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Cite this: Chem. Commun., 2012, 48, 10642–10644

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Instant MOFs: continuous synthesis of metal–organic frameworks by
rapid solvent mixingw
Miquel Gimeno-Fabra,a Alexis S. Munn,b Lee A. Stevens,a Trevor C. Drage,a
David M. Grant,a Reza J. Kashtiban,c Jeremy Sloan,c Edward Lester*a and
Richard I. Walton*b
Received 22nd June 2012, Accepted 7th September 2012
DOI: 10.1039/c2cc34493a

A continuous flow reactor allows the preparation of porous metal–
organic framework materials with crystallisation induced by rapid
mixing of streams of preheated water and solutions of reagents in
organic solvent: this gives high volume production (132 g h!1) with
crystallite size of the products from nanoscale to micron.
Metal–organic frameworks (MOFs) are extended structures of
metal ions or groups of metals (clusters, chains or sheets)
connected by polydentate organic ligands.1 In many cases they
present architectures with considerable porosity once any
occluded solvent is removed. MOFs are thus attracting intense
interest as highly functionalisable porous hosts to rival zeolites,
with potential applications in fields such as gas adsorption,
storage and sensing;2 catalysis;3 and drug delivery.4 One desir-
able characteristic of MOFs is their ability to adsorb gases such
as CO2, H2 and CH4.5 This makes them interesting industrially,
where they may engender novel approaches to energy applica-
tions and to environmental remediation technologies.6
MOFs are typically synthesised using batch solvothermal
reactions whereby solutions of chemical precursors are mixed
and heated in a vessel, with pressure generated if sealed, for
periods of hours or even days.7 This synthesis approach is
versatile due to the large combination of possible organic
ligands and metal salt precursors, the choice of solvent and
the range of temperatures possible; yet it is not always possible
to control crystal growth since a given material may only
crystallise under certain, precise combinations of reaction
conditions. There have been a number of recent reports of novel
approaches to MOF synthesis that overcome some of the limita-
tions of the simple batch solvothermal approach. This includes
the use of energy sources other than conventional heating,
such as microwaves8 and ultrasound,9 which often give
enhanced crystallisation rates, in some cases allowing some
control over the form of the product, for example, giving
nanocrystals of MOFs. Other methods that may provide
versatile approaches for preparing the materials include electro-
chemical deposition of films,10,11 and direct mechanochemical
reaction in the solid-state,12 which eliminates solvent, thereby
simplifying processing of products. These new methods, how-
ever, are not always applicable to all combinations of metal
precursors and ligand. In this communication we report the use
of a high-throughput, continuous-flow method that allows rapid
synthesis by inducing crystallisation from a stream of dissolved
reagents by rapid mixing with a pre-heated water flow. The
technology has already been proved suitable for the controlled
production of various inorganic nano-materials, such as oxide
particles.13 We herein demonstrate its first use in MOF produc-
tion by study of two porous frameworks that are of importance
for their properties in gas storage and separation.
Fig. 1 shows a schematic of the reactor design. This setup uses
a ‘‘counter current mixing reactor’’,14 consisting of a pipe-in-pipe
concentric arrangement, where preheated water is introduced
through the inner pipe (downflow), meeting the precursor stream
(upflow, injected at room temperature) at the mixing point.

a
Department of Chemical and Environmental Engineering,
University of Nottingham, University Park, Nottingham, NG9 2RD,
UK. E-mail: edward.lester@nottingham.ac.uk;
Tel: +44 (0)115 951 4974
b
Department of Chemistry, University of Warwick, Coventry,
CV4 7AL, UK. E-mail: r.i.walton@warwick.ac.uk;
Tel: +44 (0)2476523241
c
Department of Physics, University of Warwick, Coventry,
CV4 7AL, UK
w Electronic supplementary information (ESI) available: Further
XRD, SEM and TEM analysis, and results of BET and TGA. See Fig. 1 Schematic representation of the continuous synthesis system
DOI: 10.1039/c2cc34493a used for the instant production of MOFs.

