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Activation of metal–organic framework materials

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DOI: 10.1039/c3ce41232f

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Activation of metal–organic framework materials†

Joseph E. Mondloch, Olga Karagiaridi, Omar K. Farha* and Joseph T. Hupp*
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Cite this: CrystEngComm, 2013, 15,

9258
Crystalline metal–organic frameworks (MOFs) have emerged as a highly desirable class of solid-state materials.
Received 25th June 2013, Some of their most attractive features include exceptionally high porosities as well as surface areas. A key aspect
Accepted 4th September 2013 to the realization of high porosity is the removal of guest molecules from the framework while still maintaining its
structural integrity (i.e., “activation”). This contribution highlights the strategies utilized to date for activating MOFs,
DOI: 10.1039/c3ce41232f
including: (i) conventional heating and vacuum; (ii) solvent-exchange; (iii) supercritical CO2 (scCO2) exchange;
www.rsc.org/crystengcomm (iv) freeze-drying; and (v) chemical treatment.

Introduction yet more rational purification protocols are desirable.21,23

Farha et al. demonstrated that density separation, utilizing
Metal–organic frameworks (MOFs) constitute an important mixed organic solvent systems, is broadly applicable for
and rapidly growing class of solid-state compounds. MOFs the purification of MOFs.24 Density separation was utilized
are composed of inorganic nodes (metal ions or clusters) and to separate mixtures of MOF phases, mixtures of MOFs
organic linkers that are interconnected by coordination containing single and multiple ligands (e.g., in pillared
bonds of moderate strength.1–3 From a functional materials paddlewheel structures), and catenated and non-catenated
perspective, some of the most attractive features of MOFs phases.24 Controlling catenation—the interpenetration or
are: (i) their crystalline nature, allowing unambiguous struc- interweaving of two or more identical networks—has also
tural determination, which, in turn, has allowed predictive been extensively investigated.25 Concentration,26 temperature,27
materials discovery,4,5 (ii) their chemical and structural diver- templating strategies (utilizing solvents or other molecules),28,29
sity, and (iii) their permanent porosity, uniformly nanostruc- liquid-phase epitaxy,30 ligand design31 as well as judicious
tured cavities, and, to date, surface areas exceeding those of consideration of framework topology,6,32 and solvent-
all known porous materials (exceeding ca. 7000 m2 g−1 experi- assisted linker exchange (SALE)33 have all been utilized to
mentally and 14 000 m2 g−1 computationally!).6,7 control catenation.
Given these exceptional properties, MOFs are being inves- The final step en route to MOFs exhibiting permanent
tigated for a number of potential applications including gas porosity is “activation”, or the removal of guest molecules
storage8,9 and separation,10 chemical catalysis,11,12 sensing,13 (solvent or other chemicals used during the synthesis) from
ion-exchange14 and conductivity,15 drug delivery,16 biomedi- the MOF without compromising its structural integrity and
cal imaging,17 and light harvesting.18–20 Highly desirable are hence porosity.21 Robson noted the significance of this
the permanent porosities and large internal surface areas challenge in a seminal contribution, proposing that “despite
exhibited by many MOFs (vide infra) which can be of para- Nature's abhorrence of a vacuum it may be possible to devise
mount importance for successful implementation of many rods (linkers) with sufficient rigidity to support the existence
potential applications (e.g., gas storage and gas phase cataly- of solids with relatively huge empty cavities”.34 This “abhor-
sis). Significant challenges exist in the synthesis of MOFs rence of a vacuum” is exacerbated when the cavities are filled
with permanent porosity as well as tuneable pore structure with high boiling point solvents such as N,N-dimethylformamide
and volume; preparation of phase-pure, non-catenated, and (DMF), N,N-diethylformamide (DEF), or dimethyl sulfoxide
“activated” MOFs has been particularly troublesome, espe- (DMSO) that are required as a part of the MOF synthesis.
cially in the high surface area regime.21 Significant capillary forces, and hence surface tension, can be
Phase-pure MOF materials are often obtained via synthetic created (see Fig. 1) during activation, which in turn can yield
optimization that is laborious and cumbersome. High- fully or partially collapsed frameworks. In many instances, the
throughput syntheses can alleviate some of these efforts,22 experimentally observed surface areas and pore volumes are
significantly lower than those predicted from simulations
Department of Chemistry, Northwestern University, 2145 Sheridan Road,
based on single-crystal structures and often incomplete activa-
Evanston, IL, USA. E-mail: [email protected], [email protected];
Tel: +1 847 467 4834, +1 847 491 3504
tion is invoked to explain the observed data.
† Electronic supplementary information (ESI) available: A full table of all Hence, an important question and therefore focus of the
studies utilizing scCO2 activation to date. See DOI: 10.1039/c3ce41232f present contribution is, what are the most effective and general

