Bimetallic Nanoparticles in Supported Ionic Liquid Phases as Multifunctional Catalysts for the Selective Hydrodeoxygenation of Aromatic Substrates

Article abstract of DOI:10.1002/anie.201806638

Bimetallic iron–ruthenium nanoparticles embedded in an acidic supported ionic liquid phase (FeRu@SILP+IL-SO₃H) act as multifunctional catalysts for the selective hydrodeoxygenation of carbonyl groups in aromatic substrates. The catalyst material is assembled systematically from molecular components to combine the acid and metal sites that allow hydrogenolysis of the C=O bonds without hydrogenation of the aromatic ring. The resulting materials possess high activity and stability for the catalytic hydrodeoxygenation of C=O groups to CH₂ units in a variety of substituted aromatic ketones and, hence, provide an effective and benign alternative to traditional Clemmensen and Wolff–Kishner reductions, which require stoichiometric reagents. The molecular design of the FeRu@SILP+IL-SO₃H materials opens a general approach to multifunctional catalytic systems (MM′@SILP+IL-func).

Full text of DOI:10.1002/anie.201806638

Angewandte
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International Edition: DOI: 10.1002/anie.201806638
German Edition: DOI: 10.1002/ange.201806638
Nanocatalysis
Bimetallic Nanoparticles in Supported Ionic Liquid Phases as
Multifunctional Catalysts for the Selective Hydrodeoxygenation of
Aromatic Substrates
Lisa Offner-Marko, Alexis Bordet, Gilles Moos, Simon Tricard, Simon Rengshausen,
Bruno Chaudret, Kylie L. Luska, and Walter Leitner*
Abstract: Bimetallic iron–ruthenium nanoparticles embedded
in an acidic supported ionic liquid phase (FeRu@SILP + IL-
SO3H) act as multifunctional catalysts for the selective hydro-
deoxygenation of carbonyl groups in aromatic substrates. The
catalyst material is assembled systematically from molecular
components to combine the acid and metal sites that allow
=
hydrogenolysis of the C O bonds without hydrogenation of
the aromatic ring. The resulting materials possess high activity
=
Scheme 1. Selective catalytic hydrodeoxygenation of aromatic carbonyl
compounds as a possible route to alkyl-substituted aromatics, opening
new synthetic pathways, for example, from Friedel–Crafts acylation
products or lignin derivatives.
and stability for the catalytic hydrodeoxygenation of C O
groups to CH2 units in a variety of substituted aromatic ketones
and, hence, provide an effective and benign alternative to
traditional Clemmensen and Wolff–Kishner reductions, which
require stoichiometric reagents. The molecular design of the
FeRu@SILP + IL-SO3H materials opens a general approach
to multifunctional catalytic systems (MM’@SILP + IL-func).
moieties from aromatic substrates, despite the fact that they
rely on the use of toxic reagents and/or create large amounts
of undesired and problematic waste.[1] Current synthetic
pathways involving the hydrodeoxygenation of aromatic
substrates cannot fulfill the requirements of high yields,
selectivity, stability, productivity, safety, and environmental
compatibility.[6] Consequently, recent efforts have been
devoted to the development of selective hydrodeoxygenation
catalysts, typically based on conventional materials for
heterogeneous catalysis.[7a–j] While promising results have
been obtained in some cases for individual substrates, most of
the traditional solid catalysts show severe limitations such as
low hydrogenation selectivity,[8a–c] restriction to only benzylic
carbonyl groups,[7a–c] low stability,[7d–e] formation of side-
products,[7f] or high catalyst loadings approaching almost
stoichiometric amounts of the active metal component.[7g]
In the present paper, we describe the design, preparation,
and application of novel bifunctional catalysts for the
selective hydrodeoxygenation of aromatic substrates using
a molecular approach to assemble the key components of the
active materials.
