Synergistic Hydrogenation over Palladium through the Assembly of MIL-101(Fe) MOF over Palladium Nanocubes

Article abstract of DOI:10.1002/chem.201704119

Enhancing catalytic performance of metal nanoparticles is highly sought for many industrial catalytic processes. In this regard, assembly of crystalline porous super-tunable metal–organic frameworks (MOFs) around preformed metal nanoparticles is an attractive prospect as this strongly influences the activity of the entire nanoparticle surface. Herein, we assembled a MlL-101(Fe) MOF onto the Pd nanocubes and evaluated the catalytic properties of the hybrid material for the hydrogenation of the α,β-unsaturated carbonyl compounds cinnamaldehyde, crotonaldehyde, and β-ionone. Owing to the synergestic effects originating from the Lewis acid sites present on MOF and Pd active sites, striking improvements in the activities and selectivities were observed for the Pd?MIL-101(Fe) hybrid material. The turnover frequency (TOF) values increased up to roughly 20 fold and in all three studied substrates, C=C was preferentially hydrogenated compared to C=O. Furthermore, the Pd?MIL-101(Fe) catalyst was readily reusable and highly stable.

Full text of DOI:10.1002/chem.201704119

A Journal of
Accepted Article
Title: Synergistic Hydrogenation over Palladium through the Assembly
of MIL-101(Fe) MOF over Palladium Nanocubes
Authors: Vasudeva Rao Bakuru and Suresh Babu Kalidindi
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Synergistic Hydrogenation over Palladium through the Assembly
of MIL-101(Fe) MOF over Palladium Nanocubes
Vasudeva Rao Bakuru[a],[b] and Suresh Babu Kalidindi*[a]
Abstract: Enhancing catalytic performance of metal nanoparticles is
highly sought for many industrial catalytic processes. In this regard,
assembling of crystalline porous super-tunable metal-organic
frameworks (MOFs) around preformed metal nanoparticles is an
attractive prospect as this strongly influences the activity of the entire
nanoparticle surface. Herein, we assembled MlL-101(Fe) MOF onto
the Pd nanocubes and evaluated the catalytic properties of the
hybrid material using hydrogenation of variety of α,β-unsaturated
carbonyl compounds; namely cinnamaldehyde, crotanaldehyde and
β-ionone. Owing to the synergestic effects originated from the Lewis
acid sites present on MOF and Pd active sites, striking
improvements in the activities and selectivities were observed for
Pd⊂MIL-101(Fe) hybrid material. The turn over frequency (TOF)
values increased up to ~20 folds and for all three substrates under
study C=C preferentially got hydrogenated over C=O. Furthermore,
the Pd⊂MIL-101(Fe) catalyst was readily reusable and highly stable.
Scheme 1. a) shows MTN topology of MIL-101(Fe) MOF; the hexagonal
and pentagonal window openings are shown in b) and c); d) shows
schematic representation of Pd⊂MIL-101 architecture formation.
Transition metal nanoparticles (NPs) are widely employed in
many industrial catalytic processes which include fine chemical
manufacturing, polymer synthesis, and energy conversion.
NP surface,[7a] iii) increased reactants concentration around
metal active centers due to favorable adsorption of reactant
[1]
The catalytic properties majorly stems from the large percentage
molecules into MOF pores,[8] iv) catalytic synergy due to the
of uncoordinated surface atoms present on the surface of NPs.
additional active sites present on MOF matrix, v) modulating the
Rational tuning of the catalytic properties and preventing the
chemical environment around active center by virtue of ability to
aggregation of NPs during reaction conditions are the two major
systematically tune the pore surface chemistry of the MOF.[9] It
endeavors in this area. In this regard, recently fabrication of
is intriguing to note that only limited studies are reported
demonstrating few of these advantages. The Pd NPs which are
excellent hydrogenation catalysts have been incorporated in the
metal⊂porous matrix architectures wherein metal surface is
completely covered with porous matrix has emerged as a new
promising approach.[2] Here, the porous matrix not only prevent
pores of MOFs and/or supported on the exterior surfaces of
the aggregation of NPs but also provides the platform for the
MOFs.[10] Especially, MIL-101 MOFs are widely used as
tuning of catalytic properties via confinement/electronic effects
support/host because of its stability against water and wide pore
openings.[11] However, efforts to grow MOFs on preformed Pd
present at the interface between metal and matrix.
