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Cite this: Dalton Trans., 2012, 41, 5458
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Aqueous room temperature synthesis of cobalt and zinc sodalite zeolitic
imidizolate frameworks†
Adam F. Gross,* Elena Sherman and John J. Vajo
Received 24th January 2012, Accepted 28th February 2012
Published on 12 March 2012 on http://pubs.rsc.org | doi:10.1039/C2DT30174A
DOI: 10.1039/c2dt30174a
Sodalite zeolitic imidazolate frameworks containing Co
(ZIF-67) and Zn (ZIF-8) were synthesized at room tempera-
ture under aqueous conditions in 10 min. A trialkylamine
deprotonated the 2-methylimidazole ligand and nucleated
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the frameworks. Furthermore, the ligand acted as a structure
directing agent in place of an organic solvent.
Zeolite imidiazole frameworks (ZIFs) are air, water, and solvent
stable porous materials formed in zeolite topologies from metal
ions and imidazolate ligands.1,2 The combination of high poro-
sity with tunable pore chemistry from metal ions and
ligand functional groups leads to potential applications in gas
sorption,2–4 gas separation,5,6 and catalysis.7,8 These applications
are cost sensitive and ZIFs are more likely to be used if they can
be synthesized at low cost using energy and material efficient
syntheses. ZIFs have traditionally been synthesized in organic
solvents, however, their cost would be significantly reduced if
syntheses could be performed in water at room temperature.
Aqueous syntheses are challenging because of the potential for
forming non-porous metal hydroxide or metal organic com-
pounds.9,10 Here, we describe the room temperature synthesis in
water of Co and Zn sodalite topology ZIFs enabled by the
addition of a trialkylamine base.
Syntheses of Zn containing ZIFs at room temperature are well
established. Zinc 2-methylimidazolate (Zn(Me-Im)2, ZIF-8) has
been synthesized by combining a zinc salt with 2-methylimida-
zole (HMe-Im) in methanol or dimethylformamide (DMF) and
stirring from 1–24 h.11–13 These room temperature syntheses
generally produce nanocrystalline materials with surface areas of
800 to 1617 m2 g−1, corresponding to 50% to 100% of the
surface area of state of the art microcrystalline ZIF-8.11,13 The
highest surface areas are obtained in methanol when additional
coordination ligands are added that compete with HMe-Im,
control the nucleation and growth of ZIF-8, and enable the for-
mation of nanocrystalline to microcrystalline domains.11b Zn
methylimidazolate ZIFs have also been formed by layering a
methanolic HMe-Im solution on a solution of Zn(OH)2 in
aqueous ammonia.14 The crystals formed at the interface over
HRL Laboratories, LLC, 3011 Malibu Canyon Rd., Malibu, CA 90265,
USA. E-mail: afgross@hrl.com; Fax: +01-310-317-5450; Tel: +01-310-
317-5747
† Electronic supplementary information (ESI) available: Synthesis
details, analysis methods, and material characterization in Tables S1–S2
and Fig. S1–S7. See DOI: 10.1039/c2dt30174a
5458 | Dalton Trans., 2012, 41, 5458–5460
COMMUNICATION
one month and had BET surface areas up to 1030 m2 g−1. The
formation of ZIFs at liquid–liquid interfaces occurred in other
organic solvents as well.15 Additionally, zinc imidazolate poly-
mers with zeolite topologies were synthesized by mixing zinc
salts dissolved in amines with imidazole (HIm) in organic sol-
vents.15 The organic solvent acted as a structure directing agent
and controlled the Zn(Im)2 topology, however, no surface areas
were reported. This approach produced amorphous materials
when Co cations were used. Multiple ZIFs have been also pro-
duced by mechanically milling ZnO and imidazole ligands in
organic solvents at room temperature.16 The aqueous room-temp-
erature synthesis of ZIF-8 with a BET surface area of 1079 m2
g−1 was recently reported where a Zn(NO3)2·6H2O solution was
mixed with a solution containing a large excess of HMe-Im
(Zn:HMe-Im molar ratio of 1 : 70).17
Tranchemontagne et al. formed Zn and Cu based metal
organic frameworks at room temperature in organic solvents by
combining solutions of metal salts with solutions of ligands
deprotonated with triethylamine (TEA).18 Additionally, ZIF-90,
(Zn(imidazolate-2-carboxyaldehyde)2) was formed by diffusing
TEA into a solution of zinc nitrate and ligand in DMF.19 In both
of these syntheses, TEA deprotonates the ligand dissolved in
organic solvent and initiates framework formation. These efforts
led us to hypothesize that TEA could deprotonate imidazole
based ligands for aqueous ZIF syntheses without unwanted for-
mation of metal hydroxides. This idea was reinforced by Cravil-
lon et al. finding that the properties of ZIF-8 formed at room
temperature in methanol were improved through the addition of
competing ligands to HMe-Im, such as alkylamines, that
increase the rate of ZIF nucleation.11b Here, we report on the
aqueous, room temperature synthesis of ZIF-67 (Co(Me-Im)2)
and ZIF-8 by combining metal nitrate solutions with solutions of
2-methylimidazole ligands and TEA. To our knowledge this is
the first report of the synthesis of a cobalt based ZIF at room
temperature. In addition, compared to previous aqueous synth-
eses of Zn-based ZIFs, this synthesis yields comparable quality
ZIF-8 at much closer to stoichiometric Zn–HMe-Im ratios, thus
improving the reagent utilization efficiency and yields.
All the samples were synthesized by dissolving a 1 : 1 molar
ratio of HMe-Im and TEA in water and then combining this sol-
ution with Co(NO3)2·6H2O or Zn(NO3)2·6H2O dissolved in an
equal volume of water. Overall, the metal : ligand : TEA : H2O
molar ratios were 1 : (4 to 16) : (4 to 16) : 2255. Formation of
ZIFs occurred within seconds when the metal ion solution was
poured into the stirred ligand–TEA solution. The synthesis
This journal is © The Royal Society of Chemistry 2012
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Published on 12 March 2012 on http://pubs.rsc.org | doi:10.1039/C2DT30174A

