Improving the porosity and catalytic capacity of a zinc paddlewheel metal-organic framework (MOF) through metal-ion metathesis in a single-crystal-to-single-crystal fashion

Article abstract of DOI:10.1021/ic5017092

Zinc paddlewheel metal-organic frameworks (MOFs) frequently exhibit low stability or complete collapse upon the removal of axial ligands. Hence, there are very few reports on gas adsorption of zinc paddlewheel MOFs. In this work, the N₂ and H

Full text of DOI:10.1021/ic5017092

Article
pubs.acs.org/IC
Improving the Porosity and Catalytic Capacity of a Zinc Paddlewheel
Metal-Organic Framework (MOF) through Metal-Ion Metathesis in a
Single-Crystal-to-Single-Crystal Fashion
†
†
‡
,‡
‡
,†
Jie Yang, Xiaoqing Wang, Fangna Dai, Liangliang Zhang,* Rongming Wang, and Daofeng Sun*
†Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering,
Shandong University, Jinan, Shandong 250100, People’s Republic of China
‡
College of Science, China University of Petroleum (East China), Qingdao, Shandong 266580, People’s Republic of China
*
S Supporting Information
ABSTRACT: Zinc paddlewheel metal-organic frameworks (MOFs) frequently
exhibit low stability or complete collapse upon the removal of axial ligands. Hence,
there are very few reports on gas adsorption of zinc paddlewheel MOFs. In this
work, the N and H adsorption measurements were carried out for a zinc MOF
2
2
(
(
namely, SDU-1) based on two types of paddlewheel secondary building units
SBUs): [Zn (COO) ] and [Zn (COO) ]. Because of the existence of inherent
2
3
2
4
surface instability upon removal of solvates in zinc paddlewheel SBU, SDU-1
possesses a very low surface area. Through metal-ion metathesis in a single-crystal-
2
+
2+
to-single-crystal fashion, the Zn ions in SDU-1 were exchanged by Cu ions to
generate Cu-SDU-1. Through the measurements of gas adsorption and catalytic
test, the porosity and catalytic capacity of Cu-SDU-1 have been improved
significantly, compared to SDU-1.
INTRODUCTION
in a single-crystal-to-single-crystal (SCSC) fashion are still
10
■
(
rare.
The construction of porous metal−organic frameworks
MOFs) has drawn great attention in recent years, because of
their potential applications in gas separation and storage,
It is well-known that zinc paddlewheel MOFs frequently
exhibit lower-than-expected surface area or complete collapse
when the axial ligands of the paddlewheel SBU were thermally
1
−3
catalysis, and drug delivery.
Currently, the design and
11
removed. Recently, Matzger and co-workers studied
synthesis of open MOFs with permanent porosity is still a great
challenge to chemists, although many porous MOFs with high
gas storage and catalytic property have been synthesized and
Zn (btc) (abbreviated as Zn-HKUST-1; btc = 1,3,5-benzene-
3
2
tricarboxylate) by using positron annihilation lifetime spectros-
copy and reconciled the discrepancies between crystallographic
4
,5
documented. Recently, the development in two aspects of
12
porosity and guest access in Zn-HKUST-1. It is revealed that
post-synthetic modification of MOFs has made it possible to
construct porous MOFs: one is ligand exchange, through
which stable MOFs with progressively larger mesoporous
an intensified surface layer prevents the entry of even small
molecular species into the crystal framework of Zn-HKUST-1,
which has inherent surface instability upon removal of solvates.
6
7
cavities can be synthesized; the second one is metal-ion
13
However, Cu-based HKUST-1 an isostructural MOF with
8
metathesis, in which the two exchanged metal ions should
Zn-HKUST-1, possesses high stability and gas uptake, further
indicating the effect of coordination geometry of metal ions on
the stability of a SBU, even a MOF.
