Influence of the Anion on the Oxidation of 5-Hydroxymethylfurfural by Using Ionic-Polymer-Supported Platinum Nanoparticle Catalysts

Article abstract of DOI:10.1002/cplu.201700344

Platinum nanoparticles stabilized by an imidazolium-based cross-linked polymer (with chloride as the counteranion) efficiently catalyzed the oxidation of 5-hydroxymethylfurfural to form 2,5-furandicarboxylic acid in water under mild conditions with oxygen as the oxidant. This catalyst system is explored herein by varying the counteranion, that is, replacing chloride by BF₄ ^?, PF₆ ^?, bis(trifluoromethylsulfonyl)imide, hexanoate, or laurate anions, in the cationic polymer. The counteranion influences the structure of the obtained platinum nanoparticles, the surface electronic properties, and their catalytic activity. The highest reaction rates were obtained with the weakly nucleophilic bis(trifluoromethylsulfonyl)imide anion, which also favored platinum in the zero oxidation state, leading to complete conversion of the substrate and a high yield of 2,5-furandicarboxylic acid under mild conditions.

Full text of DOI:10.1002/cplu.201700344

Accepted Article
Title: Influence of the anion on the oxidation of 5-hydroxymethylfurfural
using platinum nanoparticle-ionic polymer supported catalysts.
Authors: Sviatlana Siankevich, Simone Mozzettini, Felix Daniel
Bobbink, Shipeng Ding, Zhaofu Fei, Ning Yan, and Paul J.
Dyson
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ChemPlusChem
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FULL PAPER
Influence of the anion on the oxidation of 5-hydroxymethylfurfural
using platinum nanoparticle-ionic polymer supported catalysts.
[a]
[a]
[a]
[b]
[a]
*[b]
Sviatlana Siankevich, Simone Mozzettini, Felix Bobbink, Shipeng Ding, Zhaofu Fei, Ning Yan
and Paul J. Dyson*[a]
[
7]
Abstract: Platinum nanoparticles coated with an imidazolium-based
cross-linked polymer (with chloride as the counter anion) efficiently
catalyze the oxidation of 5-hydroxymethylfurfural to 2,5-
furandicarboxylic acid in water under mild conditions using oxygen as
the oxidant. In this paper we explore this catalyst system by varying
epoxy- and urea-urethanes. Oxidation reactions are among the
most important processes for the production of platform and
specialty chemicals. From an environmental and economic
perspective it is therefore important to conduct oxidations under
mild conditions with inexpensive oxidants and in the absence of
the counter anion, i.e. replacing chloride by BF
4
-, PF
6
-,
additives.[8]
bis(trifluoromethylsulfonyl)imide, hexanoate or laurate anions, in the
cationic polymer. The counter-anion influences both the structure of
the obtained platinum nanoparticles, the surface electronic properties
and their catalytic activity. Highest reaction rates were obtained with
the weakly-nucleophilic bis(trifluoromethylsulfonyl)imide anion, which
also favors platinum in the zero oxidation state, leading to complete
conversion of the substrate and a high yield of 2,5-furandicarboxylic
acid under mild conditions.
Introduction
The transformation of lignocellulosic biomass into commodity
chemicals is of continued interest as a means of providing
alternative chemical feedstocks to those derived from
petrochemicals.[1] A variety of different chemicals may be
Figure 1. Some examples of commodity chemicals that can be obtained from
obtained from biomass and many different downstream
processes are currently under development.[2] The conversion of
5-hydroxymethylfurfural (HMF).
various cellulosic derivatives to 5-hydroxymethylfurfural (HMF)
Oxidation catalysts that convert HMF to FDCA have been
extensively explored, with particularly promising results obtained
using ruthenium, platinum and gold catalysts, usually immobilized
on titania or ceria supports.[9] Catalysts based on earth-abundant
has been identified as a key route, with HMF subsequently
transformed into a variety of other compounds, see Figure 1.[3]
The relative sustainability of the various products that can be
obtained from HMF have been evaluated[4] and 2,5-
metals have also been explored including iron[10], manganese[11]
,
furandicarboxylic acid (FDCA) has been identified as one of the
most sustainable and viable products.[5] FDCA can be used to
cobalt[12] and copper[13] systems and bimetallic catalysts also
show promise.[14]
generate a wide range of different products including plastics that
could potentially replace polyethylene terephthalate (PET).[6]
Indeed, the substitution of terephthalic acid by bio-based FDCA
would not only have a considerable impact on the sustainability of
disposable bottles, but it also appears to be economically
competitive with the petrochemical route. Other applications of
FDCA have also been identified and include the preparation of
furanic-modified amine-based curatives for polyureas, hybrid
Of the catalysts reported for the oxidation of HMF to FDCA, many
afford the required product in near-quantitative yield, although
most of the catalysts operate at high pressures and temperatures
or require additives.[5b, 11] Heterogeneous platinum catalysts are
among the most active oxidation catalysts[9i, 15] and some that
operate in water use oxygen as the oxidant in the absence of a
base.[12b, 16] In this context, we recently reported water-dispersed
platinum nanoparticles (NPs) protected with an ionic
(imidazolium-based) polymer stabilizer that catalyzes the
oxidation of HMF to FDCA using oxygen under mild conditions in
near-quantitative yield.[17] Herein, we describe the further
optimization of this system via an exploration of the cationic
polymer stabilizer counter-anion. It was found that the counter-
anion strongly influences both the structure and activity of the
resulting platinum nanocatalysts.
