Article

pubs.acs.org/crystal

Electrochemical Synthesis of Some Archetypical Zn2+, Cu2+, and Al3+

Metal Organic Frameworks
Alberto Martinez Joaristi, Jana Juan-Alcañiz, Pablo Serra-Crespo, Freek Kapteijn, and Jorge Gascon*
Catalysis Engineering, Chemical Engineering Department, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The
Netherlands
*
W Web-Enhanced Feature *
S Supporting Information

ABSTRACT: Several archetypical metal organic frameworks (MOFs),

namely, HKUST-1, ZIF-8, MIL-100(Al), MIL-53(Al), and NH2-MIL-53(Al),
were synthesized via anodic dissolution in an electrochemical cell. The
influence of different reaction parameters such as solvent, electrolyte, voltage−
current density, and temperature on the synthesis yield and textural properties
of the MOFs obtained was investigated. The characterization of the samples
involved X-ray diffraction, gas adsorption, atomic force microscopy, diffuse
reflectance infrared Fourier transform spectroscopy, and scanning electron
microscopy. In the present article, we demonstrate that electrochemical
synthesis is a robust method offering additional degrees of freedom in the
synthesis of these porous materials. The main advantages are the shorter
synthesis time, the milder conditions, the facile synthesis of MOF
nanoparticles, the morphology tuning and the high Faraday efficiencies. The
synthesized MIL-53 and NH2-MIL-53 samples exhibit suppressed framework flexibility compared to samples synthesized
solvothermally.

S ynthetic crystalline micro- and mesoporous materials have

been extensively researched during the last few decades.
They have applications in many different fields such as catalysis,
adsorption/separation/storage, electronics, health, semiconduc-
tors, the food industry, and in detergents.1 Several unique aspects
of these materials are responsible for their success: since they
have a very high and tunable adsorption capacity, active sites of
different strengths can be generated in the frameworks, the size of
their channels and cavities falls within the range of that of many
molecules of interest, and many materials present excellent ion
exchange capabilities and exciting electronic properties, ranging
from insulators to conductors and semiconductors.2,3 In
addition, owing to their periodic nature, these materials are
excellent playgrounds for scientists, since macroscopic events
may be explained on the basis of interaction at the molecular
level.
Among the different classes, metal organic frameworks
(MOFs) bridge micro- and mesoporous materials and present
unprecedented topological richness. The combination of organic
and inorganic building blocks offers an almost infinite number of
combinations, enormous flexibility in pore size, shape, and
structure, and plenty of opportunities for functionalization,
grafting, and encapsulation. These materials hold very high
adsorption capacities, specific surface areas, and pore volumes.
Their porosity is much higher than that of their inorganic
counterpart zeolites (up to 90% higher). Their thermostability is
sometimes unexpectedly high, reaching temperatures above 400
°C. Obviously, MOFs have attracted much attention, the major
studies have dealt with the synthesis of new structures,4 and most
applications have focused on adsorption/separation,5−7 storage,8
and catalysis.9
When it comes to the synthesis of porous materials, high
temperature and extreme pH conditions are usually needed to
overcome the frequently high enthalpies of formation and/or to
account for the slow kinetics of nucleation.10 Moreover, when
thinking of the application and functionalization of these
materials (i.e., the incorporation of active organo-molecules via
encapsulation11,12 or the synthesis of coatings),13 extreme
synthetic conditions constitute a tremendous drawback. In this
regard, biomimetic synthesis of crystalline inorganic frameworks
at room temperature and neutral pH has been demonstrated to
work. Morse and his co-workers14 showed that silicateins
involved in the biomineralization of sponge silica spicules are
able to catalyze in vitro the formation of silica and amorphous or
partially crystallized, nonbiological inorganic materials (titanium
dioxide, titanium phosphates, gallium oxohydride, and gallium
oxide). Later, Corma’s group showed that simple molecules such
as tromethamine, cysteamine, and ethanolamine, functional
mimics of the protein silicatein α, act as catalysts for the synthesis
of Si-based molecular sieves at neutral pH and at room
temperature.15
Although it is possible to synthesize large MOF crystals under
certain mild synthetic conditions and to accelerate their
precipitation by creating changes in the pH/solvent at room
Received: January 6, 2012
Revised: May 25, 2012
Published: May 30, 2012

