Palladium nanoparticles stabilized by novel choline-based ionic liquids in glycerol applied in hydrogenation reactions

Article abstract of DOI:10.1016/j.cattod.2019.01.052

Palladium nanoparticles stabilized by choline-based ionic liquids in glycerol were prepared from Pd(II) precursors by simply heating at 80 °C under argon; in this process, the water present in the ionic liquid was found to be responsible for the reduction of Pd(II) into zero-valent palladium species. Palladium nanoparticles were fully characterized in both liquid phase and solid state. The as-prepared metal nanoparticles exhibited remarkable catalytic activity in hydrogenation processes for a significant variety of functional groups (alkenes, alkynes, nitro derivatives, benzaldehydes, aromatic ketones).

Full text of DOI:10.1016/j.cattod.2019.01.052

Accepted Manuscript
Title: Palladium nanoparticles stabilized by novel
choline-based ionic liquids in glycerol applied in
hydrogenation reactions
Authors: Garima Garg, St e´ phanie Foltran, Isabelle Favier,
Daniel Pla, Yaocihuatl Medina-Gonz a´ lez, Montserrat G o´ mez
PII:
S0920-5861(18)31408-1
DOI:
Reference:
https://doi.org/10.1016/j.cattod.2019.01.052
CATTOD 11923
To appear in:
Catalysis Today
Received date:
Revised date:
Accepted date:
26 November 2018
11 January 2019
18 January 2019
Please cite this article as: Garg G, Foltran S, Favier I, Pla D, Medina-Gonz a´ lez
Y, G o´ mez M, Palladium nanoparticles stabilized by novel choline-based ionic
liquids in glycerol applied in hydrogenation reactions, Catalysis Today (2019),
https://doi.org/10.1016/j.cattod.2019.01.052
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Catalysis Today
Palladium nanoparticles stabilized by novel choline-based ionic liquids in glycerol applied in
hydrogenation reactions.
a,b
a,b
b
b
a,*
Garima Garg , Stéphanie Foltran, Isabelle Favier, Daniel Pla, Yaocihuatl Medina-González ,
b,*
Montserrat Gómez
a
Laboratoire de Génie Chimique, Université de Toulouse, CNRS, INPT, UPS, 4 Allée Emile Monso, CS 84234,
3
1030 Toulouse, France, yaocihuatl.medinagonzalez@ensiacet.fr.
b
Laboratoire Hétérochimie Fondamentale et Appliquée, UMR CNRS 5069, Université de Toulouse 3 – Paul
Sabatier, 118 route de Narbonne, 31062 Toulouse cedex 9, France, gomez@chimie.ups-tlse.fr.
Highlights





Palladium nanoparticles in glycerol stabilized by novel choline-based ionic liquids
Characterization of palladium nanoparticles both in solid and liquid phase
Palladium nanoparticles showing high catalytic activity in hydrogenation reactions
Selective hydrogenations for non-conjugated alkynes
Efficient reduction of carbonyl derivatives
Abstract
Palladium nanoparticles stabilized by choline-based ionic liquids in glycerol were prepared from Pd(II)
precursors by simply heating at 80 °C under argon; in this process, the water present in the ionic liquid
was found to be responsible for the reduction of Pd(II) into zero-valent palladium species. Palladium
nanoparticles were fully characterized in both liquid phase and solid state. The as-prepared metal
nanoparticles exhibited remarkable catalytic activity in hydrogenation processes for a significant variety
of functional groups (alkenes, alkynes, nitro derivatives, benzaldehydes, aromatic ketones).
