Ligand-Directed Reticular Synthesis of Catalytically Active Missing Zirconium-Based Metal-Organic Frameworks

Article abstract of DOI:10.1021/jacs.9b06179

Zirconium-based metal-organic frameworks (Zr-MOFs) based on edge-transitive nets such as fcu, spn, she, csq, and ftw with diverse potential applications have been widely reported. Zr-MOFs based on the highly connected 6,12-connected alb net, however, remain absent on account of synthetic challenges. Herein we report the ligand-directed reticular syntheses and isoreticular expansion of a series of Zr-MOFs with the edge-transitive alb net from 12-connected hexagonal-prismatic Zr₆ nodes and 6-connected trigonal-prismatic linkers, i.e., microporous NU-1600, mesoporous NU-1601, and mesoporous NU-1602. These Zr-MOFs exhibit remarkable activities toward the destruction of a nerve agent (soman) and a nerve agent simulant (DMNP).

Full text of DOI:10.1021/jacs.9b06179

Communication
Cite This: J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
pubs.acs.org/JACS
Ligand-Directed Reticular Synthesis of Catalytically Active Missing
Zirconium-Based Metal−Organic Frameworks
Zhijie Chen, Penghao Li,† Xingjie Wang, Ken-ichi Otake, Xuan Zhang, Lee Robison,†
†
†
†
†
†
†
‡
‡
†,§,∥
Ahmet Atilgan, Timur Islamoglu, Morgan G. Hall, Gregory W. Peterson, J. Fraser Stoddart,
,
†
and Omar K. Farha*
†Department of Chemistry and International Institute of Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston,
Illinois 60208, United States
‡
U.S. Army Combat Capabilities Development Command Chemical Biological Center, 8198 Blackhawk Road, Aberdeen Proving
Ground, Maryland 21010, United States
§
Institute for Molecular Design and Synthesis, Tianjin University, 92 Weijin Road, Tianjin 300072, China
∥
School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia
*
S Supporting Information
31
include but are not limited to spn (e.g., MOF-808; triangle and
33
ABSTRACT: Zirconium-based metal−organic frame-
works (Zr-MOFs) based on edge-transitive nets such as
fcu, spn, she, csq, and ftw with diverse potential
applications have been widely reported. Zr-MOFs based
on the highly connected 6,12-connected alb net, however,
remain absent on account of synthetic challenges. Herein
we report the ligand-directed reticular syntheses and
isoreticular expansion of a series of Zr-MOFs with the
edge-transitive alb net from 12-connected hexagonal-
trigonal antiprism), she (e.g., PCN-224; square and hexagon),
3
4
35
hxg (e.g., pbz-MOF-1; hexagon), the (e.g., NU-1200 /BUT-
1
36
37
38
2; triangle and cube), csq (e.g., PCN-222 /MOF-545 and
39 22
NU-1000; square and cube), flu (e.g., PCN-521; tetrahe-
40
dron and cube), reo (e.g., DUT-51; cube); ftw (e.g., MOF-
38
41
5
25 and MOF-1211; square and cuboctahedron), ith (e.g.,
31
MOF-812;4 tetrahedron and icosahedron), and shp (e.g.,
2
PCN-223; square and hexagonal prism) (see Table S2 for a
complete list). Nevertheless, an important class of Zr-MOFs
prismatic Zr nodes and 6-connected trigonal-prismatic
6
based on a highly connected edge-transitive net, the 6,12-c alb
21,24,43
linkers, i.e., microporous NU-1600, mesoporous NU-
net,
(trigonal prism and hexagonal prism; “alb” denotes
1
