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Contents lists available at ScienceDirect

Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Aqueous-phase hydrogenation of alkenes and arenes: The growing

role of nanoscale catalysts
Safak Bulut a , Zhaofu Fei a , Sviatlana Siankevich a , Jiaguang Zhang b , Ning Yan b ,
Paul J. Dyson a,∗
a
Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland
b
Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, 117585 Singapore, Singapore

a r t i c l e i n f o a b s t r a c t

Article history: In this article we highlight some of the recent developments in the aqueous-phase hydrogenation of
Received 29 April 2014 alkenes and arenes. The traditional types of water-soluble catalysts applied in aqueous media are outlined
Received in revised form 7 August 2014 together with recent trends towards the development of transition metal nanoparticle and nanocompos-
Accepted 1 September 2014
ite catalysts. In addition, we describe some palladium nanoparticle catalysts that are stabilized by ionic
Available online xxx
polymers, which demonstrate superior activities in the aqueous-phase catalytic hydrogenation of styrene,
used as a model substrate, compared to related palladium nanoparticles.
Keywords:
© 2014 Elsevier B.V. All rights reserved.
Biphasic catalysis
Hydrogenation
Aqueous-phase hydrogenation
Polymer stabilizers
Nanocatalysts
Nanoparticles

1. Introduction water-soluble phosphine ligands and complexes derived from

The hydrogenation of alkenes and arenes is an important indus-
trial reaction used to produce both bulk and fine chemicals [1,2].
The reaction is usually carried out in a solvent, as opposed to
solvent-free conditions, with organic solvents being favoured,
although some processes operate in water, which is considered to
be the ideal green solvent. The use of water as a solvent should help
industry to meet increasingly stringent requirements for food, drug
and healthcare products [3–5].
Some reactions can easily be transferred to water providing
yields and selectivities comparable, or sometimes even superior,
to those conducted in organic solvents. Water, however, cannot
systematically replace organic solvents in catalysis as the use of
water introduces new challenges and problems. For example, many
substrates are hydrophobic, some catalysts are insoluble in water
or are rapidly deactivated by water. Traditional studies on aque-
ous biphasic catalysis have focused on the design and synthesis
of water-soluble catalysts and their use in hydrogenation (and
other) reactions, often with an emphasis on recycling and reuse.
Early reviews highlight the design, synthesis and application of
∗ Corresponding author. Tel.: +41 21 693 98 54; fax: +41 21 693 97 80.
E-mail address: paul.dyson@epfl.ch (P.J. Dyson).
them [6] and supported aqueous-phase catalysts [7] and two excel-
lent books on these topics are available [8,9].
It is well established that the hydrogenation of arenes is
achieved using nanoparticle (or colloidal) catalysts and, many
examples of apparently homogeneous molecular arene hydrogena-
tion catalysts have been shown to actually decompose to give
nanoparticle catalysts [10–13]. It has also been shown that for
unactivated, or weakly activated alkenes, nanocatalysts tend to
be considerably superior to molecular catalysts [14,15]. Based on
these observations much recent interest has been devoted to the
development of dispersed and immobilized nanoparticle catalysts
for aqueous-phase hydrogenation reactions. Several reviews have
been published on various aspects of nanocatalysis [15–17], and it
would appear that many of the new concepts are driven by sus-
tainability and environmental issues [16]. The area has also been
facilitated by general developments in nanotechnology, in partic-
ular to improvements in characterization techniques.
The design of new water-soluble ligands and catalysts derived
from them remains an important area, especially for reactions
where regioselective, chemoselective or enantioselective trans-
formations are required, as water is seldom used for these
transformations in industry. However, with simple alkene sub-
strates and arenes greatest strides have been made in the design of
nanoparticle catalysts. In this article we highlight some new trends

http://dx.doi.org/10.1016/j.cattod.2014.09.002
0920-5861/© 2014 Elsevier B.V. All rights reserved.

