Microenvironment Engineering of Ruthenium Nanoparticles Incorporated into Silica Nanoreactors for Enhanced Hydrogenations

Article abstract of DOI:10.1002/anie.201908602

It is a challenging task to promote the activity and selectivity of a catalyst via precisely engineering the microenvironment, an important factor related with the catalytic performance of natural catalysts. Motivated by the water effect in promoting the

Full text of DOI:10.1002/anie.201908602

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Accepted Article
Title: Microenvironment engineering of Ru nanoparticles incorporated
in silica nanoreactors for enhanced hydrogenations
Authors: Xiaomin Ren, Miao Guo, He Li, Chengbin Li, Liang Yu, Jian
Liu, and Qihua Yang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201908602
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10.1002/anie.201908602
Angewandte Chemie International Edition
COMMUNICATION
Microenvironment engineering of Ru nanoparticles incorporated
in silica nanoreactors for enhanced hydrogenations
Xiaomin Ren,†[a,b] Miao Guo,†[a] He Li,[a] Chengbin Li,[a] Liang Yu,*[a] Jian Liu*[a,c] and Qihua Yang*[a]
Dedicated to the 70th anniversary of the Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Abstract: It is a challenging task to promote the activity and selectivity
of a catalyst via precisely engineering the microenvironment, an
important factor related with the catalytic performance of natural
catalysts. Motivated by the water effect in promoting the catalytic
activity explored in this work, we reported that the nanoreactor
modified with phosphine ligand enabled the efficient hydrogenation of
benzoic acid (BA) over Ru nanoparticles (NPs) in organic solvent
under mild conditions, which cannot be achieved in unmodified
nanoreactors. Both density functional theory (DFT) calculations and
catalytic performance tests showcased that the phosphine ligands can
manipulate the adsorption strength of BA on Ru NPs by tuning the
surface properties as well as preferentially interacting with the
carboxyl of BA. The insights obtained in the present study provide a
novel concept of nanoreactor design via anchoring ligands near
catalytic active centers.
physicochemical properties such as, the size, shape and
interactions with supports.[4] Additionally, previous investigations
have showcased the importance of microenvironments in tuning
the catalytic performance of metal NPs by affecting its adsorption
energy and adsorption modes of substrates,[9-13] which could be
realized via the generating a steric hindrance around metal
NPs,[14-17] introducing the binding site with specific functional
group near metal NPs,[18-21] and so on.
The catalytic hydrogenation of benzoic acid (BA) is of pivotal
importance in industry. However, negligible conversion of BA was
obtained in aprotic organic solvents under similar conditions (60
oC, 1 MPa) over metal NPs.[22-24] Previous studies showed that
both activity and selectivity of metal NPs could be improved by
the presence of water.[25-27] For example, Anderson and co-
workers reported that the hydrogenation of aromatic ring was
favoured over carbonyl group using water as solvent and the
opposite tendency was observed using cyclohexane as solvent.[28]
Recently, Resasco elucidated the alternative hydrogenation path
in the presence of water was related with charge separation using
of hydrogenation of furfural as model reaction.[29] The promotion
effect of water was also observed for BA hydrogenation, but it has
not been clarified yet.[22-24]
Enzymes, the natural catalysts, can efficiently catalyze the
chemical reactions under mild conditions to afford both high
activity and high chemo/stereo/chiral selectivity. In comparison,
metal complexes possessing with similar molecular structures to
the active sites of enzymes do not always show high activity and
selectivity.[1] This is due to the loss of specific microenvironment
around the active sites.[1-2] Previous investigations suggest that
amino acid residues around the catalytic active sites of enzymes
could assist enriching, organizing and activating substrates via
non-covalent interactions.[3]
Herein, we reported that silica nanoreactors modified with
phosphine ligand behave as high active catalyst for
hydrogenations through microenvironment engineering of Ru
nanoparticles. In addition, the acceleration effect of water in the
hydrogenation was elucidated by tuning the adsorption mode of
BA over Ru NPs.