Considering this information, recently, we have started to
construct porous MOFs through metal-ion metathesis. In this
paper, we report the metal-ion metathesis strategy on the
improvement of the porosity and catalytic capacity of a MOF in
a single-crystal-to-single-crystal fashion.
have similar coordination geometries. Generally, the stability of
an MOF is highly determined by the rigidity of the secondary
building units (SBUs) and the coordination geometry of metal
ions that constitute the SBUs. Hence, an unstable SBU with
coordinated solvates may be changed to stable one if metal ions
constituting the SBU are replaced by other metal ions with
different coordination geometry. Normally, through metal-ion
metathesis, some new isostructural MOFs that are hard to
obtain by conventional methods can be successfully con-
9
EXPERIMENTAL SECTION
structed and, sometimes, the stability can also be significantly
■
Preparation of SDU-1. The H TMBHB (0.8 mg, 0.0013 mmol)
improved. Thus, metal-ion metathesis has been considered as a
promising tool for synthesis of new materials. Although many
functional MOFs have been synthesized through metal-ion
metathesis process in the past decade, the reports on
construction of porous MOFs through metal-ion metathesis
6
and Zn(NO ) ·6H O (13 mg, 0.045 mmol) were dissolved in
3
2
2
Received: July 20, 2014
Published: September 25, 2014
©
2014 American Chemical Society
10649
dx.doi.org/10.1021/ic5017092 | Inorg. Chem. 2014, 53, 10649−10653

Inorganic Chemistry
Article
Å3, corresponding to 65.5% of unit cells of SDU-1, after the
removal of the axial ligands.
DMF:EtOH:H O (v:v:v = 1:1:1, 1 mL). Upon addition of a drop of
2
HBF , a colorless solution was obtained, which was heated in a sealed
4
tube, slowly heated to 90 C from room temperature in 5 h, kept at 90
Although SDU-1 possesses a high solvent-accessible volume
and large cages that can store gas molecules, poor porosity
°
C for 48 h, and then slowly cooled to 30 °C in 10 h. The colorless
polyhedral crystals were obtained by filtration (yield: 42% based on
2
−1
(
BET surface area: 165 m g ) was found for SDU-1 by N
2
Zn). Elemental analysis: Calc. (%) for C H O N Zn : C 43.07, H
8
9
136 45
7
7
adsorption surface area measurements, which may be derived
−1
5
3
1
.52, N 3.95. Found: C 42.88, H 5.13, N 5.38. IR data (KBr, cm ):
432 (m), 2920 (s), 1645 (s), 1565 (s), 1438 (s), 1368 (s), 1242 (s),
096 (s), 920 (s), 780 (s), 718 (s), 460 (s).
12
from its inherent surface instability after solvent removal. The
recent development of post-synthetic modification of MOFs
prompted us to study the possibility of metal-ion metathesis in
a SCSC manner. Since Cu paddlewheel SBU normally
Procedure for Ion Exchange for Cu-SDU-1. In the ion exchange
experiment, the single crystal SDU-1 was soaked in a dimethyl
16
formamide/ethyl alcohol/water (DMF/EtOH/H O, v/v/v = 1:1:1)
possesses high stability upon removal of axial ligands, thus,
we select Cu2+ ions to exchange with Zn ions to construct
porous MOF. The as-synthesized crystals of SDU-1 were
2
2+
solution of CuCl for different time. During the period, the solution
2
was replaced with a fresh solution of CuCl once a day. After removing
2
the solution, the ion-exchanged crystals were washed with the mother
solution to remove any excess metal salt. Elemental analysis: Calc. (%)
for C100H174O N Cu : C 39.18, H 5.72, N 4.56; Found: C 40.88, H
immersed into 0.1 M DMF/EtOH/H O (v/v/v = 1:1:1)
2
solution of CuCl . The exchange process was monitored by
2
69
10
7
energy-dispersive X-ray spectroscopy (EDX), atomic absorp-
tion spectroscopy (AAS), and single-crystal X-ray diffraction
−1
5.23, N 4.86. IR data (KBr, cm ): 3442 (w), 2928 (w), 1655 (s), 1434
(
(
m), 1378 (s), 1253 (w), 1104 (w), 922 (w), 780 (m), 727 (m), 699
w), 664 (w), 614 (w), 483 (w).