[
[
a]
b]
Sviatlana Siankevich, Simone Mozzettini, Felix Bobbink, Zhaofu Fei,
Prof. Paul J. Dyson
Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique
Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
E-mail: paul.dyson@epfl.ch
Shipeng Ding, Prof. Ning Yan
Department of Chemical and Biomolecular Engineering. National
University of Singapore, 4 Engineering Drive 4, 117576, Singapore
E-mail: ning.yan@nus.edu.sg
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Results and Discussion
+
A series of imidazolium containing polymers, termed poly[bvbim] ,
-
with different counter-anions,
appropriate
A
were prepared from the
[bvbim]A,
1,3-bis(4-vinylbenzyl)imidazolium,
monomers 1 – 5 (see Figure 2), via free radical polymerization
using the azobisisobutyronitrile (AIBN) initiator. Monomers 3 – 5
have not been reported previously and were prepared from the
chloride salt, [bvbim]Cl, by metathesis (see Experimental). These
resulting ionic polymers IP1 – IP5 were subsequently used as
stabilizers/support matrices in the synthesis of platinum NPs (NP1
–
2 6
NP5) obtained from the reaction of H PtCl with NaOH in
ethylene glycol at 140°C in the presence of the ionic polymers.
Figure 3. TEM image of poly[bvbim][C
6
H
11 2
O ] IP4 (as a representative example).
Figure 2. Synthesis of the cationic polymer and counter-anions used in this
study: poly[bvbim][BF
4
] = IP1, poly[bvbim][PF
IP4 where
] = IP5 where C12
6
] = IP2, poly[bvbim][Tf
is the hexanoate anion and
2
is the laurate anion.
2
N] = IP3,
poly[bvbim][C
6
H
11
O
2
]
=
C
H
6
H
11O -
23O -
2
poly[bvbim][C12
H
23
O
2
Ionic polymers IP1 – IP5 were characterized by TEM (see Figure
for a representative example of the polymer) as were the
3
corresponding NPs (Figure 4). The size of the platinum NPs
varies from 1 to 6 nm depending on the stabilizer, with
poly[bvbim][Tf
2 23 2
N] IP3 and poly[bvbim][C12H O ] IP5 leading to
Figure 4. From the top: TEM images of NP1 – NP5 protected by/supported
on the ionic polymers.
slightly larger NPs than those obtained using IP1, IP2 and IP4.
The various polymer-immobilized NPs, i.e. NP1 – NP5, and
NPs prepared using poly[bvbim]Cl, termed NP-Cl, included as
a control, were evaluated as catalysts for the oxidation of HMF
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ChemPlusChem
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to FDCA in water using oxygen as the oxidant. Two different
intermediates were observed during the reaction, i.e. 2,5-
diformylfuran (DFF) and 5-formyl-2-furancarboxylic acid
not adequately stabilize NPs leading to catalyst degradation.
The relative coordinating capability, steric hindrance and bulk
of counter anions is listed in Table S1, and the catalytic
performance of the Pt NPs is compared the these properties.
No obvious correlation was observed between the catalytic
activity of the Pt NPs and the bulk or the steric hindrance of the
counter anions. In contrast, a volcano type of relationship
between activity and coordinating capability was identified.
Anions that interact (coordinate) intermediately with metals are
most active, in agreement with a previous study on the Stille
C-C coupling catalyzed by Pd NPs.[18]
(
FFCA). The first step of the transformation of HMF, which
comprises a furan ring with an aldehyde and an alcohol
substituent, involves the oxidation of the alcohol group to an
aldehyde group to afford the diformylfuran, DFF. Next, the
stepwise insertion of an O-atom into each aldehyde C-H bond
takes place, initially forming FFCA and then the FDCA product.