© 2012 American Chemical Society 3489 dx.doi.org/10.1021/cg300552w | Cryst. Growth Des. 2012, 12, 3489−3498
Crystal Growth & Design
temperature,16 in the case of certain applications and for the sake
of the fast and reproducible synthesis of large amounts of
homogeneous samples, the development and understanding of
new mild and rapid synthetic methods allowing continuous
production is still imperative. Three different alternatives have
been proposed: Son et al., who applied sonochemical methods,
concluded that ultrasound can lead to homogeneous nucleation
and to a substantial reduction in crystallization time compared to
conventional oven heating in the synthesis of MOF-5.17 Pichon
et al. demonstrated that mechanochemical, solvent-free synthesis
of a Cu-based MOF is possible when ball-milling the framework
precursors.18 Finally, using a different approach, BASF pioneered
the electrochemical room temperature synthesis of the well-
known HKUST-1.19 Electrochemical synthesis facilitates metal
salt-free and continuous production, which is a major advantage
in any industrial environment. The principle relies on supplying
the metal ion by anodic dissolution to a synthesis mixture that
contains the organic linker and an electrolyte (see Figure 1).
Figure 1. Schematic view of an electrochemical synthesis cell. Legend:
WE = working or indicating electrode (red) GND = ground connection,
protecting earth (green) RE = reference electrode (blue) CE = auxiliary
or counter electrode (black) S = sense electrode.
Despite the promising features shown by the electrochemical
method, only Hartmann et al.,20 Ameloot et al.,21 and more
recently Li and Dinca22 have employed this synthetic approach.
In the first case, HKUST-1 crystals were used in the adsorptive
separation of butene from isobutene, and later electrochemical
synthesis was used to manufacture high quality patterned
coatings of HKUST-1 on copper electrodes.21 In the last
example, electroreduction of oxoanions was shown to afford
hydroxide equivalents that induce the selective deposition of
MOF-5 on conductive Zn surfaces used as cathodes.22
In this work we present a detailed study of the main
experimental variables governing the electrochemical synthesis
of MOFs based on different metals (Cu, Zn, and Al) and linker
connectivities (bi- and tridentate carboxylic acids and
imidazoles), together with a critical assessment of the main
advantages and limitations of the method.
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2. EXPERIMENTAL RESULTS
2.1. General Considerations about Electrochemical Syn-
thesis. As was already anticipated by Müller and his co-workers,19,23
electrochemical synthesis of MOFs can be performed in batch mode or
in continuous flow operation. In the case studies presented in this paper,
the experiments were performed in batch mode. In electrochemical
synthesis, the metal ion is not supplied as salt but by oxidation of the
electrode. The energy required to oxidize the anode can be supplied in
amperometric or potentiometric mode. In the first case the voltage is
fixed and current can be used to measure the reaction rate expressed as
the speed at which the metal ions are dissolved. In potentiometric mode,
the current through the cell is fixed and variations in voltage are related
to the energy needed to dissolve the electrode. Both methods can be
applied continuously over time and in wave or square functions.
A general advantage of electrochemical synthesis is that it allows
synthesis under milder conditions than typical solvothermal or
microwave synthesis. It also reduces the time required for certain
synthesis: whereas solvothermal synthesis might take hours or days,
electrochemical methods can produce the material within minutes or
hours. Electrochemical synthesis allows more control to be exercised
over the reactant concentration in the synthesis over the course of time
since it is performed without building pressure and so not only the metal
can be added at different rates by controlling the anodic oxidation, but
the linker can also be continuously added to the solution. In addition, it
should be possible to carefully control the oxidation state of the metal
simply by adjusting the voltage provided to the electrode.
Several key points have to be carefully considered in the
electrochemical cell configuration, as presented below. The main
drawback with the electrochemical synthesis of MOFs is that in order to
dissolve the organic building blocks, organic solvents are frequently
needed, while little is known about the electrochemistry of such media.
Moreover, organic solvents display a higher resistivity than aqueous
solutions, and while it is clear that oxidation of the metal takes place at
the anode, it is not easy to understand the chemical processes or
processes taking place at the cathode of the cell. The physical location
and orientation of the anode and cathode and the use of the appropriate
reference electrode and/or potential therefore become crucial. It is also
convenient to use a corrosion cell when conducting fundamental studies
on metal oxidation in organic solvents.24
Reference electrodes can be used, but standard commercial
electrodes use a saturated KCl solution, and KCl is not soluble in
most organic solvents. To overcome this limitation, the reference
electrode can be connected to the synthesis solution by a glass frit or a
Luggin capillary that will only allow through it a very slow diffusion of
water or solvent. When this approach is followed in prolonged
experiments, a high junction potential difference is likely to develop in
the glass frit which, in combination with the low conductivity of the
organic solvent, will make it very difficult to correlate the voltage applied
with theoretical data. Li et al.22 used a Ag/Ag(cryptand)+ as a reference
electrode in the reductive electrosynthesis of MOF-5. Other reference
electrodes for organic solvents can be found elsewhere.24−27
Another matter of concern is the limitation of standard reference
electrodes for organic solvents at relatively high temperatures (>60 °C).
In this paper, we have optimized reference voltages for a given
electrochemical cell geometry. When a reference electrode was used,
Ag/AgCl was chosen because of its broader application temperature
range (−5−110 °C).28
Current distribution along the cell is the next factor to consider. It is
important that the cell geometry leads to uniform current distribution,
especially during the synthesis of thin MOF films. When no reference
electrode is used, it is strongly recommended to maintain a constant
distance between electrodes, since the current−voltage is determined by
the cell geometry. Ideally, the cathode and the anode should be
separated by a porous glass so that the products from the cathode do not
affect the MOF synthesis at the anode; however, if the system
conductivity is too low, this might not be possible.
Because of the likely production of H2 at the cathode, electrochemical
cells in aqueous solutions are usually equipped with a nitrogen bubbler
in order to deaerate the solution and avert the formation of explosive
dx.doi.org/10.1021/cg300552w | Cryst. Growth Des. 2012, 12, 3489−3498
Crystal Growth & Design
atmospheres. Many organic solvents are too volatile to be deaerated. In
many cases, the presence of water is even desired to increase
conductivity, for counter electrode reaction, and even for the synthesis
of metal species in solution prior to MOF synthesis. Ideally both the