Please cite this article in press as: S. Bulut, et al., Aqueous-phase hydrogenation of alkenes and arenes: The growing role of nanoscale
catalysts, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.09.002
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and strategies to develop highly active and stable nanocatalysts for
alkene and arene hydrogenation that operate, or could be operated,
in water.
2. Hydrogenation of alkenes and arenes using transition
metal nanoparticles
Metal nanoparticles play an important role in the hydrogena-
tion of alkenes and arenes in aqueous systems when stabilized
by polymers or surfactants. Indeed, the catalytic properties of the
nanoparticles can be modified by careful manipulation of the stabi-
lizing agent [17]. A large number of metal nanocatalysts combined
with various stabilizers have been reported and, therefore, only
a few notable examples will be discussed here to illustrate key
approaches and strategies.
The majority of nanocatalysts developed for the hydrogena-
tion of non-activated alkenes and arenes under aqueous-organic
biphasic conditions are based on precious metals. While PVP tends
to be the most widely used stabilizer, since it endows the nanopar-
ticle with good thermal stability, a variety of other stabilizers also
show promise. Rh nanoparticles stabilized by PVP are excellent cat-
alyst for the hydrogenation of alkenes and aromatic rings in water
and both the activity and the selectivity of the Rh nanoparticles
can be tuned by the modification of the stabilizer. By replacing PVP
with alkyl-substituted PVPs [18,19], the catalytic activity of the Rh
nanoparticles for the hydrogenation of toluene was enhanced by
70–90% [20]. Although the reasons for the enhanced activity are
not clear, it is possible that the additional alkyl groups provide a
hydrophobic microenvironment around the Rh nanoparticles, facil-
itating substrate diffusion to the catalyst surface. Another approach
involved the coordination of various water soluble phosphine lig-
ands onto the surface of PVP stabilized Rh nanoparticles, which
modifies the steric and electronic properties of the catalysts and
accordingly modifies the catalytic properties [21]. Remarkably, this
strategy was used to increase the selectivity of hydrogenations of
arene rings derivatized with C O bonds, such that the C O bond
remained intact. It has also been shown that the catalytic activity of
Rh nanoparticles in ionic liquids may be finely tuned by employing
purposely designed ligands that allow both activity and stability to
be enhanced simultaneously [22,23].
A large number of reports describe hydrogenations using Pd
nanoparticles in combination with different stabilizers and only
a few examples are mentioned here. Pd nanoparticles stabilized
with an organic polymer catalyze the hydrogenation of alkenes
and alkynes. An ionic copolymer was used to stabilize Pd nanopar-
ticles that showed excellent selectivity in the hydrogenation of
phenol to cyclohexanone [24] and polyelectrolyte-stabilized Pd
nanoparticles (immobilized within a multilayer film) are selec-
tive catalysts for the hydrogenation of unsaturated alcohols [25].
Alkenes with different functional groups may also be hydrogenated
by Pd nanoparticles stabilized by water-soluble aminophosphine
ligands [26]. Dendrimer scaffolds afford very small nanoparticles
with narrow dispersities and the resulting dendrimer-stabilized
Pd nanoparticles have been shown to efficiently catalyze the
hydrogenation of alkenes [27–32]. The activities of the palladium
catalysts tend to be rather low compared to other metals, but most
are inactive for the hydrogenation of arene rings, which imparts
them with an intrinsic selectivity towards alkene and alkyne sub-
stituents. Various Pt nanoparticles have also been reported and
their application in the selective hydrogenation of alkenes has been
demonstrated [27,29,33–36].
Ru nanoparticles are generally more active than palladium-
and platinum-based nanoparticles in the hydrogenation of both
alkenes and arenes. The nature of the stabilizer is also impor-
tant, not only controlling the morphology and stability of the
