Flow-synthesis of carboxylate and phosphonate based metal-organic frameworks under non-solvothermal reaction conditions

Article abstract of DOI:10.1039/c5dt01100k

A continuous flow reactor was developed for the synthesis of porous metal-organic frameworks (MOFs) under mild reaction conditions. Commodity hardware was used to assemble the device, giving it a great degree of flexibility in its configuration. The use of paraffin to encapsulate reactions and also ultrasonic treatment were employed to prevent clogging of the reactor. Reactor design was optimised through studies of the synthesis of zirconium carboxylate framework UiO-66. Synthesis of the aluminium carboxylate CAU-13 was also performed, to demonstrate the versatility of the device. Finally the reactor was used to synthesise a new cadmium phosphonate framework, bearing the STA-12 network.

Full text of DOI:10.1039/c5dt01100k

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Journal Name
RSCPublishing
ARTICLE
Flow-Synthesis of Carboxylate and Phosphonate
Based Metal-Organic Frameworks Under Non-
solvothermal Reaction Conditions
Cite this: DOI: 10.1039/x0xx00000x
Steve Waitschata, Michael T. Wharmbya,b* and Norbert Stocka*
Received 00th January 2012,
Accepted 00th January 2012
A continuous flow reactor was developed for the synthesis of porous metal-organic frameworks
(MOFs) under mild reaction conditions. Commodity hardware was used to assemble the device,
giving it a great degree of flexibility in its configuration. The use of paraffin to encapsulate
reactions and also ultrasonic treatment were employed to prevent clogging of the reactor.
Reactor design was optimised through studies of the synthesis of zirconium carboxylate
framework UiO-66. Synthesis of the aluminium carboxylate CAU-13 was also performed, to
demonstrate the versatility of the device. Finally the reactor was used to synthesise a new
cadmium phosphonate framework, bearing the STA-12 network.
DOI: 10.1039/x0xx00000x
www.rsc.org/
reaction solvent and thus under increased pressure.
Furthermore, to date there has only been one report of a new
Introduction
Metalꢀorganic frameworks (MOFs) are composed of organic
linkers which join metal ions or clusters, to form networks with
potential porosity.1 The wide diversity of attainable topologies
and the possibility of tuning properties through the addition of
functional groups to the linkers make permanently porous
MOFs candidate materials for applications such as gas storage,2
gas separation,3 drugꢀdelivery4 or heatꢀtransformation.5 Such
applications would however require the preparation of large
quantities of material6 and many MOF syntheses are only
reported as small scale batch reactions. The upscaling of such
batch reactions can be problematic, requiring much time to be
expended on reꢀoptimising the reaction conditions. One method
to produce larger quantities would be to use a continuous flow
reactor.7 Flow reactors are frequently utilized within the field of
organic synthesis,8 especially for the synthesis of peptide &
saccharide oligomers, but also for continuous production of
highꢀvalue pharmaceuticals.9 In inorganic chemistry they have
been extensively used for the synthesis of metal chalcogenide
and oxide nanoparticles,10,11 Flow synthesis of MOFs has been
demonstrated for a select range of frameworks (Tab. S1.1).7,12–
MOF synthesised in a flow reactor, Ce5(BDC)7.5(DMF)4.19
Herein we describe the development of a flow reactor for the
synthesis of MOFs under mild reaction conditions and its
application to the synthesis of the known frameworks,
UiOꢀ6620
([Zr6O4(OH)4(BDC)6],
BDC = 1,4ꢀ
benzenedicarboxylate) and CAUꢀ1321 ([Al(OH)(CDC]·1.5H2O,
CDC = transꢀ1,4ꢀcyclohexaneꢀdicarboxylate). In addition we
were also able to prepare
a
L
new metal phosphonate,
N,N'ꢀ
[Cd2(H2O)2 ]·xH2O (H4
L
=
piperazinebis(methylenephosphonic acid), which is a new
member of the STAꢀ12 family of compounds.22
Experimental
X-Ray Crystallography
Initial characterisation was performed using a Stoe Stadi P
diffractometer fitted with an xyꢀstage, in transmission geometry
using Cu Kα1 radiation and with data collected by an image
plate detector. Powder XꢀRay Diffraction (PXRD) patterns for
Pawley fitting and Rietveld refinement were measured using a
Stoe Stadi P diffractometer in transmission geometry using
Cu Kα1 radiation and with data collected using a Mythen
detector.