601, and mesoporous NU-1602. These Zr-MOFs exhibit
“
aluminum diboride”), has yet to be reported, most likely
remarkable activities toward the destruction of a nerve
agent (soman) and a nerve agent simulant (DMNP).
because of the lack of synthetic accessibility of the rigid trigonal-
prismatic ligands and suitable assembly conditions. Higher
connectivity in MOF structures permits an increased degree of
controllability and designability. It is important to note that the
synthesis of alb-MOFs based on rare-earth polynuclear clusters
and indium trimers employing reticular chemistry has been
1
−3
etal−organic frameworks (MOFs),
inorganic nodes and organic linkers, are a class of porous
crystalline materials with a wide range of applications, including
composed of
M
24,43
reported recently by the Eddaoudi group.
4
−9
but not limited to heterogeneous catalysis,
selective
and gas storage and
Herein we report the reticular synthesis of a Zr-MOF with the
1
0−12
13,14
sensing,
separation.
water remediation,
rare 6,12-c alb net, NU-1600, constructed from threefold-
1
5−19
20−25
42,44
Reticular chemistry
permits the rational
disordered Zr
triptycene (H
6
nodes
and the peripherally extended
25,45
top-down design and precise assembly of MOFs at the molecular
level from the diverse choices of inorganic and organic building
units. Consequently, MOFs have highly programmable
structures with tunable pore sizes and apertures, high surface
6
PET-1) ligands
with a rigid trigonal-prismatic
shape. Single-crystal X-ray diffraction (SCXRD) analysis
revealed that the 6-c trigonal-prismatic PET-1 ligands and the
1
2-c Zr nodes act as rare hexagonal-prismatic secondary
6
7
,15−17,26−29
building units (SBUs), leading to the assembly of 3-periodic
NU-1600 with the alb net (Figure 1). NU-1600 is microporous,
with an apparent Brunauer−Emmett−Teller (BET) surface area
areas, and diverse functionality.
Zirconium-based MOFs
28,30
(Zr-MOFs) represent a remark-
able MOF subclass on account of the strong Zr−O coordination
bond, and they have received considerable attention in the field
since the first Zr-MOFi.e., UiO-66 (where “UiO” denotes
2
−1
of 2085 m g and an experimental pore volume (PV) of 0.82
3
−1
cm g , as revealed by its N adsorption isotherm at 77 K. The
2
expanded mesoporous isoreticular structuresi.e., NU-1601
“
1
University of Oslo”) with Zr inorganic building blocks and the
6
3
−1
3
and NU-1602, with experimental PVs of up to 2.36 cm g 
can be readily synthesized (Figure S1) with extended ligands,
namely, H PET-2 and H PET-3, respectively. On account of the
2-connected (12-c) fcu topologywas reported. Tremen-
dous efforts have been devoted to the development of Zr-MOFs
based on edge-transitive netsi.e., nets with one type of edge
because of the upsurge in reticular chemistry and versatile
6
6
Lewis acidic Zr sites, NU-1600 exhibits excellent catalytic
28
connectivity of polynuclear Zr clusters. Many applications of
these Zr-MOFs have been investigated, from heterogeneous
Received: June 10, 2019
4
,8
31,32
catalysis to water capture.
These edge-transitive networks
©
XXXX American Chemical Society
A
DOI: 10.1021/jacs.9b06179
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