T
he catalytic hydrodeoxygenation of carbonyl groups to
methylene units in the side chains of aromatic substrates has
attracted considerable attention for the production of alkyl-
substituted aromatic structures in commodity and fine
chemicals.[1] It is also considered an important enabler for
the deoxygenation of building blocks from lignocellulosic
biomass towards value-added chemicals and tailor-made
fuels.[2a–f] However, the large-scale synthetic application of
this transformation has been hindered by the lack of suitable
catalysts that allow for selective catalytic hydrodeoxygenation
of aromatic ketones without concomitant hydrogenation of
the aromatic ring (Scheme 1).[3] Stoichiometric methods such
as the Clemmensen[4] and Wolff–Kishner[5] reductions often
remain the methods of choice for the removal of carbonyl
[*] M. Sc. L. Offner-Marko, Dr. A. Bordet, M. Sc. G. Moos,
M. Sc. S. Rengshausen, Dr. K. L. Luska, Prof. Dr. W. Leitner
Institut fꢀr Technische und Makromolekulare Chemie
RWTH Aachen University
Worringerweg 2, 52074 Aachen (Germany)
E-mail: walter.leitner@cec.mpg.de
The design of the catalyst was based on the analysis of the
desired sequence of bond-breaking and bond-forming events
to achieve the overall transformation, exemplified for benzy-
lideneacetone (1) as a prototypical substrate in Scheme 2. The
M. Sc. L. Offner-Marko, Dr. A. Bordet, M. Sc. G. Moos,
M. Sc. S. Rengshausen, Prof. Dr. W. Leitner
Max-Planck-Institut fꢀr Chemische Energiekonversion
45470 Mꢀlheim an der Ruhr (Germany)
=
=
metal-catalyzed hydrogenation of the C C and C O bond
À
leads to the corresponding alcohol 1b. Then, the C O bond is
Dr. A. Bordet, Dr. S. Tricard, Prof. Dr. B. Chaudret
Laboratoire de Physique et Chemie de Nano-Objets
Universitꢁ de Toulouse, INSA, UPS, LPCNO, CNRS-UMR5215
135 Avenue de Rangueil, 31077 Toulouse (France)
broken through an acid-catalyzed E1- or E2-type mechanism,
resulting in a carbocation or olefin intermediate (only the
latter is shown for clarity in Scheme 2). A second metal-
catalyzed hydrogenation leads to butylbenzene (1d) as the
desired product. The catalytic hydrogenation of the aromatic
ring must be strictly avoided at each stage. Thus, the challenge
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.201806638.
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relative to 1) within 16 h
at 1508C under H2
(50 bar
at
RT)
(Table S4). Based on
these promising results,
the controlled prepara-
tion
of
the
Fe25Ru75@SILP + IL-
SO3H material sketched
in Figure 1 was targeted
Scheme 2. The complex reaction network to be controlled for selective deoxygenation of aromatic substrates,
exemplified for benzylideneacetone (1).
for catalyst design was to combine a highly selective metal
component for hydrogenation with a sufficiently acidic
À
functionality to facilitate the C O bond cleavage.
A recently emerging approach to prepare multifunctional
catalytic systems is based on well-defined metal nanoparticles
(NPs) synthesized from organometallic precursors that are
embedded in ionic liquid (IL) matrices.[9a–g] Herein, we
present a version of such materials that combines covalently
grafted non-functionalized IL-type structures with physisor-
bed functionalized ILs on silica as support (supported ionic
liquid phases, SILPs). This approach allows the controlled
formation of NPs on the non-functionalized SILP and
provides a large degree of freedom for post-modification
with the functionalized IL. The resulting materials are
denoted as MM’@SILP + IL-func, in which MM’ defines the
metal(s), SILP the covalently grafted IL, and IL-func the
physisorbed IL (e.g., IL-SO3H for the acidic IL used in this
study).[10a–e]
To address the present synthetic challenge, the combina-
tion of bimetallic iron–ruthenium nanoparticles (FeRu NPs)
with an acidic support appeared very promising. Recently,
Fe25Ru75 NPs immobilized on a non-functionalized SILP
(Fe25Ru75@SILP) were shown to exhibit high activity for the
Figure 1. Schematic of iron–ruthenium nanoparticles immobilized on
a sulfonic acid-functionalized supported ionic liquid phase
(Fe25Ru75@SILP+IL-SO3H) as a bifunctional catalyst for the hydro-
deoxygenation of carbonyl-substituted aromatic substrates.