Data analysis for all three compounds was performed using the
TOPASꢀAcademic V5 suite.23 The PXRD patterns of all three
compounds were indexed and subsequently Pawley fits were
performed to confirm the unit cell and space groups obtained
from the indexing routine. For STAꢀ12(Cd), the profile
parameters, unit cell and space group were used as the starting
17
HKUSTꢀ1, which readily forms under a wide range of
parameters, has been synthesised in flow under both mild
(p ~ ambient; T = 60°C)12 and more severe (p = 250 bar;
T = 100ꢀ400°C)13 reaction conditions. Syntheses in flow of
other widely studied frameworks, including CPOꢀ27,13
MILꢀ53(Al),7 MILꢀ88B(Fe)17 and UiOꢀ66,15,16,18 have
relatively recently been reported. It should be noted that, with
the exception of MILꢀ88B(Fe) and HKUSTꢀ1, all other flow
synthesis studies were performed under solvothermal reactions
conditions, i.e. at temperatures above the boiling point of the
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point for a Rietveld refinement. STAꢀ12(Mn)22 was used as the mixers, which in the simplest form of the system are either
initial model for the refinement, with Mn2+ replaced by Cd2+. three way Yꢀconnectors or four way Xꢀconnectors. From these
Restraints were applied to all coordinative bonds around the mixers, the solution flows into the reactor itself, a coil of PTFE
Cd2+ ion and also to all bonding distances within the organic tubing immersed in an oil bath for heating. The length and
ligand. After several cycles of refinement of the framework, all internal diameter of this tube, in combination with the total
pore water molecules were removed and new positions pumping rate, determine the reaction time, whilst the molar
determined from Fourier difference maps. Occupancies of these ratio of the reaction is determined by varying the pumping rate
sites were then refined. In the final cycles of refinement, of each pump individually (ESI S3).
framework and water positions were refined together with
isotropic displacement parameters.
Physical Measurements
Infrared spectra were recorded on a Bruker ALPHAꢀP A220/Dꢀ
01 FTIR spectrometer fitted with an ATR unit, over the spectral
range 4000ꢀ40 cmꢀ1. Thermogravimetric analysis was carried
out using a NETSCH STA 429 CD analyser with a heating rate
Fig.1. Schematic of the flow reactor in a two pump configuration, showing the
hotplate and oil bath in which the coil of PTFE tube forming the reactor is
immersed.
of 4 K minꢀ1 and under flowing air (flow rate 75 ml minꢀ1) or a
TA Instruments TGA Q500 with a heating rate of 5 K minꢀ1 and
under flowing air (60 ml minꢀ1). Elemental analysis was
Zirconium Terephthalate UiO-66
Zrꢀbased UiO 66 ([Zr6O4(OH)4(BDC)6]) is one of the most
performed using a EuroVector EuroEA elemental analyser.
NMR spectroscopy was performed using a Bruker DRX 500
spectrometer. Scanning Electron Micrographs were collected
using an FEI Quanta FEG 600 electron microscope, whilst N2
sorption isotherms were recorded at 77 K with a BELSORPꢀ
max apparatus (BEL Japan Inc.).
-
intensively studied MOFs and thus was selected for the initial
test of the reactor. Initial reaction conditions were chosen to
mimic the reported batch syntheses (1:1 ZrCl4:H2BDC, 120 °C,
24 hrs).25 The first attempts utilised a two syringe pump setꢀup,
with one pump loaded with ZrCl4 in DMF and a second
containing H2BDC in DMF (Table 1). However, this design led
to precipitates forming in the tube and clogging of the reactor.
The design was then modified to add a third syringe containing
either DMF or paraffin as a transport medium to prevent
clogging.24 Amounts of solid obtained with the additional DMF
were found to be too low, whilst with paraffin, although more
Results & Discussion
Design of the Flow Reactor
The flow reactor was designed to be easy to set up whilst
having sufficient flexibility to allow a wide variety of reaction
parameters to be investigated, including molar ratios and
heating method (ESI S3). The device is built up from two
syringe pumps, which contain respectively the metal salt and
the organic linker in solution (Fig. 1 and Fig. S3.1). In cases
where the amount of precipitate causes the reactor to block, a
third pump can be added, to pump a transport medium (e.g.
paraffin) to encapsulate the reaction as droplets in flow.24
Additionally an ultrasonic probe can be used to both improve
mixing and also to prevent clogging of the reactor.
solid was recovered, isolation of the UiO-66 product could only
be achieved by repeated washing steps with dichloromethane or
toluene, which resulted in significantly lower yields. BET
surface area values were also found to be significantly lower
than literature values (Table 2). The reactor configuration was
therefore changed again, back to a two pump setꢀup, with an
ultrasonic probe fitted which improves mixing of the reagents
and most importantly prevents clogging of the reactor
(Table 1). Following optimisation of the synthesis conditions,
Solutions are combined by pumping along PTFE tubing to
Table 1. Summary of the reaction conditions tested for the synthesis of UiO-66, using the two syringe (top), three syringe (middle) and two syringe
with ultrasonic probe (bottom) reactor configurations.
