Nanocomposite Hydrogel of Pd@ZIF-8 and Laponite: Size-Selective Hydrogenation Catalyst under Mild Conditions

Article abstract of DOI:10.1002/chem.202004345

The composite hydrogel of a nanoscale metal–organic framework (NMOF) and nanoclay has emerged as a new soft-material with advanced properties and applications. Herein, we report a facile synthesis of a hydrogel nanocomposite by charge-assisted self-assembly of Pd@ZIF-8 nanoparticles with Laponite nanoclay which coat the surface of Pd@ZIF-8 nanoparticles. Such surface coating significantly enhanced the thermal stability of the ZIF-8 compared to the pristine framework. Further, the Pd@ZIF-8+LP hydrogel nanocomposite shows better size-selective catalytic hydrogenation of olefins than Pd@ZIF-8 nanoparticles based on selective diffusion of the substrate.

Full text of DOI:10.1002/chem.202004345

Accepted Article
Accepted Article
Title: Nanocomposite Hydrogel of Pd@ZIF-8 and Laponite®: Size-
Selective Hydrogenation Catalyst at Mild Condition
Authors: Papri Sutar, Vasudeva Rao Bakuru, Pooja Yadav, Subhajit
Laha, Suresh Babu Kalidindi, and Tapas Kumar Maji
This manuscript has been accepted after peer review and appears as an
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To be cited as: Chem. Eur. J. 10.1002/chem.202004345
Link to VoR: https://doi.org/10.1002/chem.202004345
01/2020

10.1002/chem.202004345
Chemistry - A European Journal
COMMUNICATION
Nanocomposite Hydrogel of Pd@ZIF-8 and Laponite®: Size-
Selective Hydrogenation Catalyst at Mild Condition
Papri Sutar,[a] † Vasudeva Rao Bakuru, [a,c] † Pooja Yadav,[a] Subhajit Laha,[a] Suresh Babu Kalidindi*[ b]
and Tapas Kumar Maji*[a]
Abstract: The composite hydrogel of the nanoscale metal-organic
framework (NMOF) and nanoclay emerged as a new soft-material
with advanced properties and applications. Here, we report a facile
synthesis of a hydrogel nanocomposite by charge-assisted self-
assembly of Pd@ZIF-8 nanoparticles with Laponite® nanoclay which
coat the surface of Pd@ZIF-8 nanoparticles. Such surface coating
significantly enhanced the thermal stability of the ZIF-8 compared to
the pristine framework. Further, Pd@ZIF-8+LP hydrogel
nanocomposite shows size-selective catalytic hydrogenation of
olefins compared to bare Pd@ZIF-8 nanoparticles based on
selective diffusion of the substrate.
Metal-organic framework (MOF) based nanocomposites
are the new class of hybrid materials that have attracted
Scheme1. Schematic representation showing self-assembly of Pd@ZIF-8
and Laponite® to form Pd@ZIF-8+LP hydrogel nanocomposite that
increasing research attention due to their synthetic diversities,
exhibits selective hydrogenation catalysis.
unique
functionalities,
and
architectures.1
These
nanocomposites usually consist of two integrated components; a
nanoscale MOF (NMOF) and another one or more active
ingredients such as graphene oxide,2a-b porous silica,2c-d organic
polymers,2e inorganic clay,2f-g, and boron nitride2h. Such
integration not only mitigates the shortcoming of the NMOF but
also results in advanced properties that are notably different
molecule. In general, MOFs are structurally fragile to high-
temperature treatment compared to inorganic counterparts like
zeolites, which limits their industrial application in heterogeneous
catalysis. In this regard, we envisage that the surface coating of
ZIF-8 with hard LP clay would increase the thermal stability of
the hydrogel nanocomposite and provide an opportunity to study
for size-selective heterogeneous catalysis using metal
nanoparticles (MNPs) encapsulated ZIF-8.
from
the
individual
components.