Keywords: palladium nanoparticles, choline-based ionic liquids, amino acid, glycerol, hydrogenation
1. Introduction
Palladium nanoparticles (PdNPs) due to their high efficiency, selectivity and their ability to perform
various kinds of catalytic reactions have emerged as an important tool in organic synthesis. PdNPs are
one of the most used and efficient catalysts to build C–C bonds and to perform other chemical
transformations such as carbon-heteroatom bond formation, hydrogenation, carbonylation and oxidation
processes [1]. Well-defined PdNPs are appropriate catalysts for hydrogen activation and hydrogen
spillover [2,3]. However, the choice of the right type of stabilizer is a key parameter for the synthesis of
PdNPs precluding agglomeration and leaching of metal [4]. For this purpose, stabilizers like surfactants,
ligands, polymers and ionic liquids have been widely used [5] to tailor PdNPs size, composition and
morphology, thereby tuning the reactivity and selectivity of these systems [6]. In this context, ionic
liquids (ILs) have emerged as promising contenders for the stabilization of nanoparticles. As mentioned
by Dupont et al., ILs exhibit dispersive forces with polar and nonpolar nano-domains and can form
extended networks of hydrogen bonds due to which they are to be considered as supramolecular fluids
and not homogeneous solvents [7]. Imidazolium-based ionic liquids represent the most commonly used
molten salts applied in catalysis, in particular for the stabilization of metal-based nanoparticles [8].
Choline chloride, a quaternary ammonium salt, has also emerged as a popular choice for bio-sourced

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ILs and its use in synthesis of nanoparticles in the form of deep eutectic solvents (DESs) or otherwise
have also been reported [9].
In our group, PdNPs stabilized by [BMI][PF ] have been generated in previous studies leading to high
6
catalytic activity in Suzuki cross-coupling reaction without palladium leaching up to ten cycles [10, 11].
In this frame, in particular, PdNPs stabilized by thioether-phosphine ligands had been used as catalytic
precursors in Heck–Mizoroki cross-coupling and C=C hydrogenation reactions [12]. However, the
above-mentioned ILs have environmental concerns, which consequently led to the search of an
environmental friendly medium. In this context, our team has developed the synthesis of nanoparticles
in glycerol medium [13-14]. Glycerol is produced in high amounts as waste in biodiesel production. Its
low-cost, non-toxicity, high boiling point (290 °C), negligible vapor pressure (< 1 mmHg at 293 K),
high solubilizing ability for organic (except those completely apolar) and inorganic compounds, and low
miscibility with other organic solvents such as ethers and alkanes, constitute striking properties that
make it especially interesting for applications in catalysis. It plays an important role as support for the
immobilization of PdNPs, permitting an easy recycling of the catalytic phase [13]. Our team has
synthesized PdNPs in both solution and solid state, using naturally occurring cinchona-based alkaloids
in neat glycerol and successfully applied in dihydrogen-based processes, such as hydrogenation of
unsaturated functional groups (alkenes, alkynes, imines, and nitro-based substrates) and
hydrodehalogenation of halo-aromatic compounds [14].
In order to extend our research in sustainable chemistry, we report here the synthesis of PdNPs using
choline based ionic liquids in neat glycerol; the synthesized PdNPs were applied in hydrogenation
reactions. Choline based ILs are environmentally friendly with good biocompatible properties and
presenting interesting solvent properties: non-flammability, negligible vapor pressure at ambient
conditions and high solubility [15]. Furthermore, we also avoid the plausible reactivity of ILs (such as
in case of imidazolium-based ILs) with the metal surface [16].
2. Experimental
2.1.Materials and methods
Unless otherwise stated, all chemical reagents were obtained from commercial suppliers and used
without further purification. All manipulations were performed using Schlenk techniques under argon
atmosphere. Glycerol was dried under vacuum at 80 °C for 18 h prior to use. N-tosyl-alanine was
prepared following previously reported methodology [17]. High-pressure reactions were carried out in
a Top Industrie Autoclave. NMR spectra were recorded on a Bruker Advance 300 spectrometer at 293
1
13
15
K (300 MHz for H NMR, 75.5 MHz for C NMR and 50.6 MHz for N). GC analyses were carried
out on a GC Perkin Elmer Clarus 500 with ionization flame detector, using SGE BPX5 column
composed by 5% phenylmethylsiloxane, coupled to a Perkin Elmer Clarus MS560 mass detector. TEM
images of PdNPs dispersed in glycerol were obtained from a JEOL JEM 1400 instrument running at 120
kV. PdNPs size distributions and average diameters were determined from TEM images applying
Image-J software associated to a Microsoft Excel macro. IR spectra were recorded in the range of 4000-
-1
4
00 cm on a Varian 640-IR FTIR Spectrometer. Powder X-ray diffraction analyses were collected on
a XPert (Theta-Theta mode) Panalytical diffractometer with α(Cu Kα1, Kα2)=1.54060, 1.54443 Å.