Please cite this article in press as: S. Bulut, et al., Aqueous-phase hydrogenation of alkenes and arenes: The growing role of nanoscale
catalysts, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.09.002
nanocatalyst, but also influencing the selectivity of the reaction.
Some examples of Ru nanoparticle catalysts with different types
of stabilizers, including ligands, surfactants and polymers, are
listed in Table 1 [36, 58–61]. Iron nanoparticles stabilized with an
amphiphilic polymer catalyze the hydrogenation of alkenes, but
are unable to catalyze the hydrogenation of arenes. Like Pd and
Pt nanoparticles this property makes them useful for the selective
hydrogenation of alkene-substituted arenes [37]. This work also
illustrates another important aspect of the field, that is to replace
precious metals with earth-abundant metals, i.e. first row transi-
tion metals, and in this respect more active systems are needed
that can catalyze the hydrogenation of arenes. In this context, Co
nanoparticles dispersed in an aqueous phase catalyze the hydro-
genation of glucose [38], maltose [39], and butyraldehyde [40].
Cobalt nanoparticle catalyzed arene hydrogenation in water has
seldom been reported, but has potential as arene hydrogenation
over Co catalysts in organic phases is not uncommon [41–43].
Ni/ZSM-5, prepared by in situ decomposition of Ni(CO)4 over
the zeolite, exhibit high activity in the hydrogenation of arenes,
and are able to fully hydrogenate polymethylbenzenes into sat-
urated hydrocarbons, these being particularly difficult substrates
to hydrogenate [44]. Egg-shell type Ni/Al2 O3 shows a higher activ-
ity than Ni/Al2 O3 prepared by conventional impregnation methods
in the hydrogenation of arenes [45]. Furthermore, a skeletal Ni
catalyst prepared from rapidly quenched Ni–Al alloy ribbons was
found to selectively hydrogenated biphenyl to cyclohexylbenzene
with a selectivity of >99% [46]. Although some of these studies
did not use water as the solvent, transferring these catalysts into
an aqueous phase should not be problematic, as many Ni cata-
lysts are stable in water [47]. Iridium nanoparticles coated with
ammonium-based surfactants are very effective catalysts for the
hydrogenation of various arenes, including benzene, toluene, phe-
nol, anisole and ethylbenzoate [48]. Rh nanoparticles stabilized by
ionic or molecular surfactants are also very effective catalysts for
the hydrogenation both alkenes and arenes [49–52].
In certain processes it is desirable to suppress the hydrogenation
of aromatic rings. For example, in the hydrogenolysis (depolymer-
ization) of lignin into aromatic chemicals hydrogenation of the
aromatic rings is clearly undesirable, as it leads to extra consump-
tion of hydrogen and a decrease in the targeted aromatic products.
One approach towards this goal is to dilute highly active precious
metals with less active (and usually cheaper) metals to afford selec-
tive bimetallic nanoparticles [53,54]. Core–shell structured Ni–Ru
nanoparticles, in which the Ru accumulates within the core and
the Ni preferentially resides on the surface, obtained via the co-
reduction of NiCl2 and RuCl3 with NaBH4 in water, have an apparent
activation energy for toluene hydrogenation ca. 20 kJ/mol higher
than related Ru nanoparticles [55]. Similarly, the hydrogenation
of benzene may be reduced when (inert) Au atoms are incorpo-
rated into Ni nanoparticles [56]. As these reactions are conducted
in water, pH can also be used to tune the activity of the nanocat-
alyst in arene hydrogenation reactions. A recent study indicates
that the activity of arene hydrogenation is promoted under acidic
conditions and is inhibited under basic conditions. The competi-
tive absorption of aromatic ring versus hydroxide ions appears to
account for the reduced activity at pH values >7 [57].
The properties of nanocatalysis can also be modified by immobi-
lization on nanoscale supports, which can be inert, e.g. nanotubes
[62,63] and graphene [64], or active, e.g. nanosized metal oxide
supports. Chen et al. [62] reported Pd nanoparticles supported on