Well-defined porous crystalline materials such as metal-
NPs are still scarce,[12] [7a] especially synergetic effects arising
organic frameworks (MOFs) will be advantageous as matrix as
out of such architecture are yet to be comprehensively evaluated.
they offer exceptional control over the pore surface chemistry. [3]
In this context, we have grown MIL-101(Fe) MOF[13]
MOFs are formed by the coordination linkage between organic
{Fe3OCl [(O2C)-C6H4-(CO2)]3(H2O)2]·nH2O} on preformed Pd
linker/ligand and metal ions/metal clusters (secondary building
nanocubes (NCs) to generate a bifunctional catalyst with Pd
units, SBUs).[4] Though, various metal-MOF nanocomposites
active centers on the metal nanoparticle and Lewis acid centers
with different nanostructure are known,[5] metal⊂MOF
on SBUs of MOF. The cooperative catalytic properties aroused
out of this combination of active sites were established for the
hydrogenation of α, β-unsaturated carbonyl compounds i.e.
cinnamaldehyde, crotanaldehyde, and β-ionone. Remarkably,
architectures[6] wherein MOFs are assembled on to the
preformed metal NPs are chosen for the present study to
strongly influence the activity of the entire nanoparticle surface.
These architectures have various apparent advantages (Table
significant improvement in the activities and selectivities were
S1) which include i) sieving of reactant molecules through MOF
noted before and after coating Pd NCs with MIL-101(Fe) MOF.
[6a,c,e,f]
matrix,
ii) modulation of electronic structure of metal
The turn over frequency (TOF) values increased up to ~20 folds.
The Pd NCs were synthesized (Figure S1) from Na2PdCl4
by using ascorbic acid as reducing agent, PVP as stabilizer and
KBr as a shape directing agent. [14] MIL-101(Fe) was coated on
preformed Pd NCs (~80 mg) by storing in DMF at 120 ˚C for 12
h in the presence of terephthalic acid (0.7 mmol) and FeCl3 (0.7
mmol). The brown solid was isolated and washed with fresh
DMF and ethanol. The powder X-ray diffraction (PXRD) data
(Figure 1a) of the as-synthesized solid confirms the presence of
both MIL-101(Fe) and Pd face centered cubic crystalline phases
in the material. The Pd crystallite size calculated from PXRD
active sites through the charge transfer between SBU and metal
[a] V. R. Bakuru, S. B. Kalidindi
Materials science division, Poornaprajna Institute of Scientific
Research, Devanahalli, Bangalore Rural 576164, India.
Email: sureshk@poornaprajna.org
[b] V. R. Bakuru
Graduate Studies, Manipal University, Manipal-576104, India
Supporting information for this article is given via a link at the end of the
document
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electron microscopy(SEM) analysis of the MOF samples showed
particles with well-defined morphologies, octahedral for MIL-
101(Fe) and spindle like elongated octahedral for Pd⊂MIL-
101(Fe) (Figure 1b,1c). The fact that we did not observe isolated
phases of Pd NCs and MOF in Pd⊂MIL-101(Fe) materials rules
out the formation of physical mixture. This was further confirmed
by transmission electron microscopy(TEM) analysis. The bright
field-TEM images of Pd⊂MIL-101(Fe) samples revealed the
presence of MOF matrix around Pd NCs (Figure 1d). As evident
from the images almost all the Pd NCs are clearly embedded
inside MOF matrix. Very few particles are seen near the surface
with partial encapsulation (figure 1e).The average particle size
was found to be 12.5 ± 0.8 nm which is in good agreement with
the crystallite size calculated using PXRD data. This shows that
majority of Pd NCs are single crystalline in nature. The
distribution of MIL-101(Fe) over various Pd NCs is also evident
from scanning transmission electron microscopy energy
dispersive X-ray (STEM-EDX) data (Figure S2), throughout the
line scan Fe signal is present. The variations in Pd signal is in
accordance with the location of Pd NCs. The weight percentage
of Pd in the Pd⊂MIL-101(Fe) sample was estimated to be
59.5 % using inductively coupled plasma optical emission
spectrometry. The samples were analysed for porosity using N2
sorption measurements at 77 K (Figure 1f). The BET surface
areas of neat MIL-101(Fe) and Pd⊂MIL-101(Fe) were found to
be 1387 m2/g and 536 m2/g, respectively. A decrease of 61% in