Therefore,
MOF
nanocomposites are widely explored as advanced materials that
show promising applications in gas storage/separation,2f-g
Encapsulation of pre-synthesized MNPs in MOFs have
been the subject of considerable research for the past few years
because of their better efficiency in heterogeneous catalysis
than free MNPs.5 Owing to the high surface energy; free MNPs
show fast aggregation that not only affects their intriguing
properties but also hampers long-term storage, processing, and
applications.6,7 In this regard, Huo et al. described a strategy for
controlled encapsulation of various polyvinylpyrrolidone (PVP)-
heterogeneous catalysis,3a-e drug delivery3f-h and sensing3i-j
.
Among different MOF nanocomposite reported to date,
fabrication of ‘soft’ nanocomposite hydrogel from the
supramolecular self-assembly of crystalline NMOF and another
active component is rare. Recently, our group has reported an
easy room-temperature synthesis of a nanocomposite hydrogel
(ZIF-8+LP) by the charge-assisted self-assembly of ZIF-8
(zeolitic imidazolate framework) nanoparticles (ZIF-8 NPs)
having a positive surface charge with organosilicate nanoclay,
modified Pt NPs within ZIF-8.8 The
Pt/ZIF-8 composite
catalyzed organic reactions (hydrogenation and oxidation, etc.,)
driven by the supported MNPs.9 However, such MNPs/MOF
composites could lack in catalytic selectivity due to the
disintegration of MOF structure or change of stability of MNPs
during the reaction at harsh conditions. The depletion of active
centers in such composite system could inhibit their practical
applications.9i, 10 In this context, Jiang et al., reported that surface
hydrophobization of Pd/UiO-66 composite by a thin coating of
polydimethylsiloxane (PDMS), improved catalytic selectivity
towards hydrophobic reactants, as it facilitates the enrichment of
hydrophobic substrates around the catalytic site.11 However, the
coating of PDMS on Pd/UiO-66 was carried out by a tedious
chemical vapor evaporation technique. We envisioned that
supramolecular self-assembly of LP nanoclay with Pd@ZIF-8
composite could be a facile and easy way to coat the surface of
Pd@ZIF-8 through charge assisted assembly which could also
Laponite® (LP,
a
smectite clay, commercially available
trademark product of BYK additives Ltd.) having negatively
charged faces.4 The surface coated of ZIF-8+LP nanoparticles
showed a pH-controlled release of the encapsulated drug
[a] Dr. Papri Sutar, Dr. Vasudeva Rao Bakuru, Pooja Yadav, Subhajit
Laha, and Prof. Dr. T. K. Maji
Molecular Materials Laboratory, Chemistry and Physics of
Materials Unit, School of Advanced Materials (SAMat), Jawaharlal
Nehru Centre for Advanced Scientific Research, Jakkur,
Bangalore -560 064, India.
E-mail: tmaji@jncasr.ac.in; http://www.jncasr.ac.in/tmaji
[b] Dr. Suresh Babu Kalidindi,
Inorganic and Analytical Chemistry Department, School of
Chemistry, Andhra University, Visakhapatnam, India-530003.
E-mail: ksureshu@gmail.com
[c] Dr. Vasudeva Rao Bakuru,
Materials Science Division, Poornaprajna Institute of Scientific
Research, Devanahalli, Bangalore Rural-562164, India. Manipal
Academy of Higher Education, Manipal, 576 104, India
facilitate the size-selective catalysis
using hydrogel
†
These authors contributed equally.
Supporting information for this article is given via a link at the end
of the document.
nanocomposite. In this communication, we report the synthesis
and characterization of Pd@ZIF-8+LP nanocomposite hydrogel.
Hydrogelation results uniform coating of LP onto the Pd@ZIF-8
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NPs that results significantly high thermal stability and
introduced selective hydrogenation for linear alkenes by
controlled diffusion.
hexagonal nanoparticles with diameter in the range of 300-600
nm, similar to ZIF-8 NPs (Fig. 1b and Fig S3). The high-
resolution TEM images of Pd@ZIF-8 confirm the formation of
hexagonal core-shell nanoparticles with the Pd NPs well
encapsulated by the ZIF-8 shell (Fig. 1e and Fig. S4). The N2
adsorption isotherm at 77 K of desolvated Pd@ZIF-8 reveals
lower N2 uptake compared to pristine ZIF-8 NPs, and BET
surface areas are determined to be 1384 and 1152 m2/g for ZIF-
8 and Pd@ZIF-8, respectively, and the pore-size distribution
curves suggest that both materials in microporous nature (Fig.