H2BDC
Flowrate /
ml min-1
0.281
0.210
0.120
0.140
0.281
0.210
Transporta
Ultra Sound
Cycle Amplitude
Reactor
Volume / ml
ZrCl4 Flowrate /
ml min-1
Flowrate /
Temp. / °C
Time / min
ml min-1
16.87
16.80
14.45
16.83
16.87b
16.80
0.094
0.070
0.040
0.047
0.094
0.070
ꢀ
ꢀ
120
120
120
130
120
120
45
60
45
45
45
60
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
0.161 (Para.)
0.187 (DMF)
ꢀ
ꢀ
0.25
0.25
100 %
100 %
a
A transport medium in addition to the reaction solvent, used to prevent clogging of the reactor.
b
This reaction produced the most crystalline and phase pure UiOꢀ66, which is further analysed in this work. This is equivalent to a reaction ratio of 1:3
(ZrCl4:H2BDC).
2 | J. Name., 2012, 00, 1-3
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highlyꢀcrystalline, phase pure UiOꢀ66 could be obtained using a
molar ratio of 1:3 (Zr4+:H2BDC) at 120°C in just 45 min.
C
HARACTERISATION
The phase purity of the UiOꢀ66 material was confirmed by
Pawley fitting of the laboratory powder Xꢀray diffraction
(PXRD) data. A good fit to the data was obtained, however in
addition to the expected UiOꢀ66 reflections, two symmetry
forbidden reflections were also observed (Fig. 2). These have
been attributed to lower symmetry defect rich regions
incorporated within the perfect UiOꢀ66 structure.26,27
Fig. 2. N2 adsorption and desorption isotherms measured at 77 K on samples of
UiO-66 produced in a two-pump (ultrasonic probe; green & red traces) and
three-pump (paraffin transport; orange & blue traces) flow reactor.
We also provide a comparison of the surface areas of other flow
reactor prepared UiOꢀ66 materials (Table 2). The presence of
defects is potentially beneficial for applications in catalysis.28
Table 2. Comparison of the synthesis conditions and specific surface areas
(aBET) of UiOꢀ66 samples prepared in this work with reported syntheses in
batch and flow reactions.
Fig. 2. Pawley fit of UiO-66 obtained from a flow reactor in a two-syringe
ꢂ
configuration. Cell refined to a = 20.7367(4) Å (space group: ꢀꢁ3ꢁ
;
Rwp = 5.59 %, χ2 = 3.644), consistent with reported lattice parameters.20 Green
Temp. /
°C
120
220
130
Time /
min
1440
1200
10+2days
15
aBET
/
Flow/Batch Zr:BDC:HCl
Ref.
m2 gꢀ1
1187
1105a
1186
1059
arrows indicate forbidden reflections.
20
27
15
16
Batch
Batch
Flow
Flow
1:1:0
2:1:2
1:1:0
1:1:1
Given the low reaction temperature, the presence of defects in
flow reactor prepared UiOꢀ66 is unsurprising. Evidence for
their presence is also found from TGA, EDX and adsorption
experiments. TGA data (Fig S4.3) found a cluster:linker ratio of
1:3.5, significantly lower than the ideal 1:6 ratio of perfect
UiOꢀ66.27 Defects have previously been linked to lower thermal
stability of UiOꢀ66, however TGA data (Fig. S4.3) indicate our
material is stable to in excess of 400°C. Samples of the material
were activated for adsorption measurements (220°C,
p < 10ꢀ2 kPa, 12 hrs) and these were found by elemental
analysis to still contain nitrogen, which may indicate that
missing linker sites are partially occupied by DMF molecules.25
Chloride ions occupying these sites has also been suggested,
and EDX measurements indicate the presence of up to 2
chloride ions per zirconium in our sample.27 The presence of
defects in the structure influences the BET surface area
(1263 m2 gꢀ1), which is significantly higher than the surface
area of the defectꢀfree compound (1125 m2 gꢀ1).27
140
This
work
Flow
1:3:0
120
45
1263
a This is the maximum aBET expected for the ‘ideal’ framework.