10642 Chem. Commun., 2012, 48, 10642–10644 This journal is c The Royal Society of Chemistry 2012
This arrangement facilitates instant, powerful and uniform
mixing of the reactant streams and short residence times. The
final suspension of particles is evacuated through the top of
the reactor; this is then rapidly cooled as it passes through a
water jacket cooler and is collected after a manual back
pressure regulator set to maintain the system at 250 bar.
The first material we consider is the copper(II) carboxylate
HKUST-1. This material has composition Cu3(BTC)2(H2O)"xH2O
(BTC = 1,3,5-benzenetricarboxylate) and has been one of the
most extensively studied MOFs since being reported by Chui
et al. in 1999.15 It presents high chemical stability, high surface
area and pore volume together with coordination properties
towards various adsorbate gases.16 The material was also the first
MOF to be manufactured on an industrial scale, an electro-
chemical process with reaction times of 3 to 12 hours,11 and has
been commercialised under the name of Basolites C300. Powder
X-ray diffraction of a typical as-prepared HKUST-1 product
from the continuous reactorz is shown in Fig. 2, confirming the
high crystallinity and phase-purity of the material, even after a
residence time at the point of reaction of less than 1 s. Batch
synthesis of HKUST-1 is typically performed up to 150 1C,7 but
using a downflow of water at 300 1C allows rapid crystallisation.
The powder X-ray pattern for material prepared at a reaction
temperature of 400 1C, shows collapse to Cu2O, indicating an
upper limit to reaction temperature (see ESIw). SEM images of
the materials prepared at 300 1C show some variation in crystal
size and shape when the dilution and flow rate of the reagents is
changed, Fig. 3, with generally larger crystals seen at lower
dilution. It is noteworthy that the crystal morphology is not
typical of the octahedral crystals usually reported for HKUST-1.7
Reported in situ studies of HKUST-1 crystallisation show
that nucleation occurs instantaneously but continues late into
the crystal growth period;17 indeed a range of crystal sizes are
often formed in samples from batch synthesis, consistent with
the continuous nucleation for crystal growth. We can thus
propose that an advantage of our synthesis lies in the short
period of crystallisation: this prevents reaction before the
heated downflow is encountered and then crystal growth
occurs only at the nucleation sites formed during the residence
at the reaction point. Textural characterisation by N2 sorption
isotherms using a ASAP 2420 instrument show both HKUST
Fig. 2 Profile fit (Fm3% m) to powder X-ray pattern of HKUST-1
sample prepared at 300 1C with 0.03 M Cu2+.
This journal is c The Royal Society of Chemistry 2012
Fig. 3 SEM images of HKUST-1 prepared at 300 1C from reagent
solutions of (a) 0.03 M Cu2+ and (b) with 0.0075 M Cu2+.
Table 1 Textural properties of HKUST-1 and Basolite C300 (Sigma-
Aldrich). Vp is total pore volume at 0.95 p/po, and Vm micropore
volume by t-plot analysis (Harkins and Jura)
Sample BETSA (m2 g!1) Vp (cm3 g!1) Vm (cm3 g!1)
HKUST-1 1950 0.80 0.77
Basolite C300 1694 0.72 0.70
and a commercially available sample of the same composition
(Basolite C300) have Type I isotherms, indicative of micro-
porous materials (see ESIw). Both samples have equivalent
textural properties, Table 1, although our material has BET
and Langmuir surface areas that exceed the commercial
sample and are at the high end of the range of values typically
reported for this material.16 Adsorption studies of other gases
carried by thermogravimetric analysis also indicates that
HKUST-1 has similar adsorption properties and performance
to the commercially available material, with typical CO2
uptake (298 K, 1 bar) of 25% by mass, which compares well
with reported values for samples prepared in batch (ESIw).
The second MOF we studied was the Ni(II) carboxylate
CPO-27.18 This is constructed from edge-shared metal octahedra
linked by 2,5-dihydroxycarboxylate ligands to give an open
structure with B11 Å diameter, one-dimensional channels and
accessible metal sites. The structure is also known for other
metals, including Fe, Co and Zn, and these various forms have
been used in gas storage, e.g., for dihydrogen,18 H2S,19 selec-
tive binding of oxygen over nitrogen,20 and various toxic
gases.21 We effected crystallisation by using a similar approach
as for HKUST: the metal salt (Ni(II) acetate) and organic
linker dissolved in DMF (upflow) and crystallisation induced
by mixing with pre-heated water (downflow).2 Powder XRD,
Fig. 4, of the CPO-27 samples confirms the sample identity.
All peaks in the powder XRD can be indexed on the published
crystal structure18 but there is significant peak broadening due to
small particle size. Scherrer analysis gives 12 nm particle diameter
for the material prepared at the highest concentration of reagents,
and 15 nm for those prepared at the lower dilution. Fig. 5 shows
results of electron microscopy of materials prepared at 300 1C at
two different dilutions of reagents. Nanocrystalline powders are
formed at the highest concentration at 300 1C, but with increasing
dilution at 200 1C, larger, needle-like crystallites are seen, con-
sistent with the morphology seen in batch reactions using various
heating methods (conventional, microwave and ultrasound).22
Even the larger crystals are less than 20 nm in cross section,
consistent with the broadened diffraction profile.
Chem. Commun., 2012, 48, 10642–10644 10643