Elemental and ICP-AES analyses were carried out at the “Service d’Analyse” of Laboratoire de Chimie
de Coordination (Toulouse) using a Perkin Elmer 2400 series II analyser and an iCAP 6300 ICP
Spectrometer. XPS measurements were performed at room temperature with a SPECS PHOIBOS 150
-10
hemispherical analyzer (SPECS GmbH, Berlin, Germany) in a base pressure of 5x10 mbar using
monochromatic Al Kα radiation (1486.74 eV) as excitation source. Mass spectroscopy was done using
UPLC Xevo G2 Q TOF (Waters) by high-resolution electrospray technique. Viscosity was measured
using the Rheometer AR2000Ex from TA Instruments.
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2.2. Synthesis of choline N-tosylalaninate (B)
Choline hydroxide (103 mg, 0.85 mol, 46 wt.% in H
2
O) was stirred with an aqueous solution of N-
tosyl-alanine (206 mg, 0.85 mmol) at 60 °C for 12 h. After the ion exchange reaction, water was
evaporated under vacuum at 80 °C, obtaining a brownish viscous oil (294.1 mg, 99.9%). B was obtained
1
as a racemic mixture. H NMR (300 MHz, DMSO-d
6
) δ 7.72 – 7.61 (m, 2H), 7.35 – 7.22 (m, 2H), 4.08
–
=
5
3.96 (m, 2H), 3.69 – 3.60 (m, 1H), 3.50 – 3.44 (m, 2H), 3.19 – 3.12 (m, 9H), 2.29 (s, 3H), 1.20 (d, J
1
3
7.2 Hz, 3H). C NMR (75 MHz, DMSO-d ) δ 172.6, 142.4, 137.8, 129.5, 126.6, 67.0, 67.0, 66.9,
6
+
5.1, 53.2, 53.1, 53.1, 52.1 20.9, 19.6. HR-MS (ESI+) for C
5
H
14NO : Theoretical = 104.1075,
ˉ
Experimental = 104.1072; HR-MS (ESI-) for C10
H12NO
4
S : Theoretical = 242.0487, Experimental =
-1
2
1
42.0483. IR (ATR, cm ) 3256, 3045, 2954, 2922. 2866, 2853, 2427, 1718, 1598, 1456, 1397, 1324,
221, 1093, 958, 884, 816, 708, 662. Viscosity 3054 Pa.s at 25 °C and 2.973 Pa.s at 80 °C.
2.3. Synthesis of palladium nanoparticles stabilized by choline-based derivatives in glycerol
0
.05 mmol (14.1 mg) of [PdCl (cod)] and 0.85 mmol of choline-based derivative [117 mg for
2
choline chloride (A); 294.5 mg for choline N-tosylalaninate (B)] were dissolved in 5 mL of glycerol and
stirred under argon in a Schlenk flask at 80 °C for 18 h. Then, the resulting solution was washed with
dichloromethane (3x5 mL) in order to remove any insoluble IL from glycerol phase. A black colloidal
solution was then obtained.
2.4. Synthesis of palladium nanoparticles stabilized by choline tosylalaninate at solid state, PdB
After synthesis, PdNPs in glycerol were transferred to a centrifugation tube and 2 mL of ethanol
were added. Centrifugation was carried out at 4500 rpm for 1 h and then the solution was separated by
decantation. This process was repeated 3 times until complete removal of glycerol. The remaining black
powder was then dried under vacuum at 80 °C overnight. Elementary analysis (palladium content
determined by ICP-AES) for PdB: Pd 84.0%, C 7.55%, N 0.30%, H 0.40%.