The conversion and product distribution after 6 hours was
determined in order to compare the efficacy of the various NP
catalysts (Figure 5).
HMF
DFF
FFCA
FDCA
100
80
60
40
20
0
NP1 NP2 NP3 NP4 NP5 NP-Cl
Figure 5. Conversion of HMF into DFF, FFCA and FDCA catalyzed by NP1
–
NP5 and NP-Cl used as a control. Reaction conditions: HMF (0.290 mmol,
3
7 mg), catalyst (0.0145 mmol of Pt), O (1 bar), 80°C, 6 h.
2
The data presented here tends to corroborate these anion
effects, albeit based on NPs that operate in aqueous solution,
and illustrates that weakly coordinating anions provide the
optimum balance between nanocatalytic activity and stability.
It would also appear that this electronic effect overrides steric
factors as the Pt NPs coated with IP3 are among the larger
ones, i.e. 4 nm vs. 2-2.5 nm, from the series studied. Our
previous study showed that the catalytic performance of Pt
NPs was size dependent, but the activity difference of Pt NPs
in the 2.0 nm to 5.0 nm range was insignificant.[17] In this paper,
the particle size of Pt NP varied from 2.0 nm to 5.5 nm and,
also here, the difference in size of Pt NPs does not appear to
play a major role in catalytic activity.
Scheme1. Reaction pathway for the oxidation of HMF into FDCA.
Conversions approaching 100% are obtained with NP1 – NP3,
i.e. those containing the BF - PF - N- anions,
, and Tf
4 6 2
respectively. The amount of the desired FDCA product is the
highest in the reaction employing catalyst NP3, approaching
0%, considerably higher than that obtained with the
previously reported catalyst, NP-Cl. The product mixture
obtained with the NP3 catalyst contains negligible amounts of
DFF and ca. 10% of FFCA. Indeed, inspection of the product
distributions from all the catalysts evaluated shows that NP3 is
the most active. Using the NP3 catalyst under the same
conditions FDCA can be obtained in near-quantitative yield
from HMF after 30 hours reaction. It has previously been noted
9
that palladium NPs show the highest catalytic activities in Tf
2
N-
based ionic liquids and this was attributed to the weak
-
[18]
2
interaction between the Tf N anion and the NP surface, i.e.
strongly nucleophilic anions reduced activity due to the
formation of strong interactions with the NP surface blocking
access to the substrates whereas non- coordinating anions do
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ChemPlusChem
10.1002/cplu.201700344
FULL PAPER
oxidants under relatively mild conditions.[16] Since dispersed Pt
NPs are kinetically unstable, stabilizers must be employed to
prevent the aggregation. In general, the more strongly the
stabilizer interacts with the nanoparticle surface, the more
stable the NP, but also the less catalytically active.[ The
5
4
3
2
1
000
000
000
000
000
0
20]
+
amphiphilic nature of the poly[bvbim] -based polymer
employed herein helps to stabilize the NPs via steric and
electrostatic interactions and the counter-anion also plays a
key role in the stabilization process.[21] Of the different counter-
-
anions explored, the intermediately coordinating Tf
2
N anion
leads to the highest catalytic activities presumably as it may be
displaced from the NP surface in a facile manner generating
catalytically active surface sites where the substrates can bind
and react, while simultaneously offering sufficient electronic
and steric protection to stabilize the NPs during reaction.
Indeed, this anion appears to facilitate the reduction of Pt(II) to
Pt(0) which helps to maintain the active catalytic species and
prevent over-oxidation.
8
2
80
78
76
74
72
70
68
66
B.E. (eV)
3500
3000
2500
2000
1500
1000
Experimental Section
All chemicals were obtained from commercial sources and used as
received. The monomer 1,3-bis(4-vinylbenzyl)imidazolium chloride,
[
[
2
bvbim]Cl,[22] 1,3-bis(4-vinylbenzyl)imidazolium hexafluorophosphate
bvbim][PF
and its polymer were prepared according to the literature methods.
Transmission electron microscopy (TEM) was carried out on
] 1 and its polymer[23] and tetrafluoroborate [bvbim][BF ][23]
6 4
5
00
0
a
8
2
80
78
76
74
72
70
68
66
Philips/FEI transmission electron microscope operating at 100 keV.
Prior to analysis samples were washed with water and ultrasonicated
B.E. (eV)
Figure 6. XPS spectra of (top) NP-Cl and (bottom) NP3.