S5). Such a small decrease in surface area in Pd@ZIF-8 occurs
due to mass occupation by nonporous Pd NPs. Energy-
dispersive X-ray analysis (EDXA) of Pd@ZIF-8 indicates the
presence of palladium in Pd@ZIF-8 NPs (Fig. S6). The
palladium content in Pd@ZIF-8 NPs is determined to be 1.8 wt%
by inductively coupled plasma atomic emission spectroscopy
(ICP-AES) analysis. Zeta potential analysis of Pd@ZIF-8 NPs (a
ζ potential of +55 mV) indicates the surface positive charge,
resulting from the unsaturated Zn2+ sites at surfaces of Pd@ZIF-
8 NPs (Fig. S7). Next, we have studied the self-assembly of
Pd@ZIF-8 NPs with Laponite® (LP) nanoclay, similar to our
previous report.4 LP is well-known to have layered-platelet
nanostructure with negatively charged faces. We envisioned that
charge-assisted self-assembly of Pd@ZIF-8 NPs and LP could
result in the composite hydrogel. Gelation experiments were
performed in a water/MeOH mixture using various ratios of
Pd@ZIF-8 NPs and LP. The formation of stable hydrogel
(Pd@ZIF-8+LP) is realized when the dispersion of Pd@ZIF-8 (8
mg in 600 μl MeOH) was added into the aqueous solution of LP
(10 mg in 1 ml water), and the homogeneous mixture (formed
after sonication) was kept undisturbed at room temperature for
2-3 h. Pd@ZIF-8+LP hydrogel nanocomposite is transparent
and remains stable upon inversion (Fig. 1c). The wt% of
Pd@ZIF-8 and LP in Pd@ZIF-8+LP hydrogel is calculated to be
44.4% and 55.6%, respectively. PXRD analysis of Pd@ZIF-
8+LP xerogel shows a pattern similar to ZIF-8 and Pd@ZIF-8,
indicating the stability of Pd@ZIF-8 after hydrogel formation (Fig.
1a). The peaks corresponding to LP are also observed. To get
insight into the morphology of the nanocomposite hydrogel,
FESEM and TEM images were recorded. The FESEM images of
Pd@ZIF-8+LP xerogel shows the formation of an interconnected
network where the Pd@ZIF-8 particles are wrapped with layered
LP clay matrix (Fig. 1d and Fig. S8). The EDX analysis of
Pd@ZIF-8+LP xerogel indicates the presence of Pd along with C,
Figure 1. a) PXRD pattern of ZIF-8 (blue), Pd@ZIF-8 (pink), Laponite®
(solid purple) and Pd@ZIF-8+LP (green), b) FESEM image of
Pd@ZIF-8 showing formation of hexagonal particles, c) Picture of
Pd@ZIF-8+LP hydrogel, d) FESEM image of Pd@ZIF-8+LP xerogel
showing the wrapping of Laponite® over the hexagonal particles, e)
High resolution TEM images of Pd@ZIF-8 NPs showing the
encapsulated Pd NPs, and f) High resolution TEM image of Pd@ZIF-
8+LP xerogel showing the encapsulated Pd NPs.
alkenes by controlled diffusion. The core-shell Pd@ZIF-8
nanoparticles were synthesized by modifying a previously
reported procedure4 (Supporting information) and characterized
by powder X-ray diffraction pattern (PXRD), field emission
scanning electron microscopy (FESEM) and transmission
electron microscopy (TEM) analysis as shown Figure 1. The
PXRD of Pd@ZIF-8 nanocomposite shows pattern to similar
ZIF-8 NPs, suggesting structural integrity of ZIF-8 after
incorporation of Pd NPs (Fig. 1a). The FESEM images of
Pd@ZIF-8 NPs show the formation of mono-dispersed
Figure 2. a) TGA of Pd@ZIF-8 (blue) and Pd@ZIF-8+LP xerogel
(red), b) PXRD of Pd@ZIF-8 (red) and Pd@ZIF-8+LP xerogel
(maroon) and their calcined products. Conditions: Calcinated at 550
˚C under Ar for 1h.