(
XRD) analysis (see Figure 2). The colorless crystals turned
RESULTS AND DISCUSSION
■
Metal-Ion Metathesis in a Single-Crystal-to-Single-
Crystal (SCSC) Manner. Recently, a novel zinc-organic
framework (SDU-1) based on a C -symmetric tricarboxylate
3
ligand, 3,3′,3″,5,5′,5″-benzene-1,3,5-triyl-hexabenzoic acid
14
(
H TMBHB), was reported by our group. In SDU-1, there
6
are two types of secondary building units (SBUs):
Zn (COO) ] and [Zn (COO) ], which are further linked by
[
2
3
2
4
6
the backbone of TMBHB ligands, to form cubic and
trisoctahedral supermolecular building blocks (SBBs), respec-
tively. These two different SBBs were packed into a
complicated three-dimensional (3D) framework with 3D
channels (see Figure 1). In the framework, the ratio of
[
Zn (COO) ] and [Zn (COO) ] is 4:3, and different
2 3 2 4
simplification of the SBUs and SBBs can make SDU-1 possess
different topologies, common rht and rare ftw networks. The
15
solvent-accessible volume calculated by PLATON is 37 655.6
Figure 2. (a) Photographs of the SDU-1 sample before and after the
metal-ion metathesis, (b) photographs of a single crystal of SDU-1
taken during the exchange of Zn2 with Cu by immersion in a DMF/
+
2+
EtOH/H O (v/v/v = 1:1:1) solution of CuCl (0.1 M) for different
2
2
times, (c, d) EDX for the conversion of SDU-1 to Cu-SDU-1, (e)
kinetic profile of the Zn/Cu exchange process, and (f) the crystal data
for SDU-1 and Cu-SDU-1.
into pale green crystals within 24 h, then green crystals after 7
days. From AAS, it is clear that the process of metal-ion
metathesis in this work is very slow, compared to other
8
d,10b
reported results,
and the Zn ions cannot be completely
exchanged by Cu ions. On the basis of AAS, 99.58% of Zn ions
were replaced by Cu ions even after 15 days. This different
result with other reports makes us reanalyze the crystal
structure of SDU-1. In the asymmetric unit, there are four
II
crystallographically independent Zn ions (Zn1, Zn2, Zn3,
Zn4) with three different coordination environments. Both Zn1
and Zn2 are coordinated by five oxygen atoms in a distorted
square pyramidal coordination geometry, and linked by four
carboxylate groups to form a paddlewheel [Zn (COO) ] SBU.
Figure 1. SBB assembly of SDU-1 from the trigonal rigid ligand and
two types of SBUs.
2
4
Although Zn3 and Zn4 are linked by three carboxylate groups
1
0650
dx.doi.org/10.1021/ic5017092 | Inorg. Chem. 2014, 53, 10649−10653

Inorganic Chemistry
Article
to generate a [Zn (COO) ] SBU, they possess different
Low-pressure H , CO , and CH uptakes of desolvated
sample of Cu-SDU-1 were continuously determined using
volumetric gas adsorption measurements. As shown in Figure 4,
2
3
2
2
4
coordination environment: Zn3 is coordinated by six oxygen
atoms in an octahedral coordination geometry, whereas Zn4 is
coordinated by four oxygen atoms in a tetrahedral geometry. It
2
+
is known that Cu ion can normally adopt square planar,
square pyramidal, and octahedral coordination geometries.
Generally, it is quite rare or impossible for Cu2+ ion to adopt a
tetrahedral coordination geometry. Hence, it is very difficult for
2
+
the Zn4 ion to be exchanged by a Cu ion in this work.
2
+
However, under the condition of high concentration of Cu
ions, it is possible that Zn4 ions were exchanged by Cu2+ ions
over a long period of time.
Single-crystal XRD study of Cu-SDU-1 reveals that the
structure is identical to that of SDU-1 (see Figure 2f),
indicating the metal-ion metathesis is through a single-crystal-
to-single-crystal fashion. It should be pointed out that, through
the metal-ion metathesis, the crystal quality changed to poor.
There are large solvent-accessible void volumes in the crystals
of Cu-SDU-1, which are occupied by disordered DMF and
water molecules. No satisfactory disorder model could be
achieved, so the PLATON/SQUEEZE routine was used to
remove these electron densities. The structure was refined by
using the new .HKL file.
Gas Uptakes. To check if the metal-ion metathesis can
improve the stability and the porosity of the complex, the
freshly exchanged sample of Cu-SDU-1 was soaked in
methanol and dichloromethane to exchange the less-volatile
solvates, followed by evacuation under a dynamic vacuum at
appropriate temperature, generating dehydrated form. In order
to find the optimal temperature, the sample was activated at 40,
8
0, and 100 °C, then N adsorption measurements were carried
Figure 4. H , CO , and CH sorption isotherms for SDU-1 (left) and
2 2 4
2
Cu-SDU-1 (right). (For H : red symbols, 77 K; blue symbols, 87 K.
out. When the sample was activated at 40 °C, it possesses a
larger surface area (Figure 3a). Thus, following measurements
on H , CO , and CH , the sample was also activated at 40 °C.
2
For CO : red symbols, 273 K; blue symbols, 295 K. For CH : red
2
4
symbols, 273 K; blue symbols, 295 K.)