2.5. General procedure for Pd-catalyzed hydrogenation in glycerol
In a Fisher–Porter bottle (working from 1 to 3 bar total pressure) or an autoclave (working from 3
to 20 bar total pressure), the appropriate substrate (1 mmol for 1 mol% of catalyst or 10 mmol for 0.1
mol% of catalyst) was added to 1 mL of preformed nanoparticles (2.85 mg of Pd) in glycerol under
argon. The reaction mixture was put under vacuum and then pressurized with H at the convenient
2
pressure, heated up at 80 °C and stirred for the appropriate time; then cooled down to room temperature
before extraction. Organic products were extracted from glycerol by a biphasic methodology, adding
dichloromethane (5 × 3 mL); organic phases were collected and solvent removed under vacuum.
Conversion and yields were determined by GC using decane as internal standard. The obtained products
1
13
were characterized by GC-MS data and H and C NMR and compared to literature reports to confirm
spectral identity (see Supplementary Material).
3
3
=
. Results and discussion
.1. Synthesis of palladium nanoparticles stabilized by choline-based ionic liquids in glycerol
Palladium nanoparticles (PdA, PdB) were prepared by thermal decomposition of [PdCl
1,5-cyclooctadiene) in the presence of a choline-based ionic liquid [choline chloride (A); choline N-
2
(cod)] (cod
tosylalaninate (B)], using glycerol as solvent (Scheme 1). The ionic liquid B was prepared based on the
reported methodology for the preparation of choline carboxylate ionic liquids (see above, Experimental
section) [18]. In both cases, black colloidal solutions were obtained, constituted by spherical small
nanoparticles (for PdA, 1.4 ± 0.6 nm; for PdB, 1.7 ± 0.6 nm), exhibiting a very well-dispersion mainly
thanks to the supramolecular structure of glycerol which avoids agglomeration, as evidenced in our
previous works using ligands and polymers as stabilizers [13, 14, 19] (Fig. 1). It is important to highlight
that these reaction conditions do not trigger any deprotection of choline N-tosylalaninate [20].
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Scheme 1. Synthesis of palladium nanoparticles in glycerol using choline-based ionic liquids (A,
B) as stabilizers.
Control tests proved that the water present on the IL (for A, 0.25%; for B, 1.70%; determined by
Karl-Fischer titration) is the responsible of the reduction of Pd(II) into Pd(0); [PdCl (cod)] in dry
2
glycerol under the same conditions used in the synthesis of PdNPs was stable and did not exhibit
decomposition. This is in agreement with the work carried out by Hirai and coworkers, proving the
unsuccessful synthesis of zero-valent rhodium nanoparticles in anhydrous alcohols [21].
When PdNPs were synthesized in the absence of any stabilizer using wet glycerol and different
palladium precursors, Pd(0) agglomerates were formed [13(d)].
PdA
dmean = 1.4± 0.6 nm
No. of particles = 3031
PdB
200
150
100
dmean = 1.7 ± 0.6 nm
No. of particles = 2043
50
0
Diameter (in nm)
Figure 1. TEM images of PdA and PdB in glycerol with the corresponding size distribution
diagrams.
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Palladium acetate was also tested as starting metal precursor with the two choline derivatives,
obtaining in both cases aggregates; for choline chloride, anisotropic nano-objects were observed
probably due to the presence of halides at the metal surface (see Fig. S1 in the Supplementary material)
-
1
[
22]. We then added polyvinylpyrrolidone (mean molecular weight = 10000 g.mol ), in order to improve
the dispersion, but in this case very few nanoparticles could be detected by TEM (see Fig. S2 in the
Supplementary material). Curiously, when dihydrogen was used as reducing agent, an immediate
precipitation of bulk palladium took place.
We envisaged the use of choline alaninate as stabilizer (see experimental part and Scheme S1 in the
Supplementary Material) [23], instead of the protected anion N-tosylalaninate; however, choline
alaninate became unstable under atmospheric conditions, due to its high reactivity with carbon dioxide,
giving the corresponding carbamate (see Scheme S2 in the Supplementary Material) [24]. Moreover,
we also studied the effect of the solvent on the synthesis of colloidal PdNPs, using water and ethanol
instead of glycerol under the same conditions than those described in Scheme 1. In both cases, fast
precipitation of black palladium was observed, proving that glycerol avoids the agglomeration of metal-
based nanoparticles probably due to its supramolecular structure [13(a), 25, 26].