water and the organic solvent should be deaerated before being used and
mixed in the corresponding amounts before the reaction. In addition, in
view of the temperatures at which syntheses take place and the volatility
of the organic solvents, the use of a reflux condenser is strongly
recommended.
Because of the low conductivity of the reaction media, electrolytes
that enhance charge transport in solution need to be used.
Tributylmethylammonium methyl sulfate (MTBS) has been recom-
mended for syntheses carried out in organic media.29 As already
mentioned above, organic solvents, water, and the electrolyte itself may
be involved in the reduction reactions that take place at the
counterelectrode. It is therefore important that the counterelectrode
has a larger surface area than the working electrode: (i) in order to avoid
rate limiting reactions at the counterelectrode and (ii) to minimize the
effect of products from the cathodic reaction on the synthesis at the
anode.
The electrochemical cell used in this study has been designed in such
a way that the electrodes are supported by PTFE holders, which only
allow contact with the synthesis solutions through a circular opening of
25 mm in diameter. In this way, the exposed electrode surface and the
current densities can be controlled. No reference electrode is used unless
otherwise stated. Counter electrodes are stainless steel gauze electrodes
so as to increase the surface area and to ensure that the counter electrode
reaction does not limit the overall process. Following the ohmnic drop
law:30
S promote the formation of Cu2O.32,40 Because of the low temperatures
ΔV = IR = I
aC (1)
where ΔV is the voltage difference in V, I is the current in A, R is the
resistance in ohm, S is the distance between the electrodes in cm, a the
area in cm2, and C the conductivity of the solution in S cm−1; the
expected voltage required to send 50 mA through a solution of 1 mS
cm−1 conductivity is 30.56 V. The voltages used range from 2 to 30 V
(the maximum ΔV from our system is 35 V) and the current intensities
range from 1 to 20 mA/cm2.
Our cell configuration and agitation allow us to reach ca. 30 V by
passing 50 mA with a conductivity of only 530 μS cm−1 (Figure S1,
Supporting Information).
2.2. Case Study I: Electrochemical Synthesis of HKUST-1.
Copper benzene tricarboxylate was first reported in 1999 and named
HKUST-1.31 Since then, it has become one of the most studied MOFs.
It is frequently prepared under hydrothermal conditions with a copper
salt (usually nitrate) and 1,3,5-benzenetricarboxylic acid (BTC). The
precursors are dissolved and mixed in mixtures of ethanol (EtOH) and
water, and finally synthesized at temperatures between 25 and 80
°C,31,32 although synthesis at room temperature is also possible.33 It was
also the first MOF to be electrochemically synthesized.19,23
The nucleation and crystallization of HKUST-1 have been studied by
means of dynamic light scattering,34 atomic force microscopy (AFM)35
and X-ray diffraction.36,37 It was concluded that crystallization is
dominated by homogeneous nucleation and growth, with continuous
nucleation during all syntheses at all the temperatures studied. The
initial formation of nuclei is effectively instantaneous without induction
time. The activation energy for nucleation is 71.6 kJ mol−1, whereas the
activation energy for crystal growth is 63.8 kJ mol−1.37 Looking at the
relationship between cell potential and Gibbs free energy:30
ΔG = − nF ΔV (2)
−
where n is the moles of electrons transferred (6 mol e per mol of
Cu3(BTC) 2); F is the Faraday constant (96485 C mol−1 e−); and V is
the cell potential. For a standard value of 30 V in the cell, ΔG = −17.4 MJ
mol−1.
So, to overcome the nucleation activation energy of 71.6 kJ mol−1,
only 0.124 V are necessary.
The main limitation for the formation of HKUST-1 is the linker
solubility (∼3 g/L in 96% ethanol at room temperature). Increasing the
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temperature simultaneously increases the solubility and the synthesis
yield. In order to limit the influence of linker concentration during
electrochemical synthesis, a saturated solution of the linker and an
electrolyte is put in contact with two copper electrodes. By applying a
given current, the Cu in the electrode is oxidized to Cu2+ in the solution.
The rate of formation of HKUST-1 is rather high, and it already takes
place in the double layer around the electrode where thin MOF films are
formed (see video as a web enhanced object).21 The current density can
be used to control the amount of Cu2+ present in the double layer, and
therefore the formation of HKUST-1 crystals close to (or directly on)
the surface.
(a). Influence of Solvent. The ethanol−water ratio not only affects
linker solubility, but also solution conductivity and the deprotonation of
the BTC acid. The lower the ratio is, the higher the conductivity will
be,and the higher the ratio is, the higher the solubility and the
deprotonation will be.38 In order to produce HKUST-1, the ethanol
content must be above 75 vol%. If less ethanol is present, a different
coordination polymer called catena-triaqua-mu-(1,3,5-benzenetricar-
boxylate)-copper(II) is formed.13,39 Figure S2, Supporting Information
shows the influence of the water content on the morphology of the
products. At low ethanol content,the formation of other phases is
promoted.
(b). Influence of Temperature. Better solubility at a higher
temperature yields higher linker concentration. As the synthesis occurs
at atmospheric pressure, the temperature is limited by the boiling point
of the solvent or the solvent mixture. In the case of HKUST-1
synthesized in EtOH/H2O mixtures, due to process and safety reasons,
the higher synthesis temperature was 80 °C. Under hydrothermal
conditions, temperatures above 120 °C have been reported which
used in this synthesis, no Cu2O was observed, as was the case with the
room temperature synthesis previously mentioned.33 Standard synthesis
solutions of 15 mmol (3.15 g) of BTC and 33 mmol (1.038 g) of MTBS
dissolved in 100 mL 96%v/v EtOH are heated to three different
temperatures in contact with two copper electrodes separated by 3 cm.
Then, 50 mA are passed through the system for 1 h. On average ∼100
mg of dried HKUST-1 is obtained from each synthesis, showing low
temperature influence in the synthesis yield. We speculate that in the
case of HKUST-1, the synthesis velocity is clearly limited by the
dissolution and diffusion of the metal and linker. The XRD patterns of
Figure 2. XRD patterns (Co-Kα radiation) of samples electrochemically
synthesized at different temperatures compared to the simulated pattern
of HKUST-1. N2-BET surface areas (calculated between 0.01 and 0.05
p/p0) are indicated for each sample.
the reaction products are shown in Figure 2. The patterns fit in very well
with the theoretical calculated pattern, and the calculated surface areas
correspond well with those given in the literature (BET area = 1400 m2/
g, pore volume = 0.6 cm3/g).31,32 No Cu2O is observed. Scanning
electron microscopy micrographs show a wide distribution of sizes in the
resulting HKUST-1 powder. The crystal sizes range from several
hundred nanometers to several micrometers (Figure S3, Supporting
Information). Because of the fast formation of HKUST-1, it is
dx.doi.org/10.1021/cg300552w | Cryst. Growth Des. 2012, 12, 3489−3498
Crystal Growth & Design Article