2
2
4
the desolvated Cu-SDU-1 exhibits the classical reversible Type-
I isotherms for H , CH , and CO . Under the conditions of 77
2
4
2
3
−1
K and 1 bar, the desolvated Cu-SDU-1 can adsorb 94 cm g
of H molecules, whereas SDU-1 can only adsorb 57 cm g of
3
−1
2
H molecules, which is 39% lower than that of Cu-SDU-1. The
2
H isosteric heat of adsorption (Q ) was calculated by fitting
2
st
the H adsorption isotherms at 77 and 87 K to a virial-type
2
expression. At the lowest coverage, Q has estimated values of
st
1
7
.5 and 8.7 kJ mol− for Cu-SDU-1 and SDU-1, respectively,
17a
which are comparable to that of NOTT-116, but are slightly
higher than those of NOTT-112-115 and NU-100. However,
Figure 3. (a) N sorption isotherms at 77 K for Cu-SDU-1 under
17
2
different activation temperatures: 40 °C (red symbols), 80 °C (black
decreasing pore size is associated with higher Q values for
SDU-1; this negative effect exists in the competition and leads
st
symbols), and 100 °C (blue symbols). (b) N sorption isotherms at 77
2
K for Cu-SDU-1 (red symbols) and SDU-1 (blue symbols).
to a small decrease in the H uptake. It suggests that the use of
2
the metal-ion metathesis method to obtain the Cu-SDU-1
Desolvated Cu-SDU-1 displays typical Type-I adsorption
isotherms (Figure 3b), suggesting the retention of the
microporous structures after the removal of solvates from the
improves its adsorption capacity toward H , but does not
2
enhance its heat of adsorption. It indicates that a much stronger
18
interaction exists between H and the SDU-1. Cu-SDU-1
2
3
−1
crystalline sample. The total pore volume of 0.203 cm g for
exhibits low CO and CH uptakes at 273 K, with total
2
4
3
−1
Cu-SDU-1 was calculated from the N isotherm (P/P = 0.98).
adsorption amounts of 64 and 45 cm g , respectively.
However, SDU-1 can only adsorb 37 cm g of CO molecules
and 14 cm g of CH molecules, which represent values that
2
0
3
−1
3
−1
Cu-SDU-1 can adsorb 126 cm g of N molecules under the
2
2
3
−1
conditions of 77 K and 1 atm, which is almost 3 times greater
4
3
−1
than that of SDU-1 (43 cm g ). This result indicates that the
metal-ion metathesis significantly increases the porosity of the
framework. The Brunauer−Emmett−Teller (BET) surface area,
are, respectively, 42% and 69% lower than that of Cu-SDU-1.
Although Cu-SDU-1 possesses low CO uptake, Q has an
2
st
−
1
estimated value of 37.7 kJ mol , which is comparable to
amino-MIL-53 (Al; 38.4 kJ mol ), indicating that the
2
−1
−1 19
which is determined by fitting the N isotherms, is 534 m g
2
for Cu-SDU-1, which represents a 224% increase, compared to
that of SDU-1 (BET: 165 m g ).
framework of Cu-SDU-1 exhibits high affinity to CO2
molecules.
2
−1
1
0651
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Inorganic Chemistry
Article
The comparison of gas uptake for SDU-1 and Cu-SDU-1 is
Scheme 1. Lewis Acid-Catalyzed Reaction of Carbonyl
listed in Table 1, from which we can conclude that the metal-
Compounds with Cyanide
Table 1. Comparison of BET Surface Area, Pore Volume,
and Gas Uptakes for SDU-1 and Cu-SDU-1
SDU-1 Cu-SDU-1 increase (%)
BET surface area (m g−1)
2
165
534
224
186
62.7
pore volume (cm g−1)
3
0.07
0.2
H uptake at 1 atm, 77 K (wt %)
H enthalpy, Q (kJ mol−1)
0.51
8.7
0.83
7.5
2
2
st
CO uptake (cm g−1)
3
37
14
64
73.0
221
2
CO enthalpy, Q (kJ mol−1)
37.7
2
st
CH uptake (cm g−1)
3
45
4
CH enthalpy, Q (kJ mol−1)
3.7
4
st
ion metathesis has significantly improved the porosity.
