◦C
for 1.5 h.
Synthesis of PS-TsDPEN
PS-TsDPEN was synthesized as follows: 0.95 g of styrene,
0.05 g of divinylbenzene, and 0.125 g of V-TsDPEN were dis-
solved in 1 mL of DMF, followed by addition of 0.02 g of
azobisisobutyronitrile (AIBN). After heating at 80 ◦C for 36 h,
a light yellow solid product was obtained and denoted as
PS-1/8-TsDPEN (abbreviation: PCP-TsDPEN).
Acknowledgements
Synthesis of PCP-TsDPEN-Ru catalyst
PCP-TsDPEN-Ru was synthesized as follows: In a typical run,
This work is supported by NSFC (U1162201 and 21273197),
National High-Tech Research and Development program
1 g of PCP-TsDPEN was dried at 80 ◦C under vacuum for 6 h
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Superhydrophobic, chiral, and mesoporous TsDPEN copolymer
9
Dr. Liang Wang received his B.S. (2008) and
Ph.D. (2013) in the College of Chemistry, Jilin
University, China. In July 2013, he joined to
the Institute of Catalysis in Zhejiang Uni-
versity for a postdoctoral work under the
guidance of Prof. Feng-Shou Xiao. His current
research is mainly focused on heterogeneous
catalysis.
Prof. Feng-Shou Xiao received his B.S. and
M.S. degrees in the Department of Chemistry,
Jilin University, China. From there he moved
to the Catalysis Research Center, Hokkaido
University, Japan, where he was involved in
collaborative research between China and
Japan. He was a Ph.D. student there for two
years, and was awarded his Ph.D. degree at
Jilin University in 1990. After postdoctoral
work at the University of California at Davis,
USA, he joined the faculty at Jilin University
Dr. Xiangju Meng received his B.S. (1999) and
Ph.D. (2004) in the College of Chemistry, Jilin
University, China. Subsequently, he joined
the Catalytic Chemistry Division, Chemical
Resources Laboratory, Tokyo Institute of Tech-
nology, Japan for his postdoctoral work on
synthesis and applications of nanoporous
materials under the guidance of Prof. T. Tat-
sumi. After postdoctoral work in National
Institute of Advanced Industrial Science and
Technology (AIST), Japan, he returned China
and joined Prof. Xiao’s group. He was promoted to assocated pro-
fessor in Zhejiang University in 2009. His research interests include
zeolites and heterogeneous catalysis.
in 1994, where he is a full and distinguished professor of Chemistry.
He moved to Zhejiang university in 2009, and now he is a full and
distinguished professor of Chemistry. For his research in nanoporous
materials, Prof. Xiao has been recognized with the National Out-
standing Award of Young Scientists in National Science Foundation
of China in 1998 and Thomson Scientific Research Fronts Award in
2008.
Please cite this article in press as: Q. Sun, et al., Nano Today (2013), http://dx.doi.org/10.1016/j.nantod.2013.07.002