polyaniline-functionalized carbon nanotubes, over which phenol
was effectively hydrogenated to cyclohexanone with a selectivity
of >99% in aqueous media under 1 bar H2 . In another report, Pd
nanoparticles immobilized on carbon nanotubes were shown to
hydrogenate alkynes to alkenes under relatively mild conditions
[63]. The partial hydrogenation of alkynes to alkenes is a reaction
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Table 1
Aqueous-phase hydrogenation of arenes and alkenes catalyzed by Ru nanoparticles coated with different types of stabilizers.
of industrial importance and this reactions was found to work well
with Pd nanoparticles immobilized on carbon nanofibres coated
with ionic liquids rather than water [65].
Rhodium nanoparticles adhered to nanosized TiO2 particles,
termed nanocomposite Rh@TiO2 (Fig. 1), show remarkable activity
in the hydrogenation of benzene to cyclohexane with the reaction
proceeding at atmosphere pressure and room temperature [66]. As
the hydrogen pressure is increased, the catalytic activity increases
and very high TOFs may be obtained. Since the Rh@TiO2 nanocom-
posites are insoluble in water they can be easily recovered and
recycled with only a minor loss of the activity noted. The Rh@TiO2
composites were also found to selectively hydrogenate polyaro-
matic compounds such as anthracene [67]. Rhodium nanoparticles
supported on nanosilica, termed Rh@SiO2 , are less active than the
Rh@TiO2 system, apparently due to the different basicities of the
supports. In addition, by a careful design of the nanocomposites,
low noble metal loadings (as low as 0.09% by weight) with high
catalytic activities can be achieved. Other nanocomposites such
as Pd@TiO2 [68], Pt(0)@TiO2 [69] and Rh@Al2 O3 [70], have been
reported, and used as catalysts for the hydrogenation of C X (X = N,
O) bonds.
3. Aqueous-phase hydrogenation of alkenes and arenes
using nanocatalysts stabilized by ionic polymers
Ionic liquids have proven to be excellent stabilizers for metal
based nanocatalysts by providing the nanoparticles not only with
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catalysts, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.09.002
3
steric/coordinative stabilization, but also with electrostatic stabi-
lization [71–74]. In principle, ionic polymers are more effective
nanoparticle stabilizers than ionic liquids since they combine steric
and electrostatic stabilization mechanisms [75]. Indeed, highly sta-
ble Au [76] and Rh [77] nanoparticles dispersed in water phase have
been synthesized in the presence of a carboxylic acid modified PVP.
The Rh nanoparticles exhibited excellent activity in the biphasic
hydrogenation of toluene and the recycling properties were found
to be significantly better than PVP stabilized Rh nanoparticles under
the same conditions.
The detailed mechanism of hydrogenation reactions over water-
dispersed nanoparticle catalysts has been described elsewhere
[78]. Essentially, both oxidative addition and reductive elimination
steps are required and, to some extent, the nanoparticles can be
considered as pseudo-electrochemical cells with the involvement
of the surrounding water molecules. In this sense ionic stabilizers
should facilitate these processes as they are polyelectrolytes. As
mentioned above, a number of ionic polymers have been used to
stabilize metal nanoparticles and they tend to show high activities
and stabilities [79]. Since we are not aware of studies employing
Pd nanoparticles coated with ionic polymer stabilizers that have
been used as catalysts in the selective hydrogenation of styrene
to ethylbenzene we decided to evaluate this type of system. The
ionic polymers used are based on a polystyrene sulfonate anion
combined with functionalized imidazolium cations (Fig. 2). The
polymers were prepared by reacting the sodium salt polystyrene
sulfonate (30% aqueous solution, MW: 200,000) with the appropri-
ate imidazolium chloride. Following ion exchange the polymer was
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Fig. 1. HR-TEM micrographs of TiO2 (left) and Rh@TiO2 (right). The scale bar is 2 nm.