reasonable to argue that large crystals are formed on the surface of the
electrode, while small crystals are directly formed in solution.
(c). Influence of Conductivity and Current Density on Kinetics. By
controlling the current density, the Cu2+ concentration close to the
electrode can be tuned. However, current density and voltage are
interrelated through the system geometry and the solution conductivity.
A standard synthesis solution with 15 mmol of BTC and 33 mmol of
MTBS in 100 mL of 96%v/v EtOH displays a conductivity of ca. 530
μS/cm. By increasing the electrolyte concentration 5 and 15 times,
conductivity can be increased to 1.86 and 3.6 mS/cm, respectively.
Increasing conductivity improves the yield because less energy is thus
required to overcome the ohmnic drop in the solution and can therefore
be used to dissolve the electrode. As expected, higher conductivity
results in higher yield. The high impact of the ohmnic drop is remarkable
because a 3.5 times increase in conductivity only increases the yield by a
factor 1.6; and a 7 times increase in conductivity only increases the yield
by a factor of 2.

Table 1. The HKUST-1 Yield for a System with 15 mmol BTC

in 100 mL of 96% v/v Ethanol and Different Amounts of
electrolytea
current conductivity time Faraday productivity
[mA] [mS/cm] [h] efficiencyb (%) [mg/h]
50 0.530 1 37 103 ± 20
50 1.860 1 57 160 ± 25
50 3.670 1 68 215 ± 25
a
Syntheses were performed at 40°C. bFaraday efficiency is determined
with ±10% accuracy.

(d). Influence of the Current Density on the Anodic Deposition of

HKUST-1. To study the influence of the current density on the electrode
surface, a corrosion cell was used. It was only after a short period of time Figure 3. SEM micrographs of the HKUST-1 layers obtained on top of
that HKUST-1 crystals formed on the electrode. Figure 4 shows the copper electrodes under different electrochemical conditions. EtOH/
electrode surface of systems where the same number of Faradays have H2O 75:25 vol%. 3.15 g (15 mmol) of BTC and 1 g (33 mmol) of MTBS
been applied at varying current densities. Unlike with nucleation theory, per 100 mL solution. (a) 30 mA/cm2 60 s; (b) 10 mA/cm2 200 s; (c) 3
higher current density does not lead to a large number of nuclei and mA/cm2 600 s; (d) 30 mA/cm2 33 s; (e) 10 mA/cm2 100 s; (f) 1 mA/
small crystals.13 cm2 1000 s; (g) 5 mA/cm2 5 s, 0 mA/cm2 5 s; (h) 10 mA/cm2 5 s, 0 mA/
A formation of HKUST-1 films directly on the surface of the cm2 5 s; (i) 0.5 V/5 s; 0 V/5 s.
electrode via electrochemical synthesis is also possible. At the beginning
of the experiment, when fresh copper electrode is available and exposed
to the synthesis solution, the formation of the MOF layer takes place at
the electrode. As the synthesis continues, new crystals grow on the
uncovered metal surface. As the electrode surface is fully covered, the
HKUST film thickens, and the charge transfer and transport of both
Cu2+ and the linker become more difficult. If a complete film of about 10
μm is formed (one or few crystals of wide film), further dissolution of
copper would cause the MOF film to detach and the new electrode
surface would be available for further reaction. A video of a synthesis in
the corrosion cell showing the quick formation of HKUST-1 crystals on
the surface of the electrode is available.
When square wave functions are used to control Cu2+ release (Figure
3), the best results are obtained in terms of electrode coverage. In this
way the inhibiting effect of concentration polarization is alleviated. In
experiments performed for the same period of time, it was observed that
low current densities result in a large number of small crystals (Figure 3). Figure 4. AFM micrographs of HKUST-1 coatings synthesized using
Ex-situ AFM studies (Figure 4) confirmed this observation. In addition, different current densities after 60 s. The areas represented are 5 × 5
terrace-like crystal growth was observed in the [111] direction, similar to μm2.
in solvothermal synthesis.35
2.3. Case Study II: Electrochemical Synthesis of ZIF-8. ZIF-8 crystals are obtained after some minutes, and the change of crystal shape
was first reported by Huang et al.41 and a more efficient solvothermal from cubes to rhombic dodecahedra only occurs in later stages of
synthesis was described by Park et al.42 ZIF-8 has proven to be one of the growth. By XRD analysis it was deduced that ZIF-8 crystallinity
easiest MOFs to be synthesized. Cravillon et al.43 reported rapid room- increases slowly at short synthesis times (<20 min). Contrary to
temperature synthesis in methanol (MeOH), and recently Pan et al.44 HKUST-1, ZIF-8 requires an incubation time prior to nucleation (∼10
reported its synthesis in aqueous solution. The different stages in ZIF-8 min at RT). This hampers ZIF-8 growth directly on the electrode,
formation (nucleation, crystallization, and growth) have been studied by resulting in the formation of ZIF-8 in the solution and never at the
X-ray diffraction (XRD)45 and small-angle X-ray scattering.46 In the electrodes.
latter case, an excess of the ligand is used (in a similar way to the situation ZIF-8 could be electrochemically synthesized at temperatures as low
close to the electrode that produced Zn2+ ions). Nanometer-size cubical as 0 °C. In this case the linker, methyl imidazolate (MeIM), is soluble in