Supported metal nanoparticles are an important class of
catalyst materials and have been widely used in industries for
various chemical reactions, such as hydrogenation, oxidation, C-
Strikingly, a sharp increase in the BA conversion from ~0 to
~50% was observed over Ru/FDU (Ru loading amount of 3 wt%,
FDU refers to FDU-12) when only 1 v/v% of water were added
into the hexane solvent, followed by a further increase to ~99%
conversion as the water content reached to 10 v/v% with
cyclohexanecarboxylic acid (CCA) as the main reaction product
detected (Figure 1A). This acceleration effect of water is
consistent with previous reports.[22-24] DFT calculations results
show that H2O can readily dissociate to O* and H* on the
Ru(0001) surface with a free energy gain of 0.97 eV until reaching
an equilibrium coverage of 5/6 monolayer (Figure S1). The
generated O* species strongly passivate the Ru surface, resulting
in a significant decrease in the adsorption free energy of BA from
-1.93 eV on the clean surface to -1.06 eV, which is on the surface
covered by 2/3 monolayer of O* and H* (Figure 1B). As a result,
the activation barriers of the hydrogenation elementary steps are
apparently lowered on the water-mediated Ru(0001) surface. As
shown in the calculated reaction pathway of the hydrogenation of
BA (Figure 1C), the first three hydrogenation steps which require
relatively higher activation energies (0.73, 0.72 and 0.91 eV) and
are rate-limiting on pure Ru(0001), become much favored with
notably decreased activation barriers of 0.33, 0.59, and 0.75 eV,
respectively, on the surface covered by 2/3 monolayer of water. It
C
coupling and isomerization.[4-8] Generally, the catalytic
performance of metal NPs can be modulated by modifying its
[a]
X. Ren, Dr. M. Guo, Dr. H. Li, Dr. C. Li, Dr. L. Yu, Prof. J. Liu, Prof.
Q. Yang
State Key Laboratory of Catalysis
iChEM, Dalian Institute of Chemical Physics
Chinese Academy of Sciences
Dalian 116023, China
E-mail: lyu@dicp.ac.cn (LY), yangqh@dicp.ac.cn (QY)
X. Ren
University of Chinese Academy of Sciences
Beijing 100049, China
[b]
[c]
Prof. J. Liu
DICP-Surrey Joint Centre for Future Materials
Department of Chemical and Process Engineering and Advanced
Technology Institute
University of Surrey
Guildford, Surrey GU2 7XH, UK
E-mail: jian.liu@surrey.ac.uk (JL)
† These authors contributed equally.
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201908602
Angewandte Chemie International Edition
COMMUNICATION
is noteworthy that the H* from the dissociated H2O can also
participate in the reaction as the reductant. Therefore, DFT
calculations demonstrate that the water effect in promoting the
reaction kinetics originates from the dissociation of H2O on the Ru
surface whereby the generated O* species weakens the
interaction between BA and the catalyst surface and thereby
lowers the reaction barriers.
nanoreactors.[30-37] Triphenylphosphine, ethyldiphenylphosphine,
propylamine and phenyl groups incorporated FDU were denoted
as PPh3@FDU, PPh2-FDU, NH2-FDU and Ph@FDU, respectively.
PPh3@FDU and Ph@FDU were prepared by in situ
polymerization method with tris(4-vinylphenyl)phosphine and
divinylbenzene
(DVB)
as
monomers
and
AIBN
(azobisisobutyronitrile) as the initiator as we previously
reported.[38] PPh2-FDU and NH2-FDU were prepared by post
grafting method with 2-(diphenylphosphino)ethyltriethoxysilane
and
aminopropyltriethoxysilane
as
silylation
reagents
(characterization details see SI).