Aluminium Cyclohexanedicarboxylate CAU-13
To demonstrate the versatility of the flow reactor setꢀup for the
preparation of a variety of different MOFs, the synthesis of
CAUꢀ13 ([Al(OH)(CDC]·1.5H2O) was investigated.21 The
reported batch synthesis of CAUꢀ13 is performed using a 1:1
AlCl3·6H2O:H2CDC molar ratio, and a 4:1 (vol.) DMF:water
mixture, which is heated at 130°C for 12 hours. As these
conditions would lead to a buildꢀup of pressure, the synthesis
was modified to use pure DMF as the solvent (Tab. S5.1). A
two syringe pump setꢀup was again chosen. One syringe was
loaded with a 0.5 M AlCl3·6H2O in DMF solution and a second
with a 0.5 M H2CDC and 4.5 M acetic acid in DMF solution.
Acetic acid was added to act as a modulator, to favour the
formation of the ꢀ{AlꢀOꢀAlꢀO}ꢀ chains. Using a temperature of
130°C and a reaction time of 20 min, it was possible to prepare
microcrystalline CAUꢀ13.
C
HARACTERISATION
Phase purity was confirmed by Pawley fitting of the PXRD
pattern (Fig. 3), with CAUꢀ13 crystallizing in its open form.
TGA and elemental analysis results were consistent with the
reported CAUꢀ13 composition and the BET surface area was
slightly higher than reported (measured: 401 m2 gꢀ1; reported:
378 m2 gꢀ1) (Fig. 4 and ESI S5.7).
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Beyond optimization and scaled up synthesis, the flow reactor
setꢀup is well suited for the discovery of new compounds.
STAꢀ12 is a porous metal phosphonate framework, obtained
with a wide range of divalent metal cations (e.g. Mg, Mn, Fe,
Co, Ni),22 however it remains unknown with Cd2+. STAꢀ12 is
usually synthesized with a metal to ligand ratio of 2:1 and using
reaction conditions of 160ꢀ220°C for 18ꢀ72 h in water.
Alternative reaction conditions were needed for the synthesis
using the flow reactor, as under these hydrothermal conditions,
high pressures would be developed. At lower temperature
however, the linker, N,N'ꢀpiperazinebis(methylenephosphonic
Fig. 3. Pawley fit of CAU-13 obtained from a flow reactor in a two-syringe
configuration. Cell refined to a = 6.6111(4) Å, b = 9.4498(6) Å, c = 9.4652(5) Å,
acid) (H4
L), is insoluble in water. To overcome this problem,
ꢂ
α = 107.652(4)°, β = 107.690(6)° and γ = 93.185(5)° (space group: ꢃ1
;
H4 was neutralized with KOH to form its soluble sodium salt.
L
Rwp = 4.71 %, χ2 = 1.080), consistent with reported lattice parameters.21
A 0.1 M aqueous solution of this was loaded into one syringe of
a two syringe pump setꢀup, whilst the other syringe was
charged with a 0.1 M metal solution. Reaction conditions,
determined from studies of the known compounds STAꢀ12(Co)
and STAꢀ12(Ni), were carried out by screening the reaction
temperature, time and metal to linker ratios (ESI S6, Tab. S6.1
and S6.2).20,26 The best conditions are a reaction temperature of
70°C and a M:L ratio of 1:2 for STAꢀ12(Co) and 1:1 for
STAꢀ12(Ni). For the synthesis of STAꢀ12(Cd) the parameters
of STAꢀ12(Ni) were chosen and an aqueous solution of
Cd(AcO)2·2H2O was used. The reaction time was varied
between 5ꢀ20 min by controlling the total pumping rate
(Tab. S6.3). Crystallinity increases with greater residence time
(up to 15 min – Fig. 5).
To confirm this slight increase in BET surface area was due to
the presence of defect sites, occupied by acetic acid modulator
from the synthesis, a sample of CAUꢀ13 was digested in base
and analysed by solution state NMR. No additional resonances
were observed in the spectra (Fig. 4) and thus no additional
acetic acid molecules are thought to be incorporated, in
agreement with the elemental analysis.