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a variety of solvents, making the synthesis possible not only in DMF, but particle size or morphology: BET areas around 1500 m2/g and pore
also in MeOH, EtOH, or water. This variety of solvents also allows for volumes of ca. 0.6 cm3/g have been calculated in all cases. Surprisingly, at
the use of different electrolytes such as Na2SO4, KNO3, or KCl, and, in low temperatures a higher production rate is obtained and ZIF-8 can be
all cases, successful synthesis. The main difference is the energy invested formed even at 0 °C (Figure S4, Supporting Information).
in anodic dissolution, since the conductivities from the different (c). Influence of Current Density. It is the large possible variety of
solutions vary between 0.5 mS/cm for 0.3 M MTBS in EtOH and 12.9 solvents that can be used in the synthesis of ZIF-8 that allows high
mS/cm for 0.1 M KCl in H2O. conductivities to be achieved and large ohmnic losses to be avoided, as
(a). Influence of the Solvent. Similar to HKUST-1, the nature of the exemplified in the system 30 vol% AcN in H2O (9.70 mS cm−1). Unlike
solvent will affect the linker solubility and the solution conductivity. with the synthesis of HKUST-1, in the case of ZIF-8 the productivity
Furthermore, it has been observed that nucleation in DMF takes longer increases linearly with current (Figures 6 and S5, Supporting
than in MeOH.43 Organic solvents required the use of an organic Information).
electrolyte, and in this case MTBS was chosen. A solution of 0.033 M
MTBS has a conductivity of ca. 150 mS cm−1 in DMF, 500 mS cm−1 in
EtOH, or 2 mS cm−1 in H2O. Although synthesis in pure water is
possible, the combination of water with an organic solvent considerably
improves the synthesis thanks to the higher solubility of the linker in
organic solvents. A solution of 0.1 M KCl in 30 vol% acetonitrile (AcN)
in water has a conductivity of 9.7 mS cm−1. Using organic solvents as
well as mixtures of water with organic solvents results in pure ZIF-8,
whereas using a system with H2O−KCl as the solvent−electrolyte

Figure 6. The effect of current on the production rate of ZIF-8.

Experiments performed in H2O/AcN 70:30 with KCl as electrolyte at 5
°C. The electrode surface area was 4.9 cm2.

2.4. Case Study III: Electrochemical Synthesis of MIL-100 (Al).

The MIL-100 structure is built up from trivalent metal oxide clusters
coordinated by benzene tricarboxylates. This extended MTN structure
type MOF contains meso-cages of 25−29 Å connected through
Figure 5. XRD patterns of ZIF-8 samples prepared in different solvent− microwindows of 5−9 Å.47 Although the iron and chromium forms of
electrolyte systems. MIL-100 can easily be hydrothermally synthesized,48,49,49 MIL-100(Al)
crystallizes only within a very narrow pH range (0.5−0.7) after heating a
mixture of aluminum nitrate, trimethyl 1,3,5-benzene-tricarboxylate
results in fewer crystalline products (Figure 5). Although conductivity (Me3btc), nitric acid, and water at 210 °C for 3.5 h.47 The fact that acidic
plays an important role in Faraday efficiency and the amount of material pHs are needed makes the translation of batch synthesis to
electrochemical synthesis rather challenging, since H2 production at
Table 2. ZIF-8 Syntheses Results at 25°C in Different Solvents high proton concentrations results in an increasing pH during the
synthesis and in the precipitation of the linker (in the form of an ester)
solvent/ after a few reaction minutes.
electrolyte current conductivity Faraday productivity In view of these preliminary results, a thorough synthesis screening
system [mA] [mS/cm] efficiencya (%) [mg/h] was carried out using BTC in its acidic form and neutral pH. As in the
DMF/MTBS 50 3.45 81 250 case of hydrothermal synthesis, the window of operational conditions
H2O-AcN/KCl 50 9.70 60 170 under which pure phase is formed was also narrow. MIL-100(Al) could
MeOH/MTBS 50 1.84 56 159 only be formed in ethanol−water mixtures = 75−25 v/v% and at
H2O/MTBS 50 2.0 35 105 temperatures above 60 °C with two aluminum electrodes separated by 3
cm, and a current density of 10 mA/cm2. Uniform particles, smaller than
H2O-MeOH/ 50 12.9 23 60
KCl 1 μm, are obtained after 1 h of synthesis (Figure S6, Supporting
Information). Although the crystallinity of the sample is not
a
Faraday efficiency is determined with ±10% accuracy. outstanding, both XRD and N2 adsorption compare very well with
commercial MIL-100(Fe) (Figure S6, Supporting Information).
obtained, it is the interaction with the solvent that is crucial. Table 2 2.5. Case Study IV: Electrochemical Synthesis of MIL-53(Al)
shows the relationship between the solvents, electrolyte, conductivity, and NH2-MIL-53(Al). A special class of MOFs is those whose pore
and efficiency. In spite of its poor conductivity, the DMF-MTBS couple dimensions may change without breaking chemical bonds within the
results in very high efficiencies. The BET surface areas of all the materials framework. This results in special properties like the breathing effect50,51
obtained are in the range 1400−1700 m2/g, values that are even higher and the gate phenomenon7,52 where pores contract or open during
than those initially reported for ZIF-8 (1400 m2/g).41 molecule adsorption. An example of a breathing type material is the
(b). Temperature Influence. Standard synthesis solutions are placed MIL-53 series.
in a controlled temperature bath with two Zn electrodes set 3 cm apart. MIL-53 is built from MO6 octahedra (where M can be Fe3+, Cr3+,
A constant current of 10 mA is used for 1 h. XRD analyses of the Al3+, Ga3+, In3+, or Sc3+) formed from trans bridging OH ions and the
synthesized products demonstrated that ZIF-8 is formed under oxygens of coordinate, bridging 1,4-benzene-dicarboxylate linkers.51 In
electrochemical conditions. The material produced is filtered off, this way a crystalline material with 1-D diamond shaped pores is formed.
cleaned overnight in 50 mL of methanol under reflux, and finally dried at Amino-MIL-53(Al)9,53 is a material with the topology of MIL-53.
100 °C. Small (<1 μm) particles with a homogeneous size distribution During the synthesis of amino-MIL-53(Al), 2-amino terephthalic acid is
are obtained in all cases. Temperature does not seem to greatly influence used as the linker molecule instead of terephthalic acid. The isoreticular