The four different Pd nanoparticles were evaluated as catalysts

Fig. 2. Ionic polymers (IP1–IP4) used to stabilize Pd nanoparticles.
purified by repeated washing with acetone:water (water content
5%).
The Pd nanoparticles coated with IP1–IP4 were prepared by
reduction of bis(acetonitrile)palladium(II) chloride with sodium
tetrahydroborate in aqueous solutions containing the respective
ionic polymers. TEM images of the resulting Pd nanoparticles
(NP1–NP4) are shown in Fig. 3. These images show that the dif-
ferent ionic polymers provide nanoparticles with various shapes
and sizes, the most well-defined in terms of their shape being
those prepared with IP2, which is not unexpected as hydroxyl-
functionalized ionic liquids have been shown to give highly
crystalline palladium and gold nanoparticles [80]. NP1, NP3 and
NP4 are essentially spherical with sizes in the ranges 6–15, 7–18,
and 5–10 nm, respectively. With NP2 the size of the nanoparticles
are in the range 15–25 nm.
in the hydrogenation of styrene under relatively milder condi-
tions in water, i.e. a substrate/catalyst mol ratio of 1000, hydrogen
(1 atm.) at 25 ◦ C (Table 2 and Fig. 4).
The results displayed in Table 2 and Fig. 4 show that NP3,
i.e. those protected with the ether-functionalized ionic polymer
(IP3) are the most active, with essentially quantitative conversion
observed after 4 h. The alcohol-functionalized system, i.e. NP2, are
the next most active. Remarkably, both these nanoparticles are
considerable more active than those with the simple alkyl-based
imidazolium salt, i.e. NP1, despite being much larger. Catalyst NP4,
with the nitrile-functionalized imidazolium cation, are the least
active in this reaction.
The reasons for the superior catalytic performance of NP2 and
NP3 could be due to a number of reasons. Replacement of a CH2 /CH3
group with an oxygen atom or hydroxyl group results in a decrease
of the ionic volume and influences the physical properties of imid-
azolium salts [81,82]. These groups can also participate in hydrogen
bonding, influencing the stabilization of the catalyst and activation
of the substrates in catalytic reactions [83–85]. It has been well doc-
umented that ether [86], nitrile [87], and hydroxyl groups [88,89]
can weakly interact with metal nanoparticle surface and improve
the solubility, stability and the redox properties of nanoparticles.
These functional groups are also able to help activate the sub-
strate. In comparison, the aqueous-phase hydrogenation of styrene
catalyzed by polyamidoamine stabilized Pd nanoparticles under
more forcing conditions requires over 6 h to reach completion
[90].
The ability to recycle and reuse the catalysts was also explored
following product extraction with diethyl ether. Recycling exper-
iments showed different phenomena depending on the ionic
polymer used to stabilize the nanoparticles. Nanoparticles NP2

Table 2
Conversion of styrene to ethylbenzene as a function of time in the aqueous-phase using the ionic polymer stabilized Pd nanoparticles (NP1–NP4).

Time [h] Conversion [%]

NP1a NP2a NP3a NP4a NP4b

1 16.3 15.4 22.7 13.4 0.7

2 32.4 35.9 42.7 25.5 2
3 54.5 63.6 70.9 43.5 4.3
4 80.6 93.9 98.8 72.6 9.9
5 98 99.4 100 94.3 17
5.5 99.8 99.5 100 98.6 31.2
6 99.9 99.7 100 100 50.2
16c 100 100 100 100 57.7

TOF [h−1 ]d 201 235 247 182 247

Reactions were carried out using styrene (2 mmol), H2 (1 atm.) and the required amount of the catalyst in water (total volume 8 ml) at room temperature. Styrene and
ethylbenzene were quantified following extraction into Et2 O and GC analysis employing decane as an internal standard.
a
Catalyst = 0.1 mol% (2 × 10−3 mmol).
b
Catalyst = 0.01 mol% (2 × 10−4 mmol).
c
After 16 h no hydrogenation of ethylbenzene was observed.
d
The turnover frequency (TOF) was calculated after a reaction time of 4 h as [(mol product)/(mol catalyst × time)].