Ru/PPh3@FDU, Ru/PPh2-FDU, Ru/Ph@FDU and Ru/NH2-
FDU with 3 wt% of Ru NPs were prepared. The high-angle
annular dark field scanning transmission electron microscopy
(HAADF-STEM) and TEM images clearly showed the particle size
of Ru NPs on different supports was similar and distributed at ca.
2.5 nm by calculating 200 nanoparticles (Figure 2A and Figure
S4A). The dispersity of Ru measured by CO chemisorption only
varied slightly for different catalysts, further verifying the HAADF-
STEM and TEM results (Table S2). In the following discussion,
the influence of particle size on the catalytic performance of the
catalysts could be excluded.
The electronic properties of Ru NPs were analyzed by the X-
ray photoelectron spectroscopy (XPS) (Figure 2B and Table S2).
Compared with those of Ru/FDU, the Ru 3p binding energies for
Ru/PPh3@FDU, Ru/PPh2-FDU and Ru/NH2-FDU showed an
obvious red shift, indicating the electron donation from P (or N) to
Ru. The electron donating from P to Ru NPs was further
confirmed by the slight blue shift of the binding energies of P 2p
core level of Ru/PPh3@FDU in comparison with those of
PPh3@FDU. The similar binding energies of Ru/Ph@FDU and
Ru/FDU suggested the weak interaction between Ru NPs and the
phenyl rings. The solid-state 31P MAS NMR spectrum of
Ru/PPh3@FDU gave a new peak at 25.8 ppm assigned to P atom
coordinated with Ru NPs (Figure S5), showing the strong
interaction of Ru NPs with phosphine ligands. In comparison with
Ru/PPh2-FDU, the relatively larger red shift was observed for
Ru/PPh3@FDU (1.0 eV vs. 0.3 eV), demonstrating that PPh3
might donate more electrons to Ru NPs. As shown in Table S2,
the deconvoluted XPS data suggested that Ru/PPh3@FDU,
Ru/PPh2-FDU and Ru/NH2-FDU have higher Ru0/Run+ ratio than
Ru/Ph@FDU and Ru/FDU, possibly due to the electron donation
effect of P (N).
The surface structure of Ru NPs in different silica nanocages
was investigated using in situ FT-IR of CO adsorption (Figure 2C).
The CO adsorption on Ru/FDU was quite complicated with the
bands at 2132 and 2076 cm-1 assigned to CO bonded on Run+,
the band at 2026 cm-1 derived from linear CO on Ru0 surrounded
by Run+, and the broad band at 1960 cm-1 for the bridge-bonded
CO on Ru0.[39, 40] The in-situ FT-IR spectra were almost the same
for Ru/FDU and Ru/Ph@FDU, indicating that the two catalysts
have similar surface structure. Compared with Ru/FDU and
Ru/Ph@FDU, the red-shifts of linear-bonded CO were clearly
observed for Ru/PPh3@FDU, Ru/PPh2-FDU and Ru/NH2-FDU
due to the electron donating from P (N) to Ru NPs. For the linear
CO adsorbed on Ru surface, the red shifts of 32, 19 and 9
wavenumbers were observed for Ru/PPh3@FDU, Ru/NH2-FDU,
and Ru/PPh2-FDU, respectively, the negative charges on Ru NPs
decreased in the order of Ru/PPh3@FDU > Ru/NH2-FDU >
Ru/PPh2-FDU > Ru/Ph@FDU ≈ Ru/FDU. The results of XPS and
in situ FT-IR characterization showed that Ru NPs in PPh3@FDU
Figure 1. (A) Conversion of BA as
a function of solvent composition
(water/hexane) over Ru/FDU. (B) Adsorption free energy of BA on pure
Ru(0001) and water-mediated Ru(0001). (C) DFT calculated reaction paths of
BA hydrogenation on water-mediated (red) and pure (black) Ru(0001) surfaces.
On the water-mediated surface, the first hydrogenation step consumed one H*
of dissociated H2O. Insets show the atomic structures of reaction intermediates.
Red, grey, white, and dark cyan spheres represent O, C, H, and Ru atoms,
respectively.