Fig. 2 SEM images of ZIF-67 (left) and ZIF-8 (right) nanoparticles

Fig. 1 XRD of ZIFs synthesized at room temperature in water with synthesized with 1 : 16 : 16 metal : ligand : TEA molar ratios.
1 : 16 : 16 metal : ligand : TEA molar ratios. Peaks are indexed and
match the known sodalite ZIF-67 and ZIF-8 structures.
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Table 1 ZIF porosimetry data

solution was stirred for 10 minutes and then the ZIFs were separ- Metal : ligand : TEA BET surface t-Plot micropore
Material molar ratio area (m2 g−1) volume (cm3 g−1)
ated by centrifugation and washed twice with water. Finally, the
samples were dried in air at 110 °C and then under vacuum at ZIF-67 1:4:4 608 0.25
150 °C. Complete details are given in the ESI.† ZIF-67 1:8:8 636 0.26
The X-ray diffraction (XRD) patterns for metal : ligand ratios ZIF-67 1 : 16 : 16 868 0.38
ZIF-8 1:4:4 528 0.21
of 1 : 16 agree with the known patterns from syntheses with ZIF-8 1:8:8 620 0.25
ZIF-67 and ZIF-8 as shown in Fig. 1.1,9 All peaks index to a ZIF-8 1 : 16 : 16 811 0.32
sodalite structure and show excellent agreement with peak posi-
tions we calculated from the known crystal structures (Tables
S1–S2, ESI†).1,2 ZIFs were also successfully formed with metal : while we find that a 1 : 1 ratio is required in water. The difference
ligand ratios of 1 : 4 and 1 : 8 as shown by XRD in Fig. S1 and may stem from the solvent because nucleation in methanol pro-
S2 (ESI†) for ZIF-67 and ZIF-8, respectively. There is a 3× ceeds without any base.11a In water, TEA may need to first
increase in XRD peak intensities and thus crystallinity for deprotonate the HMe-Im ligands ( pKa = 7) before deprotonating
ZIF-67 when the metal : ligand ratio decreases from 1 : 4 to the zinc–methyl imidazole complex ( pKa = 10.3) for nucleation
1 : 16. However, there is only a small intensity increase for ZIF-8 to occur. Because ≥75% of the imidazole molecules in our
with decreasing Zn : HMe-Im ratios. Improvements in crystalli- experiments occur as the free ligand, more TEA than a 1 : 0.5
nity with lower metal : ligand ratios are not surprising because ligand : TEA ratio is required to deprotonate the zinc–methyl
these are closer to the 1 : 70 Zn : HMe-Im ratio used for the imidazole complex.
aqueous synthesis of ZIF-8 without added base.17 Porosimetry data for all samples are shown in Table 1 based
Cravillon et al. found that adding base to methanol based on the N2 adsorption isotherms shown in Fig. S4 (ESI†). We
ZIF-8 synthesis solutions increases the nucleation rate by depro- observe that surface areas and pore volumes improve with lower
tonating a zinc–methyl imidazole complex that forms prior to metal : ligand ratios in agreement with the improved crystallinity
ZIF-8, leading to smaller particles.11b In agreement with those observed with XRD.
results, the inclusion of TEA under aqueous conditions also The surface areas for ZIF-67 in Table 1 increase with lower
yielded nanoscale crystals, <200 nm, as shown in SEM (Fig. 2) Co : HMe-Im ratios from 45% to 65% of the 1319 m2 g−1 BET
and STEM (Fig. S3, ESI†) images. From analysis of the SEM surface area obtained at high temperature (>100 °C).9 Similarly,
images, the ZIF-67 particles have an average diameter of 99 ± the micropore volumes vary from 40% to 62% of the pore
29 nm and the ZIF-8 particles are 60 ± 22 nm in diameter. The volume from the high temperature synthesized material
growth kinetics of ZIF-67 may be faster than ZIF-8 because the (0.61 cm3 g−1).9 The corresponding values for ZIF-8 are only
less distinct ZIF-67 particles resemble the later stage 32% to 50% of the highest reported surface area and micropore
ZIF-8 grown in methanol for 24 h, while our faceted ZIF-8 par- volume (1630 m2 g−1 and 0.64 cm3 g−1, respectively).1 The
ticles are similar to the initial shape of the methanol synthesized reduced surface areas are not surprising because other room
ZIF-8 after 40–60 min growth.13a Finally, our materials have temperature ZIF-8 syntheses produce materials with 50–70% of
non-uniform shapes and sizes, which is likely due to overall the high temperature surface areas.11a,13,17 When compared to
faster growth kinetics in water (<10 min reaction time)17 as com- the only aqueous room temperature synthesis of ZIF-8, we
pared to methanol (1–24 h reactions).11–13a obtain 75% of the surface area and 103% of the pore volume,
The amount of amine required to form ZIFs was different in while requiring <1/4 the amount of ligand.17 Thus, an advantage
water and methanol. Products were previously obtained in of this synthesis is that it enables the use of aqueous solvents
methanol with both 1 : 1 and 1 : 0.5 ligand : amine ratios,11b with reduced metal : ligand ratios. We note that we attempted to