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Fig. 3. TEM images of Pd nanoparticles (NP1–NP4) stabilized by the ionic polymers (IP1–IP4 shown in Fig. 2, respectively).

and NP3, with oxygen-functionalized IPs could not be efficiently
recycled (presumably due to solubility in diethyl ether). In con-
trast, the activity of NP1 and NP4 was maintained for several
cycles with relatively minor decreases in activity observed (see
Table 3).
that lignin will become a source of key chemicals in the future.
Ionic polymer nanoparticle stabilizers could lead to some of the
most active catalysts for this reaction and may allow less active,
more abundant elements to be used in place (or potentially

4. Outlook-challenges, prospects and opportunities Table 3

Recycling experiments for the hydrogenation of styrene to ethylbenzene in the
aqueous-phase catalyzed by NP1 and NP4.
Ionic polymer stabilized nanoparticles offer much potential
in aqueous-phase hydrogenations of both alkene and arene sub- Run Conversion [%]
strates. The nature of the ionic polymer strongly influences the NP1 NP4
catalytic activity, but in general, appears to lead to more active
1 98 94
catalysts than nanoparticles coated with neutral polymers and 2 96 90
other types of stabilizers. The reasons for this remain uncer- 3 96 89
tain, but as mentioned above, the nanoparticles could be viewed
Reactions were carried out using styrene (0.5 mmol), H2 (1 atm.) and 0.1 mol%
as pseudo-electrochemical cells which benefit from the involve- (5 × 10−4 mmol) catalyst in water (total volume 2 ml) at room temperature for 5 h.
ment of a polyelectrolyte stabilizer. The ability to hydrogenate Styrene and ethylbenzene were quantified following extraction into Et2 O and GC
aromatic substrates is of growing importance since it is likely analysis employing decane as an internal standard.

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Fig. 4. The conversion of styrene () to ethylbenzene () as a function of time in the aqueous-phase using the ionic polymer stabilized Pd nanoparticles (NP1–NP4).

combined with) nanoparticles based on precious metals. Indeed,
the selectivity of the reaction can be controlled by using the
appropriate metal or by blocking certain reaction sites (see
above).
While arene hydrogenation appears to be limited to nanocata-
lysts, for alkenes and alkynes there are many alternative options.
Organocatalysts and frustrated Lewis acid catalysts show con-
siderable promise, but both tend to be used in solvents of low
polarity [91]. Organocatalysts can be used in aqueous solutions, but
are currently more limited to oxidation reactions [92]. Moreover,
hydrogen gas is not the only source of hydrogen, e.g. hydrazine
[93–95], NaBH4 [96], LiAlH4 [97], and formic acid [98] can also
be used, although each one presents its own set of problems as
well as potential benefits. In principal, the photocatalytic proper-
ties of TiO2 could be used to split water and generating hydrogen
directly from water for hydrogenation reactions that could, in the
long-term, be the ultimate way in which to perform aqueous-phase
hydrogenations.
Finally, one promising yet poorly explored direction is the
development of 2D or subnano dimensional catalysts that can
catalyze hydrogenation reactions in water. Very recently, PVP-
supported single-layered, graphene-like Rh nanosheets, which
were found to be much more active in the hydrogenation of phenol
compared to spherical Rh nanoparticles and Rh/C, were reported
[99]. A full exposure of Rh atoms in the PVP-capped single lay-
ered Rh nanosheets presumably leads to the significantly enhanced
catalytic activity, although the unique electronic structure of the
nanosheet may also play a role. The Rh nanosheets were evalu-
ated in organic solvent, however, since the material is capped by
a hydrophilic polymer it may well operate in water. Water sol-
uble Au nanoclusters with precise numbers of gold atoms have
been reported [100,101], and it will be interesting to evaluate these
sub-nanoscale materials in the hydrogenation reactions.
5. Experimental
Sodium polystyrene sulfonate (30% aqueous solution,
MW: 200,000), styrene (extra pure), NaBH4 , 1-butyl-3-
methylimidazolium chloride, hydrogen gas and decane were
obtained from commercial sources and used as received. The
imidazolium chlorides 1-(2-hydroxyethyl)-3-methylimidazolium
chloride [102], 1-(2-methoxyethyl)-3-methylimidazolium chlo-
ride [102] and 1-(3-cyanopropyl)-3-methylimidazolium chloride
[103] were prepared using literature protocols. Solution NMR
spectra were recorded in deuterated solvents at 20 ◦ C on a Bruker
DMX 400 spectrometer; data are given in ppm relative to TMS