Fig. 4 Profile fits (R3% ) to powder X-ray diffraction pattern of CPO-
27(Ni) prepared at two different temperatures and dilutions. Note the
effect of particle morphology on preferred orientation.
Fig. 5 Electron microscopy of CPO-27(Ni) (a) HR-TEM of sample
prepared at 300 1C at high concentration. Aligned pores viewed along
[001] are visible at I and detail (I 0 ). FFT of I is inset top left, HR-TEM
simulation and model are inset middle right and bottom. (b) SEM
image of 200 1C sample prepared at lower concentration.
The textural properties of the CPO-27(Ni), as studied by
BET nitrogen sorption analysis, show a typical Type I iso-
therm with a slight mesopore character at high relative pres-
sure (ESIw). A surface area of 1030 m2 g!1 and total and
micropore volume 0.67 and 0.40 cm3 g!1 respectively, are
calculated. A CO2 uptake of 19.57 wt% was measured. These
values match reported data for samples from conventional
synthesis. The method of synthesis we report should be
applicable to a wide range of MOFs, given the scope for
varying solvent or solvent mixtures along with choice of
10644 Chem. Commun., 2012, 48, 10642–10644
organic linker and metal precursors, with the potential for
fine tuning of crystal morphology for scalable production.
Notes and references
z Continuous synthesis of HKUST-1: Downflow: 20 mL min!1 deionized
water (at 100–400 1C). Upflow: 10 mL min!1 benzene-1,3,5-tricarboxylic
acid (4.20 g, 0.03 M, Aldrich) and copper(II) nitrate hemipentahydrate
(4.82 g, 0.03 M, Aldrich). These were stirred for 15 minutes in 660 mL
of solvent consisting of equal parts of N,N 0 -dimethylformamide
(Fluka) and ethanol (Fluka) before being pumped into the system.
Continuous synthesis of CPO-27(Ni): Downflow: 20 mL min!1 deionized
water (at 100–400 1C). Upflow: 10 mL min!1 nickel acetate (3.19 g,
0.15 M, Aldrich) and 2,5 dihydroxyterephthalic acid (1.26 g, 0.075 M,
Aldrich) were dissolved in at least 85 ml N,N 0 -dimethylformamide
(Fluka). In both cases the solid was allowed to settle and the cloudy
concentrate separated by decantation and dried at 70 1C.
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This journal is c The Royal Society of Chemistry 2012