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10.1002/chem.202004345
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N, O, Li, Na, Mg and Zn (Fig. S9). The ICP-AES analysis of
Pd@ZIF-8+LP confirms 0.85 wt% Pd content in the xerogel.
TEM images of Pd@ZIF-8+LP xerogel clearly show that the
hexagonal Pd@ZIF-8 particles are coated with LP clay layers
which are mainly found at the edges of Pd@ZIF-8 NPs. The
high-resolution TEM images reveal that Pd NPs are well-
encapsulated by ZIF-8 and not leached out in Pd@ZIF-8+LP
xerogel (Fig. 1f and Fig. S10). The unsaturated Zn2+ sites
present at the surface of Pd@ZIF-8 interact electrostatically with
the negative faces of LP and result in such wrapped
nanostructures. The Pd@ZIF-8 shows thermal stability up to
420 °C as evident from thermogravimetric analysis (TGA) (Fig.
2a).12 To our surprise Pd@ZIF-8+LP xerogel did not show any
major weight loss step in TGA even above 550 °C that confirms
our conjecture of LP coating would increase thermal stability.
However, we observed a gradual weight loss of about 10 % till
550 °C, which can be attributed to dehydration of the clay. To
further confirm the thermal stability, we annealed Pd@ZIF-8,
Pd@ZIF-8+LP materials at 550 °C under Ar atmosphere for 1 h
and recorded PXRD patterns (Fig. 2b). After annealing,
Pd@ZIF-8 turns black and the PXRD pattern showed peaks
corresponding to ZnO, indicating the decomposition of the ZIF-8
structure. However, under the same condition, Pd@ZIF-8+LP
remains stable as evident from the PXRD pattern, showing
peaks corresponding to ZIF-8 and LP. These observations
highlight the important role of LP in enhancing the thermal
stability (550 ˚C) of Pd@ZIF-8+LP and such observation is
unprecedented in MOF chemistry. The N2 adsorption isotherm at
77 K of Pd@ZIF-8+LP xerogel shows 190 m2/g surface area
which is less compared to Pd@ZIF-8. The low uptake of N2 is
mainly due to the mass occupation by nonporous LP clay (Fig.
S5). Also, the pore-size distribution as calculated by NLDFT
method, revealed that the material has a microporous nature
with pore-size centered at 1.01 and 0.59 nm.
The presence of Pd nanoparticles inside a matrix of ZIF-8
allows sieving of reactant molecules based on their molecular
sizes for hydrogenation of alkenes.7k, 8 In Pd@ZIF-8+LP xerogel,
the presence additional layer of LP over Pd@ZIF-8 could offer
further disparity in the diffusion of reactant molecules leading to
fine sieving of reactants. To explore this, both Pd@ZIF-8 and
Pd@ZIF-8+LP materials were evaluated for the hydrogenation of
a wide variety of alkenes with different molecular sizes. All the
reactions were carried out under 1 bar H2 at 50 °C over 0.21
mol % (Pd content) catalyst for 1h. As evident from Figure 3a,
the presence of LP offered an additional sieving effect; the
conversions are low over Pd@ZIF-8+LP compared to Pd@ZIF-8
due to longer diffusion (slow rate) substrate pathways offered by
the catalyst (Table S1). This is very much apparent for the
substrates containing cyclic C6 rings in their structure. For a
simple linear 1-hexene (2.5 Å X 8.0 Å2) Pd@ZIF-8 and Pd@ZIF-
8+LP catalysts showed a conversion of 88.8 % and 61.2 %,
respectively(Fig. S12). On the other hand, for styrene (4.0 Å X
6.7 Å2), the catalysts showed conversions of 99.8% and 21.3%,
respectively. In the case of 1-limonene (8.2 Å X 4.1 Å2), the
Pd@ZIF-8+LP catalyst did not show any conversion, whereas
Pd@ZIF-8 showed a conversion of 33.1 %. This suggests that
LP offered a high diffusion barrier to 1-limonene. For, large-size
cyclooctene (5.5 Å X 5.5 Å) both Pd@ZIF-8+LP and Pd@ZIF-8
did not show any conversion. Further, mixtures of alkenes were
subjected to hydrogenation over both catalysts as shown in
Figure 3b. Hydrogenation of 1-hexene and 1-limonene mixture
was carried out under the above-mentioned reaction conditions
over Pd@ZIF-8+LP and Pd@ZIF-8, separately. As expected,
over Pd@ZIF-8+LP, only 1-hexene underwent hydrogenation to
hexane with 58.2 % conversion, no detectable conversion of 1-
limonene was observed. On the other hand, Pd@ZIF-8 showed
83.7 % 1-hexene and 15.0 % of 1-limonene conversions under
the same reaction conditions. Therefore, Pd active sites in
Pd@ZIF-8+LP are accessible to only 1-hexene unlike Pd@ZIF-8
wherein Pd sites are accessible to both substrates (though to a
different degree). We have also carried out the hydrogenation of
1-hexene and styrene mixture over both catalysts (Fig. S13).