Given the better catalytic behavior of PdB (see below Table 1), this catalyst was selected for full
characterization. Palladium nanoparticles at solid state were isolated by centrifugation. Powder X-ray
diffraction (PXRD) analysis showed the presence of crystalline nanoparticles exhibiting face cubic
center Pd(0) structure (Fig. 2). The crystallite size found from the X-ray diffraction peaks (calculated
by the Scherrer equation) is ca. 3.7 nm; differences in size between TEM and XRD are frequently
observed because the average crystallite size (PXRD) is not necessarily the same as the particle size
(
TEM)[27]. XPS analysis corroborated the absence of any oxidized palladium species (Fig. 3 and Fig.
S3 in the Supplementary Material); XPS showed the presence of carbon, oxygen and nitrogen that
confirms the presence of the ionic liquid even after isolation of nanoparticles; the presence of chloride
probably comes from the metal precursor.
Figure 2. PXRD diffractogram of PdB at solid state (sharp blue lines correspond to the diffraction
pattern of bulk fcc Pd(0)).
(
a)
(b)
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6
5
4
3
2
1
0000
0000
0000
0000
0000
0000
0
12000
10000
8000
6000
4000
C1s
84.8
3
40.9
2
Pd3d3/2
335.6
Pd3d5/2
2
000
0
3
25
330
335
340
345
350
355
2
75
280
285
290
295
300
Binding energy (eV)
Binding energy (eV)
(c)
(d)
3
3
2
2
1
1
5000
0000
5000
0000
5000
0000
O1s
13400
N1s
400.1
5
32.5
1
1
1
1
1
3200
3000
2800
2600
2400
5
000
0
3
85
390
395
400
405
410
5
20
525
530
535
540
545
Binding energy (eV)
Binding energy (eV)
Figure 3. HR-XPS spectra of PdB at solid state for (a) Pd(0), (b) carbon, (c) oxygen and (d)
nitrogen.
It is important to highlight that PdB at solid state could be re-dispersed in glycerol without formation
of aggregates (see Fig. S4 in the Supplementary Material). This is in agreement with the XPS analysis
that shows the presence of IL at the surface of PdNPs in solid state.
3.2. Pd-catalyzed hydrogenation reactions
The surface reactivity of palladium nanoparticles is very well known, in particular applied in
hydrogenation processes involving different kinds of functions [28]. The morphology effect of PdNPs
(
(
size, shape) on reactivity is crucial [4]. PdNPs synthesized by wet methodologies contain stabilizers
salts, ligands, polymer, surfactants etc.) [29], which modify the surface state and in consequence their
catalytic behavior [30, 6c]. In ionic liquid medium, many works have been reported in the literature,
mainly focused on the hydrogenation of alkenes and alkynes [31], but only few of them concerning other
functional groups such as carbonyls [32].
In the present study, we focused on sustainable ionic liquids from choline, due to the stabilization
of PdNPs essentially by electrostatic effect, in glycerol, which helps to the dispersion of nanoparticles.
We chose the hydrogenation of 4-phenylbut-3-en-2-one as benchmark reaction. Both catalysts, PdA and
PdB, behave likewise, giving exclusively 4-phenylbutan-2-one (entries 1-2, Table 1), interesting
skeleton present in fragrances [33]. Both systems were also highly active at low Pd load (0.1 mol%,
entries 3-4, Table 1). However, at shorter times (1 h reaction), only PdB preserved the activity (entry 5
vs 6, Table 1), probably due to the non-innocent effect of the chloride anions present in PdA, which can
trigger a poison effect due to the adsorption of chloride ions at the surface [32].
