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Direct ink writing of catalytically active UiO-66
polymer composites†
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Cite this: DOI: 10.1039/c8cc10018g
Adam J. Young, ‡a Rémy Guillet-Nicolas, ‡b Ellis S. Marshall,
Received 18th December 2018, Freddy Kleitz, b Alex J. Goodhand,a Lloyd B. L. Glanville,a
Accepted 23rd January 2019
Michael R. Reithofer *c and Jia Min Chin *ac
DOI: 10.1039/c8cc10018g
rsc.li/chemcomm
Metal–organic frameworks (MOFs) hold significant potential for use
in gas storage, sensing and catalysis. To uncover this potential, MOF
processing must develop in line with MOF materials. Here, direct ink
writing-based 3D printing of UiO-66 MOF composites and their
thermal treatment give mechanically stable yet highly porous com-
posites effective for the catalytic breakdown of methyl-paraoxon, a
simulant of highly toxic organophosphate nerve agents.
Metal–organic frameworks (MOFs) can possess extremely high
porosity and surface areas, rendering them especially attractive
for applications such as catalysis,1–4 gas separation5 and gas
storage.6 Unfortunately, MOF processability is low7 due to their
general insolubility and lack of thermoplasticity. However,
integration with polymer composites8,9 has significantly enhanced
processability of the resulting materials, thereby expanding their
applications.10 Amongst processing methods, 3-dimensional
printing (3DP) has seen an exponential growth in usage within
recent years as it allows rapid yet flexible fabrication of complex
3D structures using materials such as ceramics, resins and
even novel nanocomposites.11 However, despite several examples
of 3D printed MOF composites,12–14 the use of 3DP for the
production and design of MOF-based materials still remains in
the nascent stage.
Thakkar et al. reported direct ink writing of nickel (MOF-74)
and cobalt (UTSA-16) based MOFs at 80 and 85 wt% loadings
into monolithic structures and demonstrated their use for CO2
a
Faculty of Science and Engineering, Chemistry, University of Hull,
Cottingham Road, Kingston upon Hull, HU6 7RX, UK. E-mail: j.chin@hull.ac.uk
b
Faculty of Chemistry, Department of Inorganic Chemistry – Functional Materials,
University of Vienna, Währinger Strasse 42, 1090 Vienna, Austria
c
Department of Inorganic Chemistry, Faculty of Chemistry, University of Vienna,
Währinger Strasse 42, 1090 Vienna, Austria.
E-mail: michael.reithofer@univie.ac.at
† Electronic supplementary information (ESI) available: Definition of terms,
characterisations, SEM, rheological measurements, FTIR-ATR, BET, TGA, ICP-
OES, catalysis, NMR, mechanical testing and optical photographs of samples. See
DOI: 10.1039/c8cc10018g
‡ These authors contributed equally
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a
capture,15 showing the potential of 3D printed MOF materials.
Direct ink writing based 3DP relies upon the computer-controlled
deposition of ink in a layer-by-layer manner to build a 3D object.11
A key challenge in this method is the control over the ink rheology,
so that the ink is extrudable, and yet shows shape and structure
retention after extrusion. Further, extruded filaments require
sufficient yield stress and storage moduli to allow for over-
hanging structures.16 Thakkar et al. utilized bentonite clay rheology
modifiers to achieve the requisite viscoelastic properties for direct
ink writing. However, it would be preferable to use the chemically
active MOF particles themselves as rheological modifiers. Indeed,
this possibility is supported by findings that suspensions of MOF
particles such as ZIF-8 demonstrate thixotropic properties, arising
from MOF interparticle interactions.17
Zirconium-based MOFs such as UiO-66 have been shown
to catalyse the breakdown of methyl-paraoxon, parathion and
p-nitrophenyl diphenyl phosphate,18–21 simulants of chemical
warfare agents such as VX, tabun and soman. Further, UiO-66
possesses excellent mechanical properties relative to other
MOFs, such as ZIF-8 or HKUST-1.22,23 These properties led us
to investigate the direct ink writing of UiO-66 composite
formulations and their use in the catalytic the breakdown of
the nerve agent simulant methyl-paraoxon.
UiO-66 particles were synthesized in accordance to literature
(ESI,† Fig. S1).24 Rheological studies of UiO-66 particles dispersed
in ethanol showed that the resulting suspensions possessed shear-
thinning properties (ESI,† Fig. S2), important for direct ink writing.