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using the solvent signals as a secondary reference. IR spectra
were recorded at room temperature on a Perkin-Elmer FTIR 2000
spectrometer. Gas Chromatography (GC) analysis was performed
on a Varian Chrompack CP-3380 Gas Chromatograph using N2
as carrier gas equipped with a capillary column from Agilent
(length × diameter × film: 25 m × 0.25 mm × 0.25 ␮m) and an FID
detector. The following GC oven temperature programme was
used: 40 ◦ C hold for 2 min, ramp 15 ◦ C/min to a final temperature
of 130 ◦ C (or 250 ◦ C). Transmission electron microscopy (TEM)
was carried out on a Philips/FEI CM12 microscope operating at
28 kV (NP1-2) and 100 kV (NP3) acceleration voltage or JEOL JEM-
2010 microscope operating at 200 kV (NP4) acceleration voltage.
Samples for analysis were prepared by dropping the nanoparticle
solutions in water onto a carbon-coated Cu grid and allowing the
solvent to evaporate.
5.1. Synthesis of the ionic polymers (IP1–IP4)
IP1: Sodium polystyrene sulfonate (6.28 g of 30% aqueous solu-
tion, 9.1 mmol relating to the mole mass of the monomer salt) was
added under stirring at room temperature to a solution of 1-butyl-
3-methylimidazolium chloride (1.75 g, 10 mmol) in water (10 ml).
The mixture was stirred at room temperature for further 30 min,
then acetone was added to afford an oily precipitate that was sep-
arated by decanting the water phase. The precipitate was washed
with an acetone/water mixture (water content: 5%) and the solid
was dried at room temperature under vacuum. Isolated yield: 51%.
1 H NMR (400.13 MHz, D O, 293 K): ı = 8.55 (1H, s), 7.40 (1H, s), 7.35
2
(1H, s), 7.33 (2H, br), 7.00 (2H, br), 4.10 (t, 2H, J = 6.0 Hz), 3.80 (3H,
s), 1.68 (2H, q, J = 7.0 Hz), 1.13 (2H, q, J = 7.0 Hz), 1.00–2.00 (3H, m),
0.70 (3H, t, J = 7.0 Hz). IR: ṽ (cm−1 ) = 3166, 3121, 2967, 2941, 1575,
1472.
IP2: Same procedure as that described for IP1, reagents:
sodium polystyrene sulfonate (6.28 g of 30% aqueous solution,
9.1 mmol relating to the mole mass of the monomer salt) and 1-(2-
hydroxyethyl)-3-methylimidazolium chloride (1.27 g, 10 mmol).
Isolated yield: 50%. 1 H NMR (400.13 MHz, D2 O, 293 K): ı = 8.45 (1H,
s), 7.40 (1H, s), 7.30 (1H, s), 7.33 (2H, br), 7.02 (2H, br), 4.60 (t, 2H,
J = 7.0 Hz), 4.20 (2H, t, J = 7.0 Hz), 3.80 (3H, s), 1.00–2.00 (3H, m). IR:
ṽ (cm−1 ) = 3540, 3160, 2966, 1580.
IP3: Same procedure as that described for IP1, reagents:
sodium polystyrene sulfonate (6.28 g of 30% aqueous solution,
9.1 mmol relating to the mole mass of the monomer salt) and 1-(2-
methoxyethyl)-3-methylimidazolium chloride (1.41 g, 10 mmol).
Isolated yield: 57%. 1 H NMR (400.13 MHz, D2 O, 293 K): ı = 8.60 (1H,