to ensure an intimate contact between the NPs and the acid
moieties in the bifunctional catalyst. The synthesis of Fe25Ru75
NPs immobilized on a non-functionalized SILP was accom-
plished using a reported procedure.[11] In brief, the NPs were
prepared through the in situ reduction of a mesitylene
solution of {Fe[N(Si(CH3)3)2]2}2 and [Ru(cod)(cot)] in the
presence of the SILP material under an atmosphere of H2
(3 bar) at 1508C. The oxidation state and alloy extent of the
Fe25Ru75 NPs in Fe25Ru75@SILP were previously studied by
XANES and EXAFS, evidencing zerovalent Fe and Ru atoms
organized in a homophilic bimetallic structure (bimetallic
phase with more Fe and Ru homoatomic interactions than in
a perfect bimetallic structure).[11] The physisorption of IL-
SO3H onto Fe25Ru75@SILP to prepare the bifunctional
catalyst (Fe25Ru75@SILP + IL-SO3H) was achieved by stirring
a suspension of Fe25Ru75@SILP and IL-SO3H in acetone at
RT.
As expected, the surface area and the pore volume were
significantly reduced upon physisorption of the IL-SO3H on
Fe25Ru75@SILP according to BET analysis. These data are in
good agreement with a pore-filling degree (or a factor) of 0.7.
Detailed analysis by TEM showed that the size of the metal
nanoparticles (2.9 nm) did not change significantly upon
physisorption; however, the NPs were less homogeneously
dispersed across the support than before. STEM/EDS ele-
mental mapping evidenced a clear correlation between sulfur
and metal concentration, with higher sulfur content (ca. 2-
fold) in zones containing NPs as compared to zones without
NPs. This observation indicates a preference of the NPs to
accumulate in areas with large amounts of physisorbed IL-
=
=
=
reduction of C C, C O, and C N groups in substituted
aromatic substrates, while preventing the reduction of aro-
matic moieties.[11] Another recent study also outlined a syner-
gistic effect in bimetallic FeRu@SILP catalysts used for the
hydrogenation of CO2 to hydrocarbons.[12] However, attempts
to synthesize Fe25Ru75 NPs on supports in which the acid
functions are covalently grafted prior to NP formation (SILP-
SO3H)[9e–g] proved unsuccessful owing to the unfavorable
interaction of the Fe-precursor with the acid functionality.
The hydrodeoxygenation of 1 with the resulting materials
only led to the hydrogenation intermediates 1a, 1b, 1e, and
1 f without exhibiting any deoxygenation activity (see the
Supporting Information, Tables S1 and S3 and Figure S1).
Preparing Fe25Ru75 NPs on a non-functionalized SILP and
carrying out the transformation in the presence of p-
toluenesulfonic acid (p-TsOH) as acidic additive yielded
significant amounts of the desired product 1d, albeit with only
low selectivity (1a:1b:1d = 36:31:32). Finally, excellent activ-
ity and selectivity were obtained using a sulfonic acid-
functionalized imidazolium IL, [BSO3BIM][NTf2] (IL-
SO3H), as acid additive. 1d was detected by GC essentially
as the sole product in the reaction mixture with greater than
99% yield at full conversion of 1 upon using 2.50 equivalents
of IL-SO3H with regard to the total metal loading (4 mol%
2
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SO3H. STEM/EDS elemental mapping and SEM/EDS dem-
onstrated that, despite this noticeable redistribution, the NPs
still contain both Fe and Ru (Figure 2) in an unaffected metal
ratio (see the Supporting Information, Table S2 and Fig-
ures S2, S3, and S5, for complete characterization details).
Figure 3. Reaction profile for the hydrodeoxygenation of benzylidenea-
cetone (1) using Fe25Ru75@SILP+IL-SO3H. Reaction conditions:
Fe25Ru75@SILP+IL-SO3H (58 mg of catalyst containing 0.015 mmol
total metal and 0.038 mmol (2.50 equiv.) IL-SO3H), substrate
(0.38 mmol), mesitylene (0.5 mL), H2 (50 bar), 1508C. Conversion and
product distribution were determined by GC using tetradecane as an
internal standard.
Figure 2. Scanning transmission electron microscopy with energy
dispersive X-ray spectroscopy (STEM/EDS) elemental mappings of
Fe25Ru75@SILP+IL-SO3H. a) STEM-HAADF image of
nols.[9f] With leaching of physisorbed ionic liquids being
a well-known issue in solution phase catalysis,[13a,b] the
stability of Fe25Ru75@SILP + IL-SO3H was carefully studied.