We sought to optimize the shear-thinning viscoelastic properties
of the ink through selection of suitable binders. A mixture of
commercially available acrylates, trimethylolpropane propoxylate
triacrylate (TMPPTA), offering fast curing times with its branched
acrylate system and EBECRYLs 8413, a viscous and flexible acrylate
previously utilized in elastomeric inks, were selected for use as the
binder for UiO-66 particles.25 The UiO-66 particles were dispersed
into a mixture of the polymer binder and a photoinitiator (PI) blend
(see ESI,† for details) generating a homogeneous paste. The
optimized mixture was composed of 52 wt% UiO-66, 44 wt%
polymer binder and a 4 wt% photoinitiator mixture when dried
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Fig. 1 Rheological behaviour of UiO-66 composite ink, simulating the
extrusion process at the nozzle (non-continuous extrusion when printing).
UiO-66 composite ink displays fast sol–gel transitions required for precise
3D printing of composite materials.
and displayed suitable viscoelastic properties required for direct ink
writing (Fig. 1 and ESI,† Fig. S3).26 On exposure to UV light
(365 nm), the binders crosslink, as supported by FTIR-ATR, where
the loss of the vinyl group stretching band at around 2900 cm 1
was observed (ESI,† Fig. S6).
Although Evans et al. have shown that UiO-66 can be
extruded into melt-processable filaments for fused deposition
modelling,27 to our knowledge, the use of 3D printed MOF
composites for chemical transformations has still not been
demonstrated. This would require that the MOF composite
shows structure retention in relevant reagent/solvent mixtures
and possesses catalytically accessible MOF active sites.
Direct ink writing based 3DP of the UiO-66 ink was carried
out on a Velleman 3D printer. The ink was irradiated with a
365 nm light source upon extrusion through a 16-gauge nozzle
affording simple woodpile-type 3D structures of UiO-66 com-
posite (UiO-66comp) (Fig. 2a and b). The photo-crosslinking
complements the shear-thinning properties of extruded inks,
aiding in shape-retention during 3DP. Prior to cross-linking, the
polymer binder formulation was miscible in organic solvents. In
contrast, after UV-crosslinking, the ink formulation showed
structure retention during immersion in different solvents,
including water, propan-2-ol, methanol, ethanol and hexane.
Unsurprisingly, the as-printed UiO-66comp samples were
non-porous, as observed by N2 physisorption isotherms (ESI,†
Fig. S9). In anticipation of this, the polymer binder formulation
had been chosen for its lower thermal stability compared to
UiO-66 to allow for investigations into selective binder degrada-
tion and exposure of UiO-66 catalytic sites. The selected binder
starts to degrade above 100 1C and N2 physisorption isotherms
of the UiO-66comp samples outgassed at 150 1C overnight
start to show some light porosity features (ESI,† Fig. S9 and
Table S1). In contrast, UiO-66 possesses high thermal stability,
up to approximately 500 1C, according to thermogravimetric
analysis (TGA) studies by ourselves (ESI,† Fig. S13) and
others.24,28 Further, isothermal TGA of UiO-66 at 280 1C for
200 min showed approximately 20% mass loss in the first 30 min
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Fig. 2 (a) Photograph of UiO-66comp (top); corresponding SEM image
showing aggregates of the UiO-66 MOF and polymer binder (bottom);
(b) photograph of UiO-66compD (top); the SEM image of the composite
shows the crystallites are still present (bottom); (c) PXRD analysis shows
that in UiO-66comp (grey), the patterns are obscured, but are observable
in UiO-66compD (yellow). PXRD patterns of simulated UiO-66 (blue), as
synthesized UiO-66 (orange), UiO-66D (light blue), UiO-66D
hyd (green)
and UiO-66compD
hyd (dark blue) are shown.
(mostly due to expected water loss, ESI,† Fig. S14),24 indicating
that the MOF is largely stable under such conditions. PXRD
of UiO-66 heat-treated at 280 1C under air for 30 min (yielding
UiO-66D) showed that the MOF essentially retained its structure
(Fig. 2), although a slight sample darkening from white to off-
white occurred (ESI,† Fig. S27). The UiO-66comp samples were
therefore placed in a furnace under air at 280 1C for 30 minutes,
then washed twice with dichloromethane (DCM). The resulting
material (UiO-66compD) preserved its printed structure (Fig. 2b),
although it shows a colour change from cream to brown,
attributed to polymer binder and PI degradation. PXRD analysis
shows that the previously obscured PXRD patterns can now be
observed, matching those of as synthesized UiO-66 (Fig. 2c);
further, the morphology of UiO-66 was still retained as seen in
the SEM micrograph (Fig. 2b). Subsequent analysis by ICP-MS
(ESI,† Table S2) and TGA (ESI,† Fig. S13) found that UiO-66comp
and UiO-66compD contained approximately 52 wt% and 74 wt%
MOF respectively, back-calculated from the ICP-MS determined
Zr content.