Isotopic experiments were then conducted to further validate
the dissociation of water over the Ru/FDU catalyst by using
D2O/H2 or H2O/D2 as the solvent/reductant in the hydrogenation
of BA reaction. Isotopic exchange test under D2O/N2 excludes the
effect of H/D exchange between the phenyl group and molecular
D2O on the Ru surface (Figure S2). However, as H2 was added
into the reaction system, molecular ion peaks at m/z 126-132 and
128-134 denoting 1-4 deuterated 1-cyclohexenecarboxylic acid
(CEA) and 1-6 deuterated CCA, respectively, were clearly
observed in the MS spectra of the products in the corresponding
H2O/D2 and D2O/H2 reaction systems. These results confirm the
involvement of water molecules in the reaction process via being
dissociated on the Ru surface. The H source stems from both the
dissociated H2O (or D2O) and D2 (or H2) under aqueous reaction
conditions and thereby the hydrogenated products by
a
combination of H/D were obtained in the isotopic experiments.
This further implies the generation of oxygen species from H2O
dissociation on the Ru surface which will modify the surface
properties and tailor the catalytic activity.
The above results illustrate the significant role of the BA
adsorption strength on the catalyst surface in determining the
hydrogenation of BA reaction micro-kinetics and hence the
catalytic performance. Therefore, tuning the interaction between
the BA and the Ru surface offers a feasible strategy of tailoring
the catalytic activity of Ru catalyst in organic solvents.
To tune the interaction between the BA and the Ru surface,
organic ligands were incorporated in the nanocages of
mesoporous silica FDU, which has been widely used to construct
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10.1002/anie.201908602
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had more negative charges than those in PPh2-FDU though they
had similar P content. This is probably related with the flexible
polymer network and the different molecular structure of
triphenylphosphine and ethyldiphenylphosphine.
Figure 2 (A) HAADF-STEM images (insets for Ru particle size distributions, scale bar is 20 nm), (B) Ru 3p XPS core level spectra, (C) in situ FT-IR spectra of CO
adsorption on Ru NPs in nanocages of FDU modified with and without organic ligand.
addition to CCA, CEA was detected as the only intermediate
because BA hydrogenation is a typical stepwise reaction, similar
with benzene hydrogenation.[43] Ru/PPh3@FDU afforded 64%
conversion with 98% selectivity to CCA and 99% conversion could
be obtained by prolonging reaction time to 8 h. Under similar
reaction conditions, Ru/PPh2-FDU with conversion of 10% gave
more inferior activity than Ru/PPh3@FDU. Under more hash
reaction conditions (e.g. 100 oC, 2 MPa H2), other catalysts
showed activity for the hydrogenation of BA (Figure 3B). Even
under harsh reaction conditions, the TOF decreased in the order
of Ru/PPh3@FDU
> Ru/C ≈ Ru/PPh2-FDU > Ru/FDU >
Ru/Ph@FDU ≈ Ru/NH2-FDU. To the best of our knowledge, such
high activity has rarely been obtained on metal NPs for BA
hydrogenation in aprotic organic solvents. As reported previously,
the organic additives were usually added in the catalytic system
to modify the catalytic performance of metal NPs.[44] A control
experiment was performed for BA hydrogenation over Ru/FDU
with PPh3 as the additive in hexane. However, almost no
conversion was observed, possibly due to the capping of the
active sites on the surface of Ru NPs by PPh3, which is generally
observed for reaction systems with organic compounds as
additives. This indicates that PPh3@FDU provided a unique
microenvironment for Ru NPs.
Figure 3. (A, B) The catalytic performance of Ru NPs in hydrogenation of BA
using hexane as solvent. (C) Relation of apparent TOF with the red shifted
wavenumbers of linearly adsorbed CO of Ru NPs in hydrogenation of benzene,
toluene, and trifluorotoluene under neat condition. (D) Recycling stability of
Ru/PPh3@FDU in BA hydrogenation reaction.