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Table 1
Hydrogenation of 4-phenylbut-3-en-2-one catalyzed by PdNPs in glycerol stabilized by ChCl (A) and
a
ChTsAla (B).
b
Entry
Catalyst
Conv. (yield) (%)
1
2
PdA
PdB
PdA
PdB
PdB
PdA
100 (96)
100 (93)
50 (49)
100 (91)
96 (92)
55 (51)
c
3
c
4
c,d
5
c,d
6
a
Results from duplicated experiments. Reaction conditions: 1 mmol of 1 and 1 mL of the corresponding
-2
-1
b
catalytic glycerol solution of PdNPs (10 mol L , 0.01 mmol of total Pd). Determined by GC and
GC/MS using decane as internal standard. 0.1 mol% Pd load. Reaction time 1 h.
c
d
With the aim of carrying out a scope related to functions susceptible to be reduced by PdB we firstly
analyzed the behavior of PdB in the hydrogenation of alkenes and alkynes (Table 2). The terminal non-
substituted alkene 1-dodecene (2) was converted into dodecane and internal alkenes in a ratio of 54/46
respectively under smooth conditions (3 bar H
conditions (20 bar H , 18 h), (-)-β-pinene (3) was mainly isomerized, giving only 18% of hydrogenated
product (entry 2, Table 2); PdB was not active enough to reduce (+)--pinene (entry 3, Table 2).
However, for conjugated C=C bonds (alkene 5), full conversion was achieved under 3 bar H overnight
entry 4, Table 2). In agreement with this behavior, the extended conjugated substrate 6 was fully
2
and 2 h of reaction; entry 1, Table 2). Under harsher
2
2
(
hydrogenated concerning the non-aromatic C=C bonds (entry 5, Table 2). The more sterically hindered
conjugated substrate 1,2,3,4,5-pentamethylcyclopentadiene (7) allowed the selective reduction of one
of the two endocyclic C=C bonds working at 20 bar of H
Internal aromatic alkynes (8, 9) were fully reduced obtaining the corresponding alkane derivatives
entries 7-8, Table 2). At lower H pressure (entry 9, Table 2), only the formation of the corresponding
2
pressure (entry 6, Table 2).
(
2
Z-alkene was observed, giving up to ca. 50% yield; longer reaction times led to the formation of 1,2-
diphenylethane. However, the internal alkyl-substituted alkyne, 5-decyne (10; entry 10, Table 2) gave
mainly the corresponding internal alkene; at longer time (18 h), full hydrogenation was observed (entry
1
1, Table 2).
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Table 2
a
Hydrogenation of alkenes and alkynes catalyzed by PdB in glycerol.
b
Conv. (yield)
%)
Entry
Substrate
Product
pH (bar)
2
(
c
3
20
100
100
1
d
2
2H
3H
e
2
0
88
2
f
(
3)
[65 ]
3
4
3
G
3
4
5
-
20
3
n.r.
g
g
100 (99)
100 (98)
5
6
7
5H
6H
7H
3
3
86 (n.d)
[100 (n.d)]
6
(
20)
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7
1
3
100 (97)
8
9
H
H
8
8
9
100 (99)
50 (49)
9
9
1
9
I
h,i
1
1
0
1
3
3
100 (90/10)
1
0
0
1
0H
h
100 (96)
1
0I
1
a
Results from duplicated experiments. Reaction conditions: 1 mmol of substrate (2-10) and 1 mL of the
-2
-1
catalytic glycerol solution of PdB (10 mol L , 0.01 mmol of total Pd); n.r. means no reaction; n.d.
means not determined. Determined by GC and GC/MS using decane as internal standard.
Dodecane/internal alkenes = 54/46. Dodecane/internal alkenes = 55/45. Ratio 3/3G/3H = 12/70/18.
b
c
f
d
e
g
h
i
Ratio 3/3G/3H = 35/43/22. Isolated yield. Cyclooctane as internal standard. cis-5-decene/n-decane
90/10.