The pore properties of UiO-66compD were examined using
N2 physisorption ( 196 1C) and the resulting isotherm (ESI,†
Fig. S10) showed the expected characteristics of microporous
UiO-6624 (Type 1 isotherm) but also additional features arising
from the presence of small mesopores. The BET apparent
specific surface (SBET) area29 was calculated to be 633 m2 g 1
and total pore volume, calculated using the Gurvitch rule, was
0.32 cm3 g 1, confirming the importance and efficiency of the
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thermal treatment to make the MOF pore network accessible.
One can observe that the micropore size of the composite,
calculated using the most realistic state-of-the-art NLDFT
model available,30 was found unaffected by sample processing.
To evaluate the mechanical properties of the optimized
formulations after photocuring and heat treatment, monoliths
of photocured UiO-66 inks as well as the polymer binder
mixtures were prepared. Compression testing was carried out
on ‘‘green’’ photocured monoliths as well as samples that were
heated at 280 1C for 30 minutes (ESI,† Table S4). The UiO-66
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composite monoliths showed compressive strengths of 22.4 
0.8 and 4.9  0.9 MPa before and after heat treatment, and
Young’s moduli of 24  2 and 31  5 MPa respectively.
Compression testing was also carried out on monoliths of
the photocured polymer binder/PI mixtures (without UiO-66)
to ascertain the effects of MOF particles on the composite
properties. These monoliths showed compressive strengths of
20.0  0.4 and 4.4  0.7 MPa before and after heat treatment,
and Young’s moduli of 26  2 and 13  6 MPa respectively. This
indicates that the weakening of the UiO-66 composite after heat
treatment is mainly due to polymer binder decomposition and
that the presence of UiO-66 significantly increases the stiffness
of the composites. Nevertheless, we observed that the 3D
printed UiO-66compD samples were robust enough to withstand
routine handling with tweezers and repeated immersion into
different solvents without loss of their printed structures – no
especial care was required for their handling.
As previous work has demonstrated the efficacy of UiO-66 as
a catalyst for the breakdown of the nerve agent simulant
methyl-paraoxon,2,21 we therefore investigated the catalytic
activity of UiO-66compD versus UiO-66 and UiO-66D for this
reaction, via 31P{1H}-NMR spectroscopic studies. Samples of
rehydrated UiO-66D (UiO-66D
hyd) and rehydrated UiO-66compD
(UiO-66compD
hyd) were also prepared by soaking them in water
for 16 h, and included in the catalytic studies. This was because
mechanistic studies by Plonka et al. showed the catalytic
importance of coordinated hydroxyl groups on the Zr clusters,
which would have been removed by our heat treatment of UiO-
66.19 The catalytic testing was performed using a known
literature procedure, whereby 6 mol% catalyst and methyl-
paraoxon (4 mL) were placed in H2O/D2O buffered with 0.45 M
N-ethylmorpholine and monitored via 31P{1H}-NMR.31 The
reaction half-lives were obtained by averaging duplicate experiments
and plotting ln(concentration) versus time, as the reaction follows
first order kinetics (ESI,† Fig. S16).
As the reactions proceeded, hydrolysis of methyl-paraoxon
led to 4-nitrophenol release and yellowing of the initially
colourless solution around the catalyst (Fig. 3).19,32 Kinetic
measurements (Fig. 3 and ESI,† Table S3) show that the
reaction using UiO-66compD achieved 90% conversion after
114 minutes and has a half-life (t1/2) of 38.3 min, with a
turnover frequency (TOF) of 0.48 s 1. When UiO-66 itself is
used, the reaction has t1/2 = 12 min and a TOF of 0.94 s 1
respectively. Kinetic measurements were also carried out to
evaluate the effect of heat treatment on UiO-66, and these show
that the heat treated MOF, UiO-66D, has a much longer t1/2 of
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Fig. 3 Graph comparing percentage conversion of methyl paraoxon to
dimethyl phosphate. Inset: Photographs showing UiO-66compD in a
reaction mixture of methyl paraoxon and N-methyl morpholine at the
start of the reaction (left) and after 200 minutes (right).