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material obtained has the following formula: Al(OH)[O 2 C− with 200 mmol of amino terephthalic acid, using 0.1 M KCl as the
C6H3NH2−CO2]. The MIL-53(Al) family is typically synthesized electrolyte in all cases, except pure DMF, where MTBS was used.
under hydrothermal conditions with synthesis times varying between 5
h and 3 days, depending on the solubility of the organic linker54 and the
nature of the metal.51,55,56
As is the case for MIL-100, MIL-53 is one of the possible products
that can be formed starting from similar metal and organic precursors.
For example, NH2-CAU-1,57 NH2-MIL-53,9,53 and NH2-MIL-10158
have been reported to crystallize under slightly different synthesis
conditions, when the nature of the solvent seems to play a primary role.
Recently we studied in detail, via in situ SAXS/WAXS, the competitive
formation of the MIL-53 and MIL-101 phases.59
(a). MIL-53(Al). A mixture containing water and 10 vol% DMF was
used as the solvent medium. The addition of DMF enhances the
solubility of the linker, while the presence of water drives the synthesis
toward the formation of the MIL-53 phase.59 KCl is used as the
electrolyte, although other electrolytes such MTBS or NaOH can be
used (not shown). The latter can aid the deprotonation of the linker.60

Table 3. MIL-53(Al) Electrochemical Synthesis Conditions,

Faraday Efficiency, and Productivity
solvent current Faraday
H2O/ temp density efficiencya productivity
DMF electrolyte [°C] [mA/cm2] (%) [g/h] Figure 7. XRD analysis of electrochemical NH2-MIL-53 for different
90:10 KCl 90 2 >90 0.042
H2O/DMF volume ratios.
90:10 KCl 90 20 >70 0.775
90:10 KCl 20 20 45 0.125 Elemental analyses were performed after every synthesis in order to
10:90 MTBS 90 2 40 0.010 determine whether some electrolyte was present in the crystalline
a
Faraday efficiency is determined with ±10% accuracy. structure after synthesis. In the case of MIL-53(Al) and NH2-MIL-
53(Al), amounts of potassium below 0.1 wt.% were found. The
electrolyte was KCl except in the case of pure DMF, when MTBS was
used. NH2-MIL-53(Al) was formed in every case as pure phase,
Table 3 summarizes the different syntheses performed. The use of KCl according to Al/C ratios and XRD. Different pore configurations were
or NaOH results in a conductivity of ∼9 mS cm−1 compared to 1.70 mS obtained at different H2O/DMF ratios. It was predominantly the np
cm−1 of MTBS. As the synthesis advances, protons are reduced to H2 phase that was obtained when the synthesis was carried out in pure
and substituted in the solution by Al3+, thus increasing the basicity of the water, while an almost completely open structure (lp) was obtained for
solution. The final pH can be as high as 12. By applying a current of 2 the experiments in the presence of DMF. Apparently, the presence of
mA/cm2 for 3 h, 125 mg of material is recovered (6.2% yield with respect DMF seems to stabilize the lp configuration of the material. Figure S9,
to the initial amount of linker); when the current is set at 100 mA (20 Supporting Information shows the nitrogen adsorption isotherms for
mA/cm2), ca. 750 mg of material is obtained per hour (38% yield during the different samples. The results correspond well with the XRD data.
the first synthesis hour). It has to be stressed that an increase in current When only H2O is used as a solvent, the highly crystalline material shows
does not translate into a proportional increase in yield because of the an isotherm with only micropores. As the structure is partially closed, the
intrinsic synthesis kinetics (the linker concentration is similar in both amount of N2 adsorbed is lower. When DMF is added to the system
cases). When MTBS is used as the electrolyte, conductivity drops to 1.70 microporosity is preserved. As the DMF/H2O ratio increases the
mS/cm with a subsequent decrease in productivity (1% yield of initial crystallinity of the material becomes less and particles become smaller,
linker or 10 mg product per hour). In all the syntheses high Faraday while the presence of interparticle mesopores is clearly observed at high
efficiencies were obtained, with crystals smaller than 1 μm, surface areas P/P0.
of ∼1200 m2/g and pore volumes of 0.5−0.8 cm3/g (Figure S8, Figure 8 shows the diffuse reflectance infrared Fourier transform
Supporting Information) compared to 716 m2/g and 0.4 cm3/g of (DRIFT) spectra of the regular NH2-MIL-53(Al)np (prepared by
Basolite A100 (commercial MIL-53 (Al)). hydrothermal synthesis), and electrochemically synthesized samples
The XRD pattern corresponds with the large pore configuration of synthesized using an H2O/DMF (lp). When focusing on the
the material (MIL-53lp), and no other structures like MIL-101, MIL-68, hydrothermally synthesized sample, the broad band centered around
or MIL-88 are observed. Figure S7, Supporting Information compares 3680 cm−1 along with a shoulder at 3693 cm−1 is assigned to the bridging
the XRD patterns of the large (lp) and narrow pore (np) configurations hydroxyl group of the MIL-53, that is, Al-OH-Al (μ-hydroxo groups).
with the powder XRD of MIL-53 obtained hydrothermally and The shoulder position is very close to that reported for unfunctionalized
electrochemically. The hydrothermally synthesized sample shows an MIL-53, while the main band is slightly red-shifted. We attribute the
np configuration in its hydrated form (room temperature), in contrast to main band to hydroxyl groups which directly interact with the
the electrochemically synthesized sample, which has an lp configuration. neighboring amines, while the shoulder at 3693 cm−1 corresponds to
As is illustrated by Figure S7, Supporting Information and below, all surface -OH groups not engaged in hydrogen bonding.61,62 The two
MIL-53(Al) samples (functionalized and nonfunctionalized) synthe- sharp bands at 3385 and 3495 cm−1 in the spectrum of the
sized under electrochemical conditions showed a certain degree of pore hydrothermally synthesized NH2-MIL-53(Al) represent the symmetric
opening. and asymmetric vibrations of the respective NH2 groups. For samples
(b). NH2-MIL-53. synthesized electrochemically, a clear shift is observed in the amine
(b.1). Influence of the Solvent. One of the main advantages in the vibrations along with a change in the ratio and a split between the two μ2-
synthesis of NH2-MIL-53 is the higher solubility of the linker (amino- hydroxo vibrations. We attribute this change to the opening of the
terephthalic acid) in water compared to other linkers. To study the structure in the smaller electrochemically synthesized NH2-MIL-53(Al)
influence of the solvents in the synthesis of NH2-MIL-53, four different particles: as the structure opens, H-bonding between NH2 groups and
solutions (100 mL) at varying H2O-DMF volume ratios were prepared pending hydroxyls is lost. On the other hand, the DRIFT spectra of the