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Fig. 2 Molecular representations of the small cage of Cr-MIL-101 (a) and UIO-66
(b). Cr atoms are shown in dark blue, Zr atoms are shown in grey, oxygen and fluo-
rine atoms in red, carbon atoms in black, and hydrogen atoms have been omitted
for clarity.

Fig. 1 An illustrative phase diagram of the physical phenomena encountered for boundary (see Fig. 1), significant surface tension and
conventional and solvent-exchange activation, scCO2 exchange, and benzene
capillary forces are created that cannot be offset by the
freeze-drying.
moderate coordination bond strengths in many MOFs.
Clearly additional activation strategies needed to be devel-
strategies for removing (i.e., activating) guest molecules from oped to fully access the large internal surface areas and
MOFs with increasing porosity and surface area? Herein we porosities of most MOF materials.
outline five strategies that have been effective for activating
MOFs: (i) conventional heating and vacuum; (ii) solvent- Activation by solvent-exchange
exchange; (iii) supercritical CO2 (scCO2) processing; (iv)
One alternative and effective activation strategy is to
freeze-drying; and (v) chemical treatment. Fig. 1 illustrates
exchange the high-boiling point solvent (e.g., DMF), required
the physical phenomenon that each activation strategy
for synthesis, for a lower boiling point solvent (e.g., CHCl3)
utilizes and these will be discussed further throughout this
followed by more mild activation under vacuum, a process
highlight. This contribution is not intended to be an exhaus-
often referred to as solvent-exchange. Lower boiling-point
tive review of the literature, but rather a highlight of what
solvents have weaker intermolecular interactions and hence
we perceive to be some of the most important advances in
minimize surface tension and capillary forces during the acti-
activating MOFs. Our hope is that it helps future researchers
vation process. Li et al. were apparently the first to demonstrate
who encounter some of the struggles associated with the
that solvent-exchange could be effectively used to enhance the
activation of MOFs.
activation of MOFs.40 The iconic framework, MOF-5(IRMOF-1,
Conventional activation [Zn4O(bdc)3], Fig. 3a), was synthesized in DMF–chlorobenzene.
The structure could be maintained and subsequently activated
Conventional activation is the removal of solvent and/or
after exchanging the DMF–chlorobenzene for CHCl3. The result
other guest molecules by simple heat and vacuum treat-
is a microporous solid with a Langmuir surface area of
ment. This is carried out in a manner analogous to the
2900 m2 g−1.40 A more detailed analysis of two isoreticular
strategies commonly used to activate zeolites and carbons.
MOFs (IRMOFs) was done by Nelson et al.41 Utilizing conven-
Two successful examples utilizing conventional activation
tional activation, IRMOF-3 (Fig. 3b) showed a BET surface area
include Cr-MIL-101 ([Cr3F(H2O)2O(bdc)3], Fig. 2a)35 and
of 10 m2 g−1 while no N2 uptake was observed for IRMOF-16
UIO-66 ([Zr6(O)4(OH)4(bdc)12], Fig. 2b)36 which have surface
(Fig. 3c). By exchanging DMF for CHCl3 the surface areas were
areas of 4100 m2 g−1 and 1070 m2 g−1 respectively (bdc =
increased to 1800 m2 g−1 for IRMOF-3 and 470 m2 g−1 for
benzene dicarboxylate). Both Cr-MIL-101 and UIO-66 exhibit
IRMOF-16. While impressive, even higher surface areas were
exceptional thermal and chemical stability that render
expected for IRMOF-3 and IRMOF-16 (vide infra). Thus while
them stable to conventional activation protocols. Unfortunately,
solvent-exchange has been widely and successfully utilized, in
conventional activation has found minimal utility for
some instances it still leads to materials exhibiting porosities
accessing the full porosity of many other MOFs. Indeed this
lower than those predicted from single-crystal structures.
was an early challenge for the field—one however, that has
largely been overcome—with many researchers noting the
worst case scenario of complete loss of crystallinity and lack Activation by scCO2
of porosity upon activation.37–39 The reason for this is quite The use of scCO2 is a relatively new strategy for activating
clear: as the sample passes through the liquid-to-gas phase MOFs that is proving to be quite general (vide infra).41 scCO2