It is quite interesting that only Ru/PPh3@FDU and Ru/PPh2-
FDU showed activity in BA hydrogenation using hexane as the
solvent under mild reaction conditions. The organic ligands not
only had different interaction strength with BA but also changed
the surface electronic structure of Ru NPs. To discern the key
factors for influencing the catalytic performance of Ru NPs in BA
hydrogenation, aromatic substrates (benzene, toluene and
trifluorotoluene) that do not have carboxyl groups were employed
to elucidate the influence of the surface electronic structure on the
catalytic performance of Ru NPs. All the catalysts are active for
the hydrogenation of benzene, toluene and trifluorotoluene under
The catalytic performance of Ru NPs was tested in BA
hydrogenation to CCA in hexane, which is a very important
organic intermediate.[41, 42] At 60 oC, 1 MPa H2, no conversion of
BA could be found over Ru/NH2-FDU, Ru/Ph@FDU, Ru/FDU and
commercial Ru/C, showing that these catalysts were inactive
under current conditions (Figure 3A). This is consistent with
previous reports that metal NPs were generally inactive for the
hydrogenation of BA in aprotic organic solvents under mild
reaction conditions.[22-24] Encouragingly, the CCA product was
detected with Ru/PPh3@FDU and Ru/PPh2-FDU as catalysts. In
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10.1002/anie.201908602
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current reaction conditions (Table 1). For the above-mentioned
substrates, the catalytic activity decreased in the order of
Ru/PPh3@FDU > Ru/NH2-FDU > Ru/PPh2-FDU > Ru/FDU >
Ru/Ph@FDU. No direct correlation of the activity could be found
interaction energies of BA with PPh3, NH2 and Si-OH were
calculated, which are of -0.42 eV, -0.64 eV and -0.36 eV,
respectively (Figure S6B). The strong interaction of NH2 with BA
will cause the difficulty in desorption of CCA from the catalysts
and the weak interaction of Si-OH with BA could not induce the
orientated adsorption. Consequently, Ru/NH2-FDU and Ru/FDU
showed no activity in BA hydrogenation in hexane under mild
reaction conditions. The phosphine ligands with suitable
interaction strength with BA acted as binding sites to induce the
adsorption of aromatic ring on Ru NPs, leading to efficient
hydrogenation of BA in hexane. To some extent, the phosphine
could be regarded as the binding sites around Ru NPs in a similar
way to those in enzymes.[2] The promotion effect of phosphine
ligand in BA hydrogenation was also observed using water as
solvent (Table S3). In addition to hexane and water,
Ru/PPh3@FDU also shows good to moderate activity in THF,
dioxane, ethanol and isopropanol (Table S4). Furthermore,
Ru/PPh3@FDU had high recycle stability (Figure 3D).
In summary, the transformation from inactive to active state of
Ru nanoparticles (NPs) for benzoic acid (BA) hydrogenation in
organic solvent was achieved via simply tuning the
microenvironment of the nanoreactor. Studies show that the
phosphine ligands around Ru NPs induced the preferential
adsorption of aromatic ring of BA on Ru NPs, which results in
efficient hydrogenation of BA in hexane. In addition, our results
showcased that the Ru NPs with enriched surface electrons are
advantageous for the hydrogenation of aromatic ring, such as
benzene, toluene and trifluorotoluene. Furthermore, the water
effect in the hydrogenation was elucidated. The investigation of
the microenvironment effect on the catalytic performance of
nanoreactors is in progress in our lab. The encapsulation of active
sites e.g. metal NPs in nanoreactors with precise
microenvironment mimicking the process of natural catalysts is an
efficient strategy to improve the catalytic performance of man-
made catalysts for selective chemical transformations.