(3 times) and a drop of solution was placed onto a carbon-coated Cu
grid and allowed to evaporate. NMR spectra were recorded on a Bruker
DMX 400 instrument. Electrospray ionization mass spectra (ESI-MS)
were recorded on a ThermoFinnigan LCQ Deca XP Plus quadrupole
XPS analysis of the NP-Cl and NP3 samples, i.e. with chloride
ion trap instrument in positive ion mode using a literature method[24]
.
-
and Tf
2
N counter anions respectively, show that the Pt species
Elemental analysis was performed on a Carlo Erba model 1106
instrument. X-ray photoelectron spectroscopy (XPS) spectra were
recorded on a VG ESCALAB 220I-XL system equipped with two X-ray
sources; twin-anode (Mg/Al) and twin crystal monochromated Al
sources. The data were calibrated from the C1s signal (285.0 eV). Zeta
exhibit peaks characteristic of Pt(0) at ca. 71 eV and for Pt(II)
at ca. 72.3 eV (Figure 6). Notably, the ratio of Pt(0):Pt(II)
differs, with a higher ratio of Pt(0) present in NP3, i.e.
Pt(0):Pt(II) = 3:1 in NP-Cl and 7:1 in NP3. This difference
indicates that the Tf
to Pt(0). It was previously shown that the resistance of Pd NPs
to oxidation follows the order of [Tf
OTf] > [BF
appear that NP3, with the Tf
to oxidation which prevent catalyst decomposition and
facilitates catalytic oxidation of HMF. The Zeta potentials of
NP-Cl and NP3 are 46.7 and 22.3 mV, respectively. The more
negative surface of the NP3 could be conducive to the
presence of protons that are involved at various parts of the
catalytic cycle.[
potentials of Pt nanoparticles were measured using
a Malvern
-
2
N anion promotes the reduction of Pt(II)
Zetasizer Nano-ZS instrument at 25°C. Samples were prepared by
dispersing 5 mg Pt nanoparticles in 5 mL DI water. For each analysis,
sufficient amount of sample was used to completely cover the
electrodes of the cuvette (1 mL). The sample was injected slowly to
assure there are no bubbles in the cuvette and the cuvette was placed
into the Zetasizer and equilibrated for 2 min before the measurement.
Each sample was measured for three times to obtain the final average
value.
−
−
−
2
N] > [PF
6
] > [TFA] >
−
−
[
4
] , and for the Pt NPs described here, it would also
−
[19]
2
N anion, is the most resistant
2
Preparation of [bvbim][Tf N] 3
17]
The [bvbim]Cl salt (1.008 g, 3 mmol) was dissolved in water (20 mL)
and Li[Tf N] (0.861 g, 3 mmol) was added and the mixture was stirred
2
for 1 h. A yellow precipitate formed during the reaction. The water was
removed under vacuum and the resulting waxy gel was washed with
water (5 x 10 ml). The gel was dried for 24 h under vacuum to afford a
Conclusions
Water dispersed platinum NPs have been widely explored as
oxidation catalysts as they are able to oxidize non-activated
primary alcohols in the absence of stoichiometric (expensive)
white solid. Yield: 50%. Elemental analysis for
23 21 6 3 4 2
C H F N O S
(
581.55) (%): C 47.50, H 3.64, N 7.23; Found: C 47.66, H 3.55, N 7.21.
-
ESI-MS (negative, m/z) 280 [anion] .
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We thank Swiss National Science Foundation National
Research Programme (NRP 66) for financial support.
6 11 2
Preparation of [bvbim][C H O ] 4
The salt [bvbim]Cl (2.39 g, 7.1 mmol) was dissolved in water (20 mL)
and sodium hexanoate (0.981 g, 7.10 mmol) was added and the
mixture was stirred for 1 h. The white precipitate that formed was
filtered and washed with water (5 x 10 mL). The solid was dried under
Keywords: HMF oxidation • cross-linked polymer • platinum
particle • anion
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(
Synthesis of poly[bvbim][Tf
2
N] IP3, poly[bvbim][C
6
H
H
11
O
2
] IP4 where
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3]
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C H O
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-
23
O
2
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]
=
2
=
H O
6 11 2
23 2
H O
2 6
H PtCl (0.145 mmol, 75 mg), ethylene glycol (134.5 mmol, 7.5 mL)
and NaOH (1.875 mmol, 7.5 mg) were mixed to form a yellow solution
that was heated at 140°C for 3 h under nitrogen. The solution was
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2
[
[
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