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285-fold increase over conventional activation and a 1.6-fold

increase over conventional solvent-exchange. As the frame-
work is extended, IRMOF-16 (Fig. 3c) showed a BET surface
area of 1910 m2 g−1, which is a 4-fold increase over the
material obtained by conventional solvent-exchange. (Nelson
et al. could not obtain a BET surface area for IRMOF-16
by conventional activation.) While scCO2 activation is not
always effective,55–57 we have had continued success within
our laboratories.4,6,58–63
Other researchers around the world have also effectively
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utilized the scCO2 strategy to activate a wide variety of

MOFs.45–53,55–57,64–101 We suspect this effectiveness, along
with its low cost and scalability are important factors driving
the use of scCO2 as an activation strategy. Table 1 and Fig. 4
illustrate some of the more impressive examples from around
Fig. 3 Molecular representations of (a) MOF-5, (b) IRMOF-3, (c) IRMOF-16 and (d) the world (a full catalogue is provided as ESI† for the inter-
the Zn4O node for MOF-5, IRMOF-3,16. Zn atoms are shown in blue, O atoms are
ested reader). Collectively these materials represent some of
shown in red, C atoms are shown in black, and H atoms are not shown for clarity.
the most porous MOFs known, including MOFs exhibiting:(i)
the largest known surface areas;6 (ii) the highest known
pore volumes;6,97 (iii) extreme pore and aperture sizes,52 (iv)
is “green” and non-toxic in nature, cost competitive, and scal- encapsulated reactive species;53 and (v) dynamic structural
able, making it a highly attractive candidate for the activation behavior.85 Clearly scCO2 activation is becoming an integral
of MOF materials.42,43 Activation by scCO2 builds on the con- part of MOF preparation.
ventional solvent-exchange process, as solvents such as EtOH Very recently, Koh et al. introduced the concept of “flowing”
(or other solvents miscible in liquid CO2 and compatible with scCO2 activation.102 Here the sample is placed in a column and
the instrument can also be used) are exchanged for liquid scCO2 flows through the sample (vs. static delivery and
CO2 at high pressure (i.e., >73 atm) over the course of hours. exchange cycling in conventional scCO2 activation) and effec-
Next, the sample is brought above the supercritical tempera- tively exchanges the guest solvent molecules. One important
ture of CO2 (i.e., 31 °C); the result is a framework occupied advance of the flowing scCO2 technique is that MOFs
by scCO2. Finally, the scCO2 apparatus is slowly vented while containing solvents such as DMF can be activated without
holding the temperature above the critical point. The key exchange. We note however, that direct exchange of DMF for
conceptual advance is going directly to the gas-phase from CO2 is also possible (in principle) in the static/exchange scCO2
the supercritical phase, thereby avoiding the liquid-to-gas strategy described by Nelson et al.41 (DMF is miscible in liquid
phase transition and its associated capillary forces (Fig. 1). In CO2.103) In that earlier study, EtOH was used as an intermedi-
addition, scCO2 activation likely diminishes particle-to- ate solvent because of the susceptibility of some instrument
particle aggregation.41,44 components to damage by DMF.41 Certainly different designs
The initial demonstration on the use of scCO2 for activat- and/or engineering strategies can be utilized to improve upon
ing MOFs was reported by Nelson, et al.;41 scCO2 had been the static/exchange scCO2 technique (in fact scCO2 extraction
extensively used previously to activate other porous materials is often “a semi-batch process in which CO2 flows in a continu-
such as aerogels.54 Four MOFs were studied, each containing ous mode”43), yet the fundamental science is identical. None-
Zn4O nodes and dicarboxylate linkers. IRMOF-3 (Fig. 3b) theless, flowing scCO2 has been shown to be capable of
exhibited a BET surface area of 2850 m2 g−1 representing a effectively activating otherwise delicate MOFs.48,84,98