However, Cu-SDU-1 still exhibits lower surface area than
that expected. As mentioned above, there are two different
types of SBUs in the framework: [Cu (COO) ] and
of stable MOFs have been documented, improving the stability
or functionality of known or as-synthesized MOFs through
post-modification is an attractive target for chemists. In the
present work, we have applied the metal-ion metathesis process
to improve the porosity and stability as well as catalytic capacity
of a MOF (SDU-1) previously reported by our group. The gas
2
3
[
Cu (COO) ]. As is known, the paddlewheel [Cu (COO) ]
2
4
2
4
SBU is stable after the removal of the axial ligands, but the
Cu (COO) ] SBU may be unstable after the activation
[
2
3
adsorption for zinc paddlewheel ([Zn (COO) ] and
process, which can cause partly inherent surface instability as
found in Zn-HKUST-1.
2
3
12
[
Zn (COO) ]) MOF has been measured for the first time,
2 4
although inherent surface instability upon removal of solvates
still exists in SDU-1. Through replacement of the Zn ions by
Catalytic Capacity. Porous MOFs show excellent catalytic
properties in many organic reactions. To further test if the
metal-ion metathesis can improve the stability and porosity of
SDU-1, the Lewis acid-catalyzed reaction of carbonyl
compounds with cyanide was carried out. Before the catalytic
test, the newly solvent-exchanged samples of SDU-1 and Cu-
SDU-1 were activated at 40 °C under vacuum for 4 h. Cu-
SDU-1 shows high activity in the cyanosilylation of
benzaldehyde and naphthaldehyde, and 100% conversions
were reached in 24 h at room temperature. The yields can reach
2
+
2+
Cu ions in SDU-1 via metal-ion metathesis process, the
porosity and catalytic capacity have been significantly improved.
Our research results, presented here, further confirmed the
important role of metal-ion metathesis on improving the
stability and porosity, as well as catalytic capacity, of an MOF,
and also further proved the existence of inherent surface
instability for some unstable SBUs, such as zinc [Zn (COO) ]
2
4
paddlewheel and copper [Cu (COO) ] paddlewheel upon
2
3
removal of the solvates.
9
7.25% and 94.93% after 24 h for the cyanosilylation of
benzaldehyde and naphthaldehyde, respectively. The catalytic
ASSOCIATED CONTENT
Supporting Information
X-ray crystallographic data in CIF format, IR curves (Figure
S1), PXRD patterns (Figure S2), TGA curves (Figure S3), the
catalytic capacity for Cu-SDU-1 (Scheme S1). This material is
available free of charge via the Internet at http://pubs.acs.org.
activity of Cu-SDU-1 is comparable to other Mn- or Ln-based
■
2
0
MOFs in the cyanosilylation of benzaldehyde, but is much
higher than other reported results in the cyanosilylation of
*
S
20b,21
naphthaldehyde.
When a larger 4-(tert-butyl) benzalde-
hyde was used, a significantly lower conversion/yield was
20b
obtained (79.95%/65.06%), which is similar to other reports.
However, SDU-1 shows a lower catalytic activity than that of
Cu-SDU-1. As shown in Scheme 1, after 24 h, conversions of
AUTHOR INFORMATION
Corresponding Authors
E-mail: liangliangzhang@upc.edu.cn (L. Zhang).
E-mail: dfsun@sdu.edu.cn (D. Sun).
■
*
*
6
8
2.02% and 88.26%, with corresponding yields of 44.57% and
1.29%, were reached for the cyanosilylation of benzaldehyde
and naphthaldehyde, respectively; these values are 118% and
1
4
6.8% lower, compared to Cu-SDU-1, in the yield. For a larger
-(tert-butyl) benzaldehyde, the yield was only 65.85%
Notes
The authors declare no competing financial interest.
conversion with 50.87% yield after 24 h at room temperature.
These catalytic results further confirm that the metal-ion
metathesis have significantly improved the stability and catalytic
capacity.
ACKNOWLEDGMENTS
■
This work was supported by the NSFC (Grant No. 21271117
and 21371179), NCET-11-0309, the Shandong Natural Science
Fund for Distinguished Young Scholars (No. JQ201003), NSF
of Shandong Province (BS2011CL041), and the Fundamental
Research Funds for the Central Universities (Nos.
13CX05010A, 14CX02158A).
CONCLUSIONS
The construction of functional metal-organic frameworks
MOFs) with permanent porosity have been of extensive
■
(
interest. Although several strategies on the design and synthesis
1
0652
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Article
(
9) (a) Han, Y.; Chilton, N. F.; Li, M.; Huang, C.; Xu, H.; Hou, H.;
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