Again, reinforcing the excellent sieving effect imposed by LP, the
conversions were 63.5 % and 30.2 % over Pd@ZIF-8+LP and
91.2 %, 99.9 % over Pd@ZIF-8, for 1-hexene and styrene,
respectively. Overall, these results suggest that Pd@ZIF-8+LP
can fine sieve the reactants by bringing additional disparity in
diffusion. As this material has characteristic microporous nature
(~1 nm), the linear alkene molecules can easily diffuse into the
Pd@ZIF-8+LP material. Such reduction in pore size introduces
size-selective hydrogenation.
We have also tested the stability of Pd@ZIF-8+LP and
Pd@ZIF-8 catalysts by carrying out recyclability tests (Fig. 3c).
We did not notice any significant changes in the conversions of
1-hexene over both catalysts after 4 cycles. Moreover, no
significant change in the PXRD pattern of the Pd@ZIF-8+LP
after 4 catalytic cycles suggesting high stability of the hydrogel
composite (Figure S15). Further, hot filtration tests were carried
out by isolating the catalysts during the reaction (Fig. S14). After
removal of catalyst from the reaction mixtures, no further
progress of the reactions was observed. These observations
suggest that the hydrogenation reaction was heterogeneous and
no leaching of Pd has taken place.
Figure 3. a) Hydrogenation of different substrates over Pd@ZIF-8 and
Pd@ZIF-8+LP catalysts, b) Hydrogenation of mixed 1-hexene and
limonene substrates catalyzed by Pd@ZIF-8 and Pd@ZIF-8+LP
catalysts, and c) Recyclability test in the hydrogenation of 1-hexene over
Pd@ZIF-8 and Pd@ZIF-8+LP catalysts.
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In summary, we have demonstrated the facile synthesis of
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Acknowledgements
PS is thankful to the Council of Scientific and Industrial
Research (CSIR). BVR thanks to DST and TRC-JNC/4612 for
providing fellowship. SBK thanks DST-inspire for the grant (IFA-
12/CH-166). TKM is grateful to the DST (SERB, DST, project no.
CRG/2019/005951), Govt. of India, and the JNCASR for
financial support.
Keywords:
•Metal-Organic
Frameworks
(MOFs)
•Nanocomposite hydrogel • Catalysis • Selective hydrogenation
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10.1002/chem.202004345
Chemistry - A European Journal
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
We have demonstrated
Papri Sutar,[a] † Vasudeva Rao Bakuru [a,c]
†, Pooja Yadav,[a] Subhajit Laha,[a] Suresh
Babu Kalidindi*[ b ] and Tapas Kumar
Maji*[a]
here
hydrogel nanocomposite by
charge-assisted self-
assembly of Pd@ZIF-8
nanoparticles with
Laponite® nanoclay and the
resulting Pd@ZIF-8+LP
nanocomposite showed
a preparation of a
Page No. – Page No.
Nanocomposite Hydrogel of Pd@ZIF-8
and
Hydrogenation
Condition
Laponite®:
Size-Selective
Catalyst at Mild
efficient and size selective
catalytic hydrogenation of
olefins.
This article is protected by copyright. All rights reserved.