with
the
BET
surface
area
and
surface
hydrophilicity/hydrophobicity of the catalysts (Figure S4B),
implying that the physical parameters were not the main
determining factors for the variation of the activity. As shown in
Figure 3C, there is an obvious relation of TOF with the red shifted
wavenumbers of linearly adsorbed CO on Ru NPs. The Ru NPs
with higher red-shifts wavenumbers afforded higher TOF,
implying that higher negatively-charged surface is advantageous
for the hydrogenation of aromatic rings. This indicates that the
surface electronic structure of Ru NPs may be the main factors
influencing their catalytic activity in the hydrogenation of benzene,
toluene and trifluorotoluene. The DFT calculations show that the
adsorption free energy benzene on Ru surface decreased with
increasing Ru surface electrons, thus suggesting that the surface
charge enrichment favor high activity (Figure S6A). It should be
noticed that Ru/PPh3@FDU is even more active than commercial
Ru/C in the hydrogenation of the above aromatic substrates,
confirming the positive effect of PPh3 ligands in promotion of the
catalytic activity of Ru NPs.
Table 1. The catalytic performance of Ru NPs in different silica
nanocages for the hydrogenation of arenes.[a]
Benzene
Toluene
Trifluorotoluene
Cat.
Conv.
TOF
(h-1)
Conv.
TOF
(h-1)
Conv.
(%)
TOF
(h-1)
(%)
>99
22
39
6
(%)
97
30
57
22
28
37
Ru/PPh3@FDU
Ru/PPh2-FDU
Ru/NH2-FDU
Ru/Ph@FDU
Ru/FDU
9250
2160
4560
620
3740
998
>99
55
92
8
1940[b]
520
2022
710
1380
76
Acknowledgements
9
880
933
11
86
106
Ru/C
56
6458
1233
1296
The authors are grateful to Prof. Can Li for fruitful discussions.
This work was supported by the Natural Science Foundation of
China (21733009, 21621063) and the Strategic Priority Research
Program of the Chinese Academy of Sciences (XDB17020200).
Jian Liu gratefully acknowledges the support of the Chinese
Government 1000 Young Talent Plan.
[a] Reaction conditions for benzene and toluene hydrogenation: S/C =
10000, 100 oC, 2 MPa H2, solvent free, 1 h for benzene and 3 h for toluene;
Reaction conditions for trifluorotoluene hydrogenation: S/C = 1000, 100 oC,
2 MPa H2, solvent free, 1 h; the apparent TOF was calculated with
conversion less than 30%; [b] S/C = 5000, 4 h.
Keywords: nanoparticle • hydrogenation • nanoreactor•
microenvironment • phosphine ligand
The above results showed that the surface negative charges of
Ru NPs played a main role in the hydrogenation of aromatic rings
without the carboxyl substituent. However, this is not the case for
the hydrogenation of BA. Ru/PPh2-FDU and Ru/PPh3@FDU were
active in the hydrogenation of BA. However, Ru/NH2-FDU with
similar electron rich surface did not show any catalytic activity
under mild reaction conditions. Thus, the observed activity
difference for BA hydrogenation may be related with the organic
ligands around Ru NPs rather than the surface negative charges
of Ru NPs. The phosphine, amine and Si-OH could form
interactions with the carboxyl group of BA during the catalytic
process, which will increase the possibility of BA adsorption on
Ru surface via the aromatic ring to enhance the activity. The
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This article is protected by copyright. All rights reserved.

10.1002/anie.201908602
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
The nanoreactor modified with
phosphine ligand enabled the
efficient hydrogenation of benzoic
acid (BA) over Ru Nanoparticles in
organic solvent under mild condition
which cannot be achieved in
unmodified nanoreactors, owing to
the phosphine ligands can
Xiaomin Ren, Miao Guo, He Li,
Chengbin Li, Liang Yu*, Jian Liu*,
Qihua Yang*
Page No. 1– Page No.5
Microenvironment engineering of Ru
nanoparticles incorporated in silica
nanoreactors for enhanced
hydrogenations
manipulate the adsorption strength
of BA on Ru NPs.
This article is protected by copyright. All rights reserved.