346 min, and a TOF of 0.15 s 1. The observed drop in catalytic
activity is attributed to the dehydroxylation of UiO-66,33 which
occurs from about 250 1C.34 Indeed, after rehydration, UiO-66D
hyd
recovers some catalytic activity compared to UiO-66D, with t1/2 of
173 min and a TOF of 0.30 s 1, although this is still lower than that
of initial UiO-66. Similarly, UiO-66compD
hyd also shows drastically
increased catalytic activity over UiO-66compD with t1/2 of 16 min
and an estimated TOF of 0.79 s 1 respectively.
PXRD patterns UiO-66D
and UiO-66D
hyd do not show an
appreciable drop in crystallinity when compared to UiO-66.
Further, the UiO-66D
hyd N2 physisorption isotherm at 196 1C
(ESI,† Fig. S11) exhibited similar features as compared to that
of UiO-66D in terms of isotherm shape and adsorbed volumes.
This suggests that the lower catalytic activity of UiO-66D
hyd
compared to UiO-66 is not due to bulk framework degradation.
However, the surface sites of the UiO-66 MOF particles may
be partially degraded, as supported by the faint darkening of
UiO-66D after thermal treatment (ESI,† Fig. S27). As the break-
down of methyl-paraoxon by UiO-66 is reported to be limited to
catalytic sites on the surface of UiO-66 particles,2 degradation
of the surface active sites would explain the lower catalytic
activity of UiO-66D
hyd compared to non-heat treated UiO-66.
Comparison of PXRD patterns between UiO-66compD
hyd and
UiO-66compD clearly shows an increase in peak intensities of
UiO-66compD
hyd and the resulting PXRD pattern is similar to that
of UiO-66. Further, FT-IR spectra indicate a loss of the polymer
binder signal at 1720 cm 1 after rehydration (ESI,† Fig. S5 and S6),
suggesting that the rehydration step washes out degraded polymer
binder, improving the accessibility of catalytic sites.
Here also, pore properties of UiO-66compD
hyd characterized
by N2 physisorption (ESI,† Fig. S12 and Table S1) were comparable
to UiO-66compD, indicating a non-restricted access to the catalytic
sites after rehydration. It is important to note that the 16 min
half-life of methyl-paraoxon breakdown for UiO-66compD
hyd
is significantly shorter than that for UiO-66D
hyd, suggesting
minimal degradation and high accessibility of surface catalytic
sites in UiO-66compD
hyd. The polymer binder thus appears to
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protect these catalytic sites during thermal treatment, affording
activated composites with significant catalytic activity. As UiO-66 is
known to undergo catalyst poisoning from phosphate products
formed during the hydrolysis of organophosphates,2,21 we found
that the samples were not re-usable. Nevertheless, the highly
catalytically active 3D-printed UiO-66compD
hyd materials were con-
venient to utilize, as they could simply be immersed into a reaction
mixture for organophosphate breakdown, and then removed with
tweezers at the end of the reaction for easy clean up. Therefore,
such materials possess significant potential as easily deployable
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single-use protective composites against organophosphate nerve
agents.
In summary, we have developed a 3D printable UiO-66 ink
whereby UiO-66 itself was used as the rheological modifier,
avoiding the need for additional modifiers such as clay. The
UiO-66 composites were 3D printed via direct ink writing, and
selective thermal degradation of the polymer binder in the
composites allowed recovery of UiO-66 pore accessibility. The
treated composites had a MOF content of 74 wt% and a high
apparent BET surface area of 633 m2 g 1. Lastly, this work
shows the simple deployment of 3D printed UiO-66 composites for
rapid catalytic hydrolysis of nerve agent simulant methyl-paraoxon
and the potential of 3D printed MOF materials for chemical
transformations and catalysis. As this procedure presents a general
method for the incorporation of MOFs into 3D printable inks, the
described methodology opens the way for 3D printing of a large
variety of other MOFs and functional materials.
MRR and JC thank the University of Vienna for start-up
funding. AJY, ESM, AG and LBLG thank the University of Hull
for sponsoring their PhD studies.
Conflicts of interest
There are no conflicts to declare.
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This journal is © The Royal Society of Chemistry 2019