3494 dx.doi.org/10.1021/cg300552w | Cryst. Growth Des. 2012, 12, 3489−3498

Crystal Growth & Design
Figure 8. DRIFTS spectra of hydrothermally synthesized NH2-MIL-
53(Al) and electrochemically synthesized NH2-MIL-53(Al). The
bottom graph zooms in on the amine-OH region of the top spectra.
electrochemically synthesized MIL-53 samples rule out the presence of
strong defects. For example, free terephthalic acid presents its main
vibration at 1700 cm−1, associated with free carboxylic acid groups, and
this vibration is shifted to 1640 cm−1, when carboxylic groups are
coordinated. The coordination of DMF is not likely either, since no
significant vibrations are observed around 2950 cm−1.
(b.2). Effect of Electrochemical Synthesis on the NH2-MIL-53(Al)
Breathing. The flexibility of the MIL-53 network is still a matter of
debate. The removal of guest molecules, such as linker or solvent, by
heating leads either to an expansion (in the case of Al, Ga, and Cr) or to a
contraction of the unit cell (in the case of Fe).63 Although several
attempts to rationalize the breathing dynamics of these frameworks have
been published,64,65 very little is as yet known. Recently we discovered
that the enhanced performance of the NH2-MIL-53(Al) framework in
CO2 capture and separation is mostly due to the specific flexibility that
results from a delicate interplay of weak dispersion forces controlling the
flexibility of the framework. In contrast to its unfunctionalized
counterpart, the np form is preferred at low adsorbate pressures in the
NH2-MIL-53(Al). Only at high CO2 partial pressures does the
framework expand to its lp form.61,66,67
In order to discover whether the synthesis procedure has any effect on
the breathing behavior of the electrochemically synthesized MIL-53(Al)
samples, high pressure adsorption isotherms of CO2 were measured and
compared with a NH2-MIL-53(Al) sample synthesized hydrothermally
in the presence of a similar concentration of KCl. (Figure 9). The regular
HT-NH2-MIL-53(Al)KCl displays a two-step CO2 isotherm due to the
breathing properties of the NH2-MIL-53(Al) framework, which is
identical to samples synthesized under standard conditions (in the
absence of KCl). Because of the strong interaction with the material,
CO2 adsorbs efficiently in the np, accommodating around 2 mmol g−1
CO2. The first plateau in the CO2 isotherm extends to about 1.5 MPa. A
step in adsorption capacity is visible at higher pressure; at 3 MPa the
material adsorbs up to 8 mmol of CO2 per gram. This step thus
corresponds to the transition from the np form to a mix of the np and lp
3495
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Figure 9. CO2 adsorption isotherms at 25 °C for different NH2-MIL-53
synthesized electrochemically compared with the adsorption isotherm
of the hydrothermally synthesized material in the presence of KCl.
Closed symbols represent adsorption, and open symbols show the
desorption isotherm.
form and finally to an almost pure lp form. In contrast, a single step
isotherm is found for all materials synthesized under electrochemical
conditions, with clear differences between the samples: the np displays a
lower CO2 capacity than samples with a more pronounced lp
configuration. The saturation loading for the np sample is slightly
higher than that of the NH2-MIL-53(Al)np, while the more open
framework shows a capacity slightly lower than the breathing material in
its lp configuration. Furthermore, no hysteresis in the adsorption
isotherm is found for the electrochemically synthesized samples,
confirming the absence of cell expansion/contraction during CO2
adsorption. Similar, nonbreathing behavior was found with the
electrochemically synthesized MIL-53(Al) (see Supporting Informa-
tion).
3. DISCUSSION
Through the different case studies, we have shown that
electrochemical synthesis offers many possibilities for the
synthesis of metal organic frameworks. According to our results,
highly reactive metal species are formed upon anodic dissolution.
As a result, both synthesis time and temperature can be strongly
reduced when compared to regular hydro- or solvothermal
synthesis protocols. In the literature, it has been shown that by
changing the metal source, MOF formation kinetics can be
tuned. One clear example is the use of Cu(NO3)2 vs Cu(OAc)2 in
the synthesis of HKUST-1.33 In the case of electrochemical
synthesis, it is easy to envisage that the absence of counteranions
further facilitates the formation of the MOF phase, avoiding the
generation of waste in the form of, for instance, nitrates or
residual impurities in the MOF.
On the other hand, the solubility of the linker plays a major
role. As most syntheses are carried out under quite mild
temperature conditions, this might be a drawback, due to the
relatively low linker concentrations achievable in batch mode.
However, if a continuous synthesis protocol can be adopted, high
synthesis yields with almost full linker conversion can very easily
be envisaged. Moreover, when highly soluble linkers are used, as
was the case for ZIF-8, the production of large quantities of very
pure MOF is possible.
The Faraday efficiencies can be high in all the systems studied,
although a clear interplay between kinetics and linker availability
affects the overall efficiency of the process.
The production of MOF coatings on electrodes is also an
attractive feature of electrochemistry. In the case of HKUST-1,
the formation of high quality MOF films is possible, even when
different electrodes such as copper meshes are used (see Figure
11). In this respect, electrochemical synthesis holds much
promise for optoelectronic and sensing applications, where high
dx.doi.org/10.1021/cg300552w | Cryst. Growth Des. 2012, 12, 3489−3498
Crystal Growth & Design
Figure 10. HKUST-1 coating electrochemically deposited on a copper
mesh.
Figure 11. AFM micrograph of a NH2-MIL-53(Al) sample synthesized
electrochemically.
quality coatings are required on conductive surfaces.68 However,