Table 1 Selected MOFs and some of their relevant material characteristics enabled by scCO 2 activation. Values are reported as they appear in the
original contributions
2 −1 3 −1
MOF University BET SA (m g ) Pore volume (cm g ) Ref.
NU-110 Northwestern University 7140 4.40 6
MOF-210 UCLA 6240 3.60 45
SNU-70′ Seoul National University 5290 2.17 46
Co6(btb)4(bp)3 Ulsan National Institute of Science & Technology 5200 2.10 47
UMCM-9 University of Michigan 4970 1.80 48
bio-MOF-100 University of Pittsburgh 4300 4.30 49
FJI-1 Fujian Institute of Research 4043 1.43 50
DUT-13 Dresden University of Technology 2532 1.98 51
IRMOF-74XI UCLA 1760 3.41 52
P11-16/1 University of South Florida 1009 — 53

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Fig. 5 Two Cu paddlewheel based MOFs activated by freeze-drying. Cu atoms are

shown in blue, O atoms are shown in red, C atoms are shown in black, and H
atoms are not shown for clarity.

Cu paddlewheel based MOFs vs. conventional solvent-

exchange. Interestingly, the powder X-ray diffraction pattern
of the pristine (solvent soaked) sample is different from that
of the freeze-dried sample. Ma et al. interpreted this change
as a breathing phenomenon, however one might also specu-
late that the innocence of the technique is of concern. Other
solvents can also be utilized for freeze-drying: He et al.
recently demonstrated that cyclohexane could be substituted
for benzene.104 (This is an important practical result, as
benzene is a carcinogen but cyclohexane is not.) Conven-
tional solvent exchange yielded a material (FIR-3, Fig. 5)
displaying a BET surface area of 24 m2 g−1, while cyclohex-
ane freeze-drying yielded a material with 497 m2 g−1. If freeze-
Fig. 4 Molecular-scale representations of some interesting MOFs activated by drying proves to be more general, we suspect that it will also
scCO2. Zn atoms are shown in blue, Cu atoms are shown in purple, Cd atoms in become a widely used MOF activation technique.
orange, Mg atoms in yellow, oxygen and fluorine atoms in red, carbon atoms in
black, nitrogen atoms in green, and hydrogens have been omitted for clarity.
Activation by chemical treatment
In some instances a chemical treatment is needed to activate
the MOF. One set of examples comes from the increasingly
Activation by freeze-drying popular class of MOFs constructed from Zr6-based
Activation by benzene freeze-drying is a newly developed tech- nodes.36,105–107 These materials have attracted interest, in
nique for activating MOFs.67 To utilize this technique, the MOF part, because of their exceptional stability in aqueous
must be exchanged with and left in benzene. The sample is environments, including highly acidic aqueous solutions.
then frozen at 0 °C and brought back to room temperature sev- Often a large excess of acid (e.g., benzoic acid) is utilized to
eral times. Upon the final freeze cycle, the sample is placed help modulate the nucleation and growth kinetics of the
under vacuum at a temperature and pressure below the sol- MOF during synthesis. Subsequently, that acid is removed
vent’s triple point. Finally, as the sample is warmed under either by rigorous washing or by chemical treatment. Feng
reduced pressure, the benzene sublimes (i.e., a direct solid-to- et al. noticed for a tetracarboxylate-porphyrin-containing
gas phase transition) and therefore avoids the liquid-to-gas MOF, PCN-222 (Fig. 6a; also known as MOF-545105) that treat-
phase transition and its associated capillary forces (Fig. 1). ment in concentrated HCl (and subsequent activation
Ma et al. demonstrated that benzene freeze-drying could under vacuum and heat) led to a significant increase in the
be utilized to activate two isoreticular Cu paddlewheel based pore volume of the material.106 However, the precise
MOFs ([Cu2(L)(H2O)2]) which are shown in Fig. 5.67 Signifi- action of the HCl was not elucidated. For a similar
cant increases in BET surface areas were observed for both tetracarboxylated-pyrene- and Zr6-containing MOF (NU-1000,

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EERE Fuel Cell Technologies Program, administered by ORISE

for DOE. ORISE is managed by ORAU under DOE contract num-
ber DE-AC05-060R23100. Opinions expressed in the paper do
not necessarily reflect the views of DOE, ORAU, or ORISE.

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