=
We were also interested in the hydrogenation of other organic functional groups, such as nitro and
carbonyl derivatives (Table 3). As expected, nitrobenzene gave aniline in quantitative yield (entry 1,
Table 3). PdB was also an efficient catalyst for the reduction of carbonyl groups, coming from both
aldehydes (12-14) and ketones (15-17). Concerning the formyl groups, benzaldehyde derivatives
exhibiting substituents inducing different electronic effects, were fully converted into the corresponding
benzyl alcohols under smooth conditions (3 bar H
were hydrogenated to give the corresponding secondary alcohols, but under higher hydrogen pressure
entries 5-6, Table 3). The non-conjugated ketone (1H) gave a moderate conversion to the corresponding
secondary alcohol (1I) at 40 bar H pressure (entry 7, Table 3). The 1-phenylprop-2-yn-1-one (17)
mainly gave the saturated ketone (17H) with only 15% of the corresponding secondary alcohol (17I)
entry 8, Table 3). This reactivity behavior concerning the reduction of carbonyl groups follows the
2
; entries 2-4, Table 3). Aromatic ketones 15 and 16
(
2
(
same trend than that reported recently by J. Dupont and co-workers using supported palladium
nanoparticles on poly (ionic liquid) materials based on pyrrolidinium salts [32(a)].
Alkyl ketones (such as 3-pentanone and 2,2,4,4–tetramethyl pent-3-one) and alkyl aldehydes (like
2
hexanal) were not reduced (up to 20 bar H ). Similarly, benzonitrile was not hydrogenated under harsh
conditions.
After catalysis, no leaching of Pd was detected by ICP-AES analyses. But, some aggregation was
observed by TEM preserving the zero-valent PdNPs (see Figs. S5 and S6 in the Supplementary
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Material); the formation of aggregates may be the reason for the observed decrease of the catalytic
activity and hence it was difficult to use the PdNPs for an efficient recycling (see Fig. S7 in the
Supplementary Material).
Table 3
a
Hydrogenation of nitro and carbonyl groups catalyzed by PdB in glycerol.
b
Conv. (yield)
Entry
R
1
R
2
Product
(
%)
c, d
1
NO
2
(11)
H
H
100 (99)
98 (95)
99 (97)
90 (89)
1
1
1H
2H
2
3
4
CHO (12)
CHO (13)
CHO (14)
Br
1
1
3H
4H
C(CH
)
3 3
1
0

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e
f
5
COCH
3
(15)
H
H
H
100(98)
1
1
5H
6H
e
6
COCF
3
(16)
100 (97)
40 (37)
CH
2
2
CH COCH
3
g
7
(
1H)
1I
17H
e
h
8
COC≡CH (17)
H
100 (85/15)
17I
a
Results from duplicated experiments. Reaction conditions: 1 mmol of substrate (1H, 12-18) and
-2
-1
b
1
mL of the catalytic glycerol solution of PdB (10 mol L , 0.01 mmol of total Pd). Determined
c
d
e
by GC and GC/MS using decane as internal standard. H
pressure 20 bar. Isolated yield. H
2
pressure 10 bar. Reaction for 2 h. H
2
f
g
h
2
pressure 40 bar. 17H/17I ratio.
4. Conclusions
To sum up, we efficiently prepared and fully characterized new palladium nanocatalysts, stabilized by
environmentally friendly choline-based ionic liquids in glycerol. The counter anion of the choline
derivative showed a non-innocent effect on the catalytic activity, probably due to the higher adsorption
of chloride than tosyl-alalinate at the metallic surface [34], and consequently hindering the interaction
of reagents with palladium.
PdB was active for the hydrogenation of C-C multiple bonds and also for C=O bond of aldehydes and
ketones, being more active for conjugated substrates. For non-conjugated substrates, such as internal
alkyl alkynes, PdB was highly selective to the formation of the corresponding alkene. The organic
products extracted from the catalytic glycerol phase did not contain palladium according to ICP-AES
analyses, proving the efficient immobilization of PdNPs in the glycerol phase.
Based on these results, the immobilization of the catalytic glycerol phase on solid supports in order to
improve the recyclability is under study.
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Acknowledgements
Université Fédérale de Toulouse (program IDEX Recherche – Actions Thématiques Stratégiques) and
Centre National de la Recherche Scientifique (CNRS) are gratefully acknowledged for their financial
support. Authors thank C. Pradel for his contribution in TEM analyses. G. G. thanks Université Fédérale
de Toulouse for PhD scholarship.
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