Conversion and selectivity towards the formation of butyl-
benzene (1d) were constant upon recycling of the catalyst
material for at least four times without any make-up or
regeneration (see the Supporting Information, Table S5). This
is in good agreement with quantitative SEM/EDS analysis,
which did not evidence significant leaching of the metals nor
of the acidic ionic liquid under reaction conditions. TEM
analysis showed no NP growth or aggregation, and the
conservation of their bimetallic nature was confirmed by
STEM/EDS elemental mapping. BET analysis indicated that
the textural properties of the bifunctional catalyst did not
change (see the Supporting Information, Table S2 and
Figures S2–6, for complete characterization details). The
excellent stability of the catalyst is most likely reflecting
favorable interactions between the covalently grafted and
physisorbed ionic liquid structures arising from their molec-
ular similarity.
Fe25Ru75@SILP+IL-SO3H, b) S, c) Fe, and d) Ru.
These results indicate that the physisorption of the acidic
ionic liquid onto Fe25Ru75@SILP did not affect the integrity of
the Fe25Ru75 NPs (size, metal ratio). These data substantiate
the conclusion that Fe25Ru75 NPs retain their oxidation state
and alloy structure after physisorption of the acidic ionic
liquid and consist of zerovalent Fe and Ru atoms organized in
a homophilic bimetallic structure.
The reaction profile for the hydrodeoxygenation of
benzylideneacetone (1) catalyzed by Fe25Ru75@SILP + IL-
SO3H is shown in Figure 3. A mixture of hydrogenation
intermediates 1a and 1b (58%) and the deoxygenation
product 1d (42%) was formed already after 1 h. As the
reaction progressed, the hydrogenation intermediates, 1a and
1b, were gradually consumed and an almost quantitative yield
of 1d was obtained after 12 h. During the entire reaction
sequence, no species resulting from the hydrogenation of the
aromatic moiety were observed.
The close vicinity of the IL-SO3H with the bimetallic
particles as evidenced by the STEM/EDS data appears to be
crucial for efficient hydrogenolysis. In contrast to
Fe25Ru75@SILP + IL-SO3H, a physical mixture of non-func-
tionalized Fe25Ru75@SILP and metal-free SILP-SO3H
resulted in only slow formation of 1d (7%) with 1a (70%)
and 1b (18%) being the main products after 16 h under
identical reaction conditions (see the Supporting Information,
Table S4). Similar synergistic effects were observed for
Ru100@SILP-SO3H in the deep hydrodeoxygenation of phe-
The substrate scope for the selective hydrodeoxygenation
using the bifunctional Fe25Ru75@SILP + IL-SO3H catalyst was
assessed with a range of carbonyl-substituted aromatic
substrates (Table 1 and Table S7). Interestingly, while benzy-
lideneacetone (1) was converted to the deoxygenation
product 1d in quantitative yields at 1508C (Table 1,
Entry 1), the efficient hydrodeoxygenation of 1-phenyl-1-
butanone (2) to give the same product 1d required a temper-
ature of 1758C (Table 1, Entry 2). The hydrodeoxygenation of
the 1,3-diketone (3) at 1758C also proceeded smoothly to give
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Table 1: Hydrodeoxygenation of carbonyl-substituted aromatic sub-
strates using Fe25Ru75@SILP+IL-SO3H.[a]
non-benzylic ketone is favored over the benzylic ketone. This
was confirmed by comparative rate studies for the hydro-
deoxygenation of 2 and 1a, demonstrating a two-fold higher
reaction rate for 1a (Figure 4 and Figure S8). This unique
reactivity pattern is in sharp contrast to previously reported
hydrodeoxygenation catalysts.
The hydrodeoxygenation of Friedel–Craft acylation prod-
ucts such as 2 provides an interesting alternative to classical
Friedel–Crafts alkylation reactions, which are prone to over-
Entry
1
Substrate
Product [%][b]
>99[c]
>99[c]
94
2
3
4
5
6
7
8
9
82[d]
91
92
95
>99
>99
[a] Reaction conditions: Fe25Ru75@SILP+IL-SO3H (58 mg catalyst con-
taining 0.015 mmol total metal and 0.038 mmol (2.50 equiv.) IL-SO3H),
substrate (0.38 mmol, 25 equiv.), mesitylene (0.5 mL). [b] Yield deter-
mined by GC, conversion >99%. [c] 1508C. Remainders of reaction
mixtures were composed of dimeric by-products or [d] 4a (12%) and
dimeric by-products (6%).