the surface area is attributed to the 59.5 wt% of Pd content in
Pd⊂MIL-101(Fe) material. Thermo gravimetric analysis (TGA)
revealed that Pd⊂MIL-101(Fe) is stable up to 280 ˚C which is
about 50 ˚C less compared to pristine MOF (Figure S3). The X-
ray photo electron spectroscopy (XPS) analysis ( Figure S4)
showed that electronic structure of Pd remains unchanged
before and after MOF coating on Pd NCs. The positions of Pd3/2
and Pd5/2 peaks remained same. It should be noted that at
metal-MOF interface charge transfer is possible and has been
observed in few metal-MOF hybrid materials. [7]
To explore the possible catalytic synergy that can originate
out of the presence of Lewis acid centers and Pd active sites in
Pd⊂MIL-101(Fe), hydrogenation of α, β-unsaturated carbonyl
compounds (Scheme 2a.) was carried out. Hydrogenated
products of α,β-unsaturated carbonyl compounds are widely
used in perfume industry.[15] However, achieving high yields
under mild conditions with good chemo- and regio- selectivities
is a challenge for this class of reactions as multiple products are
formed due to the hydrogenation of C═C and/or C═O. The
possible hydrogenated products of CAL are shown in Scheme
2b.
We carried out hydrogenation of CAL in a Fischer bottle in
isopropanol solvent under 3 bar H2 pressure in the presence of
1.5 wt%(Pd relative to the reactant) catalyst at 40 ˚C. The
superior hydrogenation ability of Pd⊂MIL-101(Fe) compared to
Pd NCs is evident from the 2 folds increase (to 991.2 ± 26.1 h-1
from 469.6 ± 10.4 h-1, at ~21% conversion) in TOF values. To
confirm that indeed MOF coating is responsible for the
enhancement of catalytic activity, we compared the activities
with Pd+MOF physical mixture and Pd NCs supported on MIL-
101(Fe) catalysts. As shown in Figure 2a and Figure 2b,
Pd⊂MIL-101(Fe) catalyst outperforms all the other catalysts in
terms of activity and selectivity.
Figure 1. a) Powder XRD patterns of simulated and as-synthesized
MIL-101(Fe) and Pd⊂MIL-101(Fe) samples; b) and c) scanning electron
microscopy (SEM) images of MIL-101(Fe) and Pd ⊂ MIL-101(Fe)
materials; d) and e) bright field-TEM images of Pd⊂ MIL-101(Fe)
catalyst; and f) N2 adsorption isotherms of Pd NCs and Pd⊂MIL-
101(Fe).
data using Scherrer equation was 12.3 nm. The scanning
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Scheme 2. a) Selected α,β-unsaturated carbonyl compounds for
study; b) Possible products from hydrogenation of cinnamaldehyde
Figure 2. a) and b) activity and products selectivity (at 100% conversion)
for the cinnamaldehyde hydrogenation over Pd⊂MIL-101(Fe), Pd NCs,
Pd+MIL-101 (physical mixture) and Pd/MIL-101 (supported) catalysts; c)
Recyclability of Pd⊂MIL-101(Fe) for hydrogenation of cinnamaldehyde
This emphasizes the fact that the observed catalytic properties
of Pd⊂MIL-101(Fe) are not simple linear combination of
individual counterparts but due to the synergetic effects that
arise out of metal⊂MOF architecture. Complete conversion of
CAL was noted for both Pd NCs and Pd⊂MIL-101(Fe) after 1.5 h
of reaction time (Scheme S5). Over Pd NCs, the selectivities of
saturated aldehyde HCAL and saturated alcohol HCOL were
found to be 34.4 % and 65.6 %, respectively. This shows that
both C═C and C═O readily got hydrogenated over Pd NCs. In
contrast, Pd⊂MIL-101(Fe) catalyst showed preference for C═C
over C═O. The selectivities of HCAL and HCOL were found to
be 86.4 % and 13.6%, respectively at 100 % conversion. This is
one of the rare examples in which HCAL selectivity as high as
86.4 % is observed for Pd particle size regime of > 10 nm (Table
S2). It is well documented in the literature that the η4(di-π) mode
of CAL is responsible for the formation of HCOL (Scheme
S3).[16], [17] But, over Pd⊂MIL-101(Fe), CAL can readily bind to
Fe(III) Lewis acid centers of MIL-101 through C═O group.[7c]
The presence of Lewis acid centers in Pd⊂MIL-101(Fe) was
confirmed using NH3-temperature programmed desorption
hydrogenation of another important fragrance chemical, i.e. β-
ionone. The TOFs increased by 20 folds and the values were
42.2 ± 0.7 h-1 and 830.1 ± 19.1 h-1 for Pd NCs and Pd⊂MIL-
101(Fe), respectively. For both substrates, Pd NCs and
Pd⊂MIL-101 (Fe) showed 100% selectivity towards only C═C
hydrogenated products.