as we show, electrochemical coating is not trivial for other MOF
structures. Under the studied conditions, a certain induction time
was observed for the synthesis of all other MOFs, so resulting in
homogeneous nucleation in the liquid phase rather than in the
formation of coatings on top of the electrodes. Indeed, the few in
situ studies of the formation of ZIF-8 or MIL-53 point at
separated nucleation and crystal growth processes.36,37,59 It goes
without saying that if nucleation is the rate-determining step,
then the growth of films at the double layer close to the electrode
will not be trivial. A way to overcome this limitation could be to
use elevated temperatures and to begin the electrochemical
deposition after temperature stabilization. To this end, electro-
chemical pressure cells should be designed to withstand
hydrothermal conditions and to cope with the gases generated
during electrochemical synthesis.
It is fair to admit that we are a long way from understanding the
phenomena taking place during electrochemical synthesis. More
fundamental research to unveil the different chemical processes
happening at both the anode and the cathode during the
formation of MOFs is needed. In order to realize such ideas, new
reference electrodes, applicable under MOF synthesis con-
ditions, need to be developed.
The impact of synthesis on the flexibility of MIL-53(Al) and
NH2-MIL-53(Al) deserves special attention. Pure phase MIL-53
can be produced electrochemically. However, synthesis con-
ditions have a strong effect on the resulting unit-cell parameters.
More importantly, in contrast to the hydrothermally synthesized
MIL-53s, those that are electrochemically synthesized do not
show any breathing through the adsorption of CO2. XRD
collected after the adsorption of solvents like toluene or
methanol did not show any cell expansion either, as would be
expected for MIL-53 analogues.69 It has been proposed that
particle size might have a marked effect on breathing
behavior.64,65 As shown in Figure 11, NH2-MIL-53(Al) grains
smaller than 100 nm are found after electrochemical synthesis.
However, the complete absence of hysteresis in the CO2
isotherms together with the low loading obtained for the np
configuration samples suggest that the small size of the
synthesized particles is only indirectly responsible for the
absence of breathing. Although AFM analysis, FTIR spectros-
3496
Article
copy, TGA, elemental analysis, and XRD do not indicate the
existence of defects like free linker or aluminum (hydr)oxide
within the pores of the materials, we speculate that it is because of
the rapid kinetics of formation (due to the presence of highly
reactive Al3+ species in solution) that intergrown MOF particles
containing a large density of grain boundaries are formed. Such
grain boundaries within a single particle would stabilize the
structure thus impeding the breathing. The fact that the kinetics
of formation strongly influences the degree of structure opening
confirms our hypothesis: samples synthesized in the presence of
DMF and at high temperatures (higher linker solubility) show a
high fraction of lp over np form, while samples synthesized in
pure water and at low temperature are mostly in the np form.
Although additional work is needed to fully understand this
phenomenon, the results presented here demonstrate that
nonbreathing analogues of breathing structures can be
synthesized electrochemically and that unit cell parameters can
be tuned by varying the synthesis conditions. These materials can
be used as models of metastable phases for fundamental research
and might offer several advantages for applications where crystal
breathing is not desired (i.e., in coatings or even in the shaping of
pellets, where the continuous expansion and reduction of crystals
may result in the formation of cracks).
4. CONCLUSIONS
MOFs based on copper, aluminum, or zinc and linkers with
different coordinating moieties and connectivities can be
synthesized via anodic dissolution. Electrochemical MOF
synthesis has various advantages:
• Faster synthesis at lower temperatures than conventional
synthesis
• Metal salts are not needed and therefore separation of
anions such as NO3− or Cl− from the synthesis solution is
not needed prior to solvent recycle. No anionic residues
end up in the MOFs
• Virtual total utilization of the linker can be achieved, in
combination with high Faraday efficiencies.
Although this approach appears promising for the synthesis of
coatings, it seems to be limited to situations where nucleation
takes place almost instantaneously. A fine-tuning of the synthesis
conditions will therefore be needed for MOFs like MIL-53, MIL-
100, or ZIF-8.
Last but not least, the synthesis method has a clear effect on the
breathing behavior. The electrochemically synthesized MIL-53s
show that the breathing effect upon adsorption is absent.
■
ASSOCIATED CONTENT
*
S Supporting Information
Experimental details and additional figures. This material is
available free of charge via the Internet at http://pubs.acs.org.
*
W Web-Enhanced Features
A video of a synthesis in the corrosion cell showing the quick
formation of HKUST-1 crystals on the surface of the electrode in
AVI format is available.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: j.gascon@tudelft.nl.
Notes
The authors declare no competing financial interest.
dx.doi.org/10.1021/cg300552w | Cryst. Growth Des. 2012, 12, 3489−3498
Crystal Growth & Design
■
ACKNOWLEDGMENTS
Prof. Mark Koper, Dr. Gonzalo Garcia,́ and Dr. Paramaconi
Rodriguez-Perez from Leiden University are acknowledged for
the fruitful discussions they provided. Marcel Bus (TU Delft) is
gratefully acknowledged for the AFM characterization.
J.G. gratefully thanks the Dutch National Science Foundation
(NWO-CW-VENI) for its financial support.
■
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3498 dx.doi.org/10.1021/cg300552w | Cryst. Growth Des. 2012, 12, 3489−3498