high yields of 1d (Table 1, Entry 3). Performing this reaction
at 1008C evidenced the presence of 2 (22%) and 4-phenyl-2-
butanone (1a) (8%) as intermediates (see the Supporting
Information, Table S9). 4-phenyl-2-butene (1c) was also
observed as an intermediate of the reaction at 1008C
(Table S9), which supports the reaction pathway discussed
in Scheme 2. The greater amount of intermediate 2 as
compared to 1a indicates that the deoxygenation of the
Figure 4. Comparative rate studies for the hydrodeoxygenation of 1-
phenyl-1-butanone (2) and 4-phenyl-2-butanone (1a) using
Fe25Ru75@SILP+IL-SO3H. Reaction conditions: Fe25Ru75@SILP+IL-
SO3H (58 mg catalyst containing 0.015 mmol total metal and
0.038 mmol (2.50 equiv.) IL-SO3H), substrate (0.38 mmol), mesitylene
(0.5 mL), H2 (50 bar), 1508C. Conversion was determined by GC using
tetradecane as an internal standard.
4
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alkylation
and
carbocation
rearrangements.
The
Josef Vaeßen (ITMC, RWTH Aachen University) for N2(g)
adsorption measurements, Heike Bergstein (ITMC, RWTH
Fe25Ru75@SILP + IL-SO3H catalyst proved to be very versa-
tile in this context. The hydrodeoxygenation of acetophenone
(4) and its derivatives 5 and 6 gave the corresponding
deoxygenation products in over 90% yield, irrespective of the
presence of electron-donating (5) or electron-withdrawing (6)
groups in the para-position. Acylated naphthalene (7) was
converted to 2-ethylnapthalene (7a) in quantitative yields
under standard reaction conditions. Notably, the conversion
of diphenylketone (8) to diphenylmethane (8a) was also
quantitative, indicating that the formation of an olefinic
intermediate is not required in case sufficiently stable
carbocations can be formed.
Aachen University) for ICP measurements, and Vanessa
Soldan (METI), Simon Cayez (LPCNO), Maria Teresa
Hungria, and Lucien Datas (Centre de MicroCaractꢀrisation
Raimond Castaing) for help concerning TEM, STEM/EDS
and SEM/EDS analyses. Special thanks are due to Prof.
Serena DeBeer for valuable discussion concerning material
characterization.
Conflict of interest
Using Fe25Ru75@SILP + IL-SO3H, the hydrogenation of
aromatic moieties was not observed for any of the substrates,
even at prolonged reaction time. In sharp contrast, the use of
monometallic Ru100@SILP + IL-SO3H catalysts under similar
reaction conditions led to deep hydrogenation of all sub-
strates, yielding completely saturated deoxygenation products
or product mixtures (for detailed results, see the Supporting
Information, Table S8). Monometallic Fe100@SILP catalysts
The authors declare no conflict of interest.
Keywords: bimetallic nanoparticles · hydrodeoxygenation · iron ·
ruthenium · supported ionic liquid phases
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[11]
=
C O bonds. This emphasizes how the bimetallic FeRu@-
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Acknowledgements
This work was supported by the Cluster of Excellence “Tailor-
Made Fuels from Biomass”, which is funded under contract
EXC 236 by the Excellence Initiative by the German federal
and state governments to promote science and research at
German universities. The authors would like to thank Karl-
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Manuscript received: June 8, 2018
Version of record online: && &&, &&&&
6
www.angewandte.org
ꢀ 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2018, 57, 1 – 7
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Nanocatalysis
A bimetallic, bifunctional catalyst com-
posed of iron–ruthenium nanoparticles
immobilized on an acid-functionalized
supported ionic liquid phase (FeRu@-
SILP+IL-SO3H) was developed. This
catalyst showed high activity for the
hydrodeoxygenation of aromatic ketones
and excellent selectivity towards aromatic
deoxygenation products.
L. Offner-Marko, A. Bordet, G. Moos,
S. Tricard, S. Rengshausen, B. Chaudret,
K. L. Luska, W. Leitner*
&&&& — &&&&
Bimetallic Nanoparticles in Supported
Ionic Liquid Phases as Multifunctional
Catalysts for the Selective
Hydrodeoxygenation of Aromatic
Substrates
Angew. Chem. Int. Ed. 2018, 57, 1 – 7
ꢀ 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7
These are not the final page numbers!