The facile hydrogenation of α,β-unsaturated carbonyl
compounds over Pd⊂MIL-101(Fe) might be due to presence of
nanoreactors (MOF pores) around Pd active sites wherein both
substrate and H2 should be relatively more localized due to the
favorable interaction with Lewis acid centers and Pd active sites,
respectively. The H2 adsorption measurements were performed
over the catalysts under study at 298 K (Figure S8). The Pd⊂
MIL-101(Fe) catalyst shown ~30 % higher H2 uptake compared
Pd NCs and Pd/MOF. It is consistent with earlier reports that
MOF coating has pronounced positive effect on the hydrogen
storage properties of Pd in Pd@MOF core-shell material[ 7a] and
accounts for the observed superior catalytic performance of the
Pd⊂MIL-101(Fe) .
In summary, the Pd NCs (12.5 ± 0.8 nm) were coated with
MIL-101(Fe) and its structure was confirmed by PXRD, TEM and
SEM analysis. The positive effect of MOF assembly around Pd
NCs clealry demonstrared for the hydrogenation of α, β-
unsaturated carbonyl compounds, TOFs increased several folds
(upto 20 folds for β-ionone). The reusable Pd⊂MIL-101(Fe)
catalyst also exhbited high selectivity for C=C over C=O for all
the substrates. These results shows that coating of MOF onto
metal NPs can enhance NPs catalytic performance remarkably
due to the synergy between active centers present on metal
NPs and MOF, and highlights the scope of MOFs as an
encapsulating matrix.
analysis (Figure S9).
As C═O can participate in these
secondary interactions, CAL is less likely to participate in planar
η4(di-π) kind of mode. In this scenario, the most likely adsorption
reported in the literature (Table S2) for CAL hydrogenation.
These findings indicate that MIL-101 effectively enhances the
catalytic performance of Pd NCs in Pd⊂MIL-101(Fe) material.
Moreover, Pd⊂MIL-101(Fe) catalyst was readily reusable
(Figure 2c) and highly stable (Figure S7), both conversion and
chemoselectivity remained almost unaltered up to 5 cycles. Hot
filtration test (Figure S6) carried out by removing the catalyst
after 20 min of reaction time confirms that catalysis is
heterogeneous in nature.
Further, hydrogenation of crotanaldehyde(Scheme S1)
and β-ionone (Scheme S2) was carried out over Pd NCs and
Pd⊂MIL-101(Fe) under same reaction conditions as CAL.
Reinforcing positive effect of MOF coating on Pd NCs catalytic
performance, the catalysts display TOF ( below 20% conversion)
of 2268.8 ± 59.9 h-1 and 9837.6 ± 134.3 h-1 for Pd NCs and
Pd⊂MIL-101(Fe), respectively. Similar effect is also noticed for
Acknowledgements
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Entry for the Table of Contents
COMMUNICATION
MOF assembly around preformed Pd
nanocubes enhanced the catalytic
performance of Pd several folds for
hydrogenation of α, β-unsaturated
carbonyl compounds owing to synergy
between functional sites present on
metal nanopartice and MOF.
Vasudeva Rao Bakuru[a],[b] and Suresh
Babu Kalidindi*[a]
Page No. – Page No.
Synergistic Hydrogenation over
Palladium through the Assembly of
MIL-101(Fe) MOF over Palladium
Nanocubes
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