Fig. 4. N2 adsorption isotherm measured for CAU-13 – aBET = 401 m2 g-1. Inset
shows the solution state 1H NMR spectrum of CAU-13; only resonances
attributable to H2cdc were identified and thus no acetic acid was incorporated.
Fig. 5. Samples of STA-12(Cd) prepared in the flow reactor with reaction times
increasing from 5 to 20 minutes. Dashed box indicates the (140) reflection, which
narrows with increasing reaction time, indicating an increase in particle size.
Synthesis Scaling
C
HARACTERISATION
Once the reaction is running, the space time yield for syntheses
of UiOꢀ66 and CAUꢀ13 is 428 kg mꢀ3 dꢀ1 (yield: 194 mg, 87%)
and 3049 kg mꢀ3 dꢀ1 (yield: 615 mg, 53%), respectively.
Although in this study only product amounts of 200ꢀ600 mg per
synthesis were obtained, this setꢀup can be used in principle for
obtaining larger amounts by running the flow synthesis in a
steady state for a longer period of time.
The final product was analysed by PXRD and the structure was
confirmed by Rietveld refinement (Fig. 6, left); the final
refinement gave Rwp = 6.43 %, RBragg = 1.56 % and χ2 = 1.141
(Tab. S6.4). STAꢀ12(Cd) was refined in a trigonal unit cell in
ꢂ
the space group ꢄ3 and unit cell parameters of
a = b = 27.4100(8) Å c = 6.7279(2) Å. The structure consists of
helical Cd2+ phosphonate chains, parallel to the
cꢀaxis, bridged
by piperazinyl linker units, which coordinate the Cd2+ ions
Cadmium Phosphonate STA-12(Cd)
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through the N atoms (Fig. 3, right). The structure differs characterisation of the title compounds, crystallographic data of
slightly from previously reported STAꢀ12 frameworks in that STAꢀ12(Cd). See DOI: 10.1039/c000000x/
the piperazinyl ring plane is in the cꢀdirection, whereas in other
structures it is perpendicular.22 STAꢀ12(Cd) is porous to N2
(Fig. S6. 8), with a pore volume of 0.08 cm3 gꢀ1 and a BET
surface area of 134 m2 gꢀ1. N2 uptake is lower than the Co2+ and
Ni2+ compounds, which is partly attributed to the greater mass
of the framework forming cation.
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2
3
4
5
6
7
8
9
Conclusions
We have developed a highly flexible and easy to set up flow
reactor system for the preparation of porous MOFs under mild
(i.e. subꢀsolvothermal) conditions, using commodity hardware.
Using this device we have demonstrated the synthesis of three
MOFs: two reported metal carboxylate compounds (UiOꢀ66
and CAUꢀ13) and
a
new porous metal phosphonate
F. Lévesque and P. H. Seeberger, Angew. Chem. Int. Ed., 2012, 51,
1706–1709.
(STAꢀ12(Cd)), the structure of which was confirmed by
Rietveld refinement. All three compounds are porous to N2 gas,
and UiOꢀ66 shows a higher than expected BET surface area,
attributed to defects, which may make it interesting for catalytic
applications. The flow reactor design should allow simple and
cheap scaleꢀup of the syntheses of all three MOFs, making its
development significant for industrial applications of this class
of compounds.
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Acknowledgements
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SEM images; Achim Fölster (CAU, Kiel) is thanked for for the
preparation of Figure 1.
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Notes and references
a
Institute für Anorganische Chemie, Christian-Albrechts-Universität,
20 J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga
and K. P. Lillerud, J. Am. Chem. Soc., 2008, 130, 13850–13851.
21 F. Niekiel, M. Ackermann, P. Guerrier, A. Rothkirch and N. Stock,
Inorg. Chem., 2013, 52, 8699–8705.
Max-Eyth-Straße 2, D 24118 Kiel, Germany
b
Diamond Light Source Ltd., Diamond House, Harwell Science and
Innovation Campus, Didcot, Oxfordshire, OX11 0DE, United Kingdom
22 M. T. Wharmby, G. M. Pearce, J. P. S. Mowat, J. M. Griffin, S. E.
Ashbrook, P. A. Wright, L.ꢀH. Schilling, A. Lieb, N. Stock, S. Chavan,
† Electronic Supplementary Information (ESI) available: description of
the flow reactor system, in depth description of the synthesis and
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VJieowuArrtnicalelONnlainme e
DOI: 10.1039/C5DT01100K
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Table of Contents Figure
Development of a flow reactor for facile subꢀsolvothermal
synthesis of MOFs.
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