s), 7.40 (1H, s), 7.30 (1H, s), 7.33 (2H, br), 7.00 (2H, br), 4.35 (t, 2H,
J = 6.0 Hz), 3.85 (3H, s), 3.75 (2H, t, J = 7.0 Hz), 3.40 (3H, s), 1.00–2.00
(3H, m). IR: ṽ (cm−1 ) = 3140, 2988, 1567, 1197, 1065.
IP4: Same procedure as that described for IP1, reagents:
sodium polystyrene sulfonate (6.28 g of 30% aqueous solution,
9.1 mmol relating to the mole mass of the monomer salt) and 1-
(3-cyanopropyl)-3-methylimidazolium chloride (1.86 g, 10 mmol).
Isolated yield: 67%. 1 H NMR (400.13 MHz, D2 O, 293 K): ı = 8.20 (1H,
s), 7.55 (1H, s), 7.53 (1H, s), 7.34 (2H, br), 7.02 (2H, br), 4.30 (t, 2H,
J = 7.0 Hz), 3.82 (3H, s), 2.50 (t, 2H, J = 7.0 Hz), 2.20 (t, 2H, J = 7.0 Hz),
1.00–2.00 (3H, m). IR: ṽ (cm−1 ) = 3023, 2920, 2243, 1692.
5.2. Synthesis of the Pd nanoparticles (NP1–NP4)
Bis(acetonitrile)palladium(II) chloride (26 mg, 0.1 mmol) was
added to a solution of appropriate ionic polymer (IP1–IP4, 0.5 g)
in water (100 ml). The resulting mixture was stirred for 8 h at room
temperature and then NaBH4 (8 mg, 0.21 mmol) was added at room
temperature and the solution stirring for an additional 2 h. The
colour of the suspension turned black.
Please cite this article in press as: S. Bulut, et al., Aqueous-phase hydrogenation of alkenes and arenes: The growing role of nanoscale
catalysts, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.09.002
7
5.3. Hydrogenation of styrene
All hydrogenation reactions were carried out at room tempera-
ture under hydrogen (1 atm.) in water. For this purpose, 0.002 mmol
of the Pd nanoparticles (0.1 mol%, 2 ml from a 1 mM aqueous solu-
tion) and 50 mg decane as internal standard for GC were placed in a
two-neck flask (10 ml). After completion the reaction volume with
water to a total volume of 8 ml, the flask was connected to a vac-
uum line/hydrogen setup and the air inside the flask was removed
via vacuum-hydrogen flow (4 times). The reaction mixture was
put under a hydrogen atmosphere (1 atm.) with stirring for 15 min
and then styrene (2 mmol, 208 mg) was added via a septum (time
point = 0). Samples (0.3–0.4 ml) were removed after 5, 15, 30, 60,
120, 180, 240, 300, 360 and 960 min and extracted with Et2 O (2 ml).
After separation of the phases the organic phase was analyzed by
GC.
Acknowledgments
We thank EPFL and the Swiss National Science Foundation
National Research Programme (NRP 66) for the financial support.
We thank Prof. Alain Roucoux for providing the original TEM
images used in Fig. 1 and the Interdisciplinary Centre for Elec-
tron Microscopy (CIME) at the EPFL for the facility enabled TEM
measurements.
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