This journal is © The Royal Society of Chemistry 2012 Dalton Trans., 2012, 41, 5458–5460 | 5459

improve the porosity using longer reaction times, up to 1 h;
however, surface areas did not improve.
The samples were analyzed by thermogravimetric analysis
(TGA) in air to understand the cause of the limited surface areas
(Fig. S5, ESI†). ZIF-67 begins to lose mass above 200 °C,
which probably corresponds to the loss of guest molecules, and
shows a sharp drop in mass at 300 °C corresponding to
decomposition. A residual mass of 33% is observed instead of
the expected 36% from Co3O4 formed from Co(Me-Im)2. Thus,
there is likely extra organic material in the pores. For ZIF-8, the
loss of guest molecules is observed below 350 °C and these mol-
ecules may explain the low surface area. The 37% residual mass
Published on 12 March 2012 on http://pubs.rsc.org | doi:10.1039/C2DT30174A
from 350 °C to 700 °C agrees with the expected 36% residual
mass of ZnO from Zn(Me-Im)2. The presence of some organic
material in the pores of both materials is corroborated by elemen-
tal analysis (ESI†) and FTIR spectroscopy (Fig. S6, ESI†). The
FTIR data matches the spectrum for Me-Im but additionally
shows a small amount of residual TEA and HMe-Im. Lastly, the
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thermal stability of ZIF-8 was studied by heating the samples in
air for one hour. The XRD patterns showed no change up to
300 °C, a loss of the structure at 350 °C, and ZnO at 400 °C
(Fig. S7, ESI†). These results agree well with data for other
ZIF-8 nanocrystals.11b,17
We attempted our synthetic approach with other water soluble
ligands, however, only ligands with structure directing functional
groups produced ZIFs in water. Zinc and cobalt solutions were
reacted with aqueous imidazole + TEA. The XRD pattern for the
Zn-Im system did not match the Zn-imidzaolate polymers in ref.
15, ZIF-1, ZIF-3, or ZIF-4. It was hypothesized that the methyl
group on Me-Im acts as a structure directing agent and performs
the task of the organic solvent.15 In agreement with this hypoth-
esis, no ZIF type structure was obtained for the Zn-Im system
without an organic solvent or ligand acting as a structure
directing agent. The need for a solvent or on-ligand structure
directing agent to template the ZIFs was reinforced by the Co-Im
system, which formed Co(OH)2 and Co3O4.
In summary, we have synthesized ZIF-67 and ZIF-8 under
aqueous conditions at room temperature. This is the first room
temperature synthesis of a Co ZIF in any solvent. These synth-
eses are enabled by the methyl group on Me-Im acting as a struc-
ture directing agent in place of an organic solvent and the
addition of TEA, which initiates the nucleation of ZIF materials
without forming metal hydroxides. Although TEA is required,
the total moles of TEA and HMe-Im is <1/2 the amount of
HMe-Im needed without TEA.17 The excess TEA and ligand are
also not consumed and, therefore, may possibly be reused in a
scaled-up synthesis. In the future, the porosity of these materials
may be improved by slowing the reaction using lower tempera-
tures or by the addition of other basic molecules that alter the
5460 | Dalton Trans., 2012, 41, 5458–5460
View Online
rates of nucleation and growth in methanol based ZIF-8
syntheses.11b
Acknowledgements
The authors thank Robert E. Doty for electron microscopy
imaging. This material is based upon work supported by the
Defense Advance Research Projects Agency under Contract no.
HR0011-10-C-0052.
Notes and references
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