Journal of the American Chemical Society
Communication
Figure 1. Top-down design and synthesis of a highly connected Zr-MOF with rigid trigonal-prismatic linkers, NU-1600, based on the 6,12-c edge-
transitive alb-net. Atom color scheme: C, gray; Zr, bright green; O, red. H atoms have been omitted for the sake of clarity.
performance toward the destruction of nerve agent simulants in
the presence of both liquid and solid bases.
The alb net, constructed from 6-c trigonal-prismatic SBUs
Indeed, single crystals of NU-1600 (Figure 2) with suitable
sizes for SCXRD investigation were obtained after careful fine-
tuning of the synthetic conditionsi.e., ZrCl
acidic modulators were dissolved in N,N-diethylformamide
DEF), and the mixture was then kept at 130 °C for 4 days.
, PET-1, and
4
and 12-c hexagonal-prismatic SBUs, is one of the most intriguing
21
(
binodal edge-transitive nets. The (6,12)-c alb net is a highly
connected net that could potentially be realized in Zr-MOFs by
rational design and precise control of the geometry of the
organic linkers. In this work, the augmented alb (alb-a) net was
used to illustrate the topological network. Threefold-disordered
SCXRD analysis revealed that NU-1600 crystallizes in space
group P2/m (a = 21.632(1) Å, b = 12.2815(5) Å, c = 21.627 (1)
Å, and β = 119.975(2)° at 100 K) with an ideal formula Zr (μ -
6
3
O) (μ -OH) (HCOO)(OH)(H O)(PET-1) , without consid-
2
3
6
2
2
ering the missing-linker defects (Table S1 and Figure S2). Each
42
44
Zr nodes have been observed in PCN-223 and NU-904
6
PET-1 ligand of NU-1600 is coordinated to six Zr nodes, and
6
with the overall topology of the 4,12-c shp net, where the Zr6
nodes can be viewed as rare hexagonal-prismatic SBUs. We
anticipated that the use of rigid trigonal-prismatic PET-1 ligands
each threefold-disordered Zr node is coordinated to 12 PET-1
6
linkers, rendering the expected 6,12-c alb net. The 12-c Zr node
6
of NU-1600, which can be viewed as a hexagonal-prismatic SBU,
is different from the 12-c Zr6 node of UiO-66i.e., a
cuboctahedron SBU (Figure S3). To the best of our knowledge,
the alb net was a missing edge-transitive net for the well-
would guide the in situ formation of 12-c Zr nodes as
6
hexagonal-prismatic SBUs, thus resulting in a 3-periodic
structure with the alb net.
B
DOI: 10.1021/jacs.9b06179
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Journal of the American Chemical Society
Communication
Figure 2. (A) Structures of organic ligands used in this work. (B) Representative structures of NU-1600, NU-1601, and NU-1602 viewed along the b
axis. (C−E) Optical images of single crystals of (C) NU-1600, (D) NU-1601, and (E) NU-1602.
developed functional Zr-MOFs until we uncovered it. NU-1600
distribution based on a density functional theory (DFT)
can alternatively be further analyzed as an (3,3,12)-c alb-derived
ury net if the ligand is deconstructed into two 3-c SBUs.
model from the N adsorption isotherm revealed one type of
2
24,43
main pore centered at 1.2 nm (Figure 3B), which agrees with the
size of the diamond-shaped channels. Extra pores ranging from
1.5 to 2.2 nm could be associated with the missing-linker defects.
Highly connected edge-transitive nets induce higher degrees
of designability with precise choices of building units. They offer
more possibilities toward elongated isoreticular structures
NU-1600 contains one type of diamond-shaped channels with
a dimension of ca. 1.1 nm along the b axis and two-dimensional
honeycomb-shaped channels in the ac plane (Figure S4). The
microcrystalline sample of NU-1600 was synthesized with sizes
of 1−2 μm, as revealed by scanning electron microscopy (SEM)
24,26,49−51
(Figure S11). The phase purity of the bulk NU-1600 was
without catenation.
Solvothermal reactions of longer
confirmed by the well-matched simulated and as-synthesized
powder X-ray diffraction (PXRD) patterns (Figure S5). The
permanent porosity of NU-1600 was confirmed by the N2
adsorption isotherm at 77 K with an estimated apparent BET
peripherally extended triptycene ligandsi.e., H PET-2 and
6
H PET-3and ZrCl under synthetic conditions similar to
6
4
those for NU-1600 yielded colorless hexagonal block crystals of
NU-1601 and NU-1602, respectively. SCXRD studies revealed
that both materials have noncatenated structures crystallizing in
space group P2/m (NU-1601: a = 28.130(3), b = 16.735(2), c =
28.174(3) (1) Å, and β = 120.036(4)° at 275 K; NU-1602: a =
31.678(8), b = 19.591(4), c = 31.774(1) Å, and β = 119.631(2)°
at 275 K). The phase purities of bulk NU-1601 and NU-1602
were confirmed by the well-matched simulated and as-
synthesized PXRD patterns (Figures S6 and S7). Topological
analysis revealed that NU-1601 and NU-1602 have the same
underlying 6,12-c alb topology as NU-1600 with threefold-
2
−1
surface area of 2085 m g (Figures 3 and S14). It is interesting
3
−1
to note that the experimental total PV of 0.82 cm g is higher
3
−1
than the simulated valuei.e., 0.69 cm g for the structure
when PET-1 has 100% occupancy inside NU-1600 but agrees
3
−1
well with the simulated PVi.e., 0.83 cm g when PET-1
has 70% occupancy (Table S5). In fact, the best crystallographic
refinement of the SCXRD data was obtained for NU-1600 when
the occupancy level of PET-1 is around 70%, indicating the
4
6−48
presence of missing-linker defects.
The pore size
C
DOI: 10.1021/jacs.9b06179
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

Journal of the American Chemical Society
Communication
Figure 3. (A) Experimental N adsorption and desorption isotherms at
2
7
7 K and (B) DFT pore size distributions for NU-1600, NU-1601, and
NU-1602.
disordered Zr nodes and extended PET ligands as 12-c
6
hexagonal-prismatic and 6-c trigonal-prismatic SBUs, respec-
tively.
N adsorption isotherms of NU-1601 and NU-1602 at 77 K
2
after supercritical CO activation revealed that both structures
2
are mesoporous MOFs with experimental total PVs of 1.75 and
3
−1
2
1
.36 cm g , respectively, at P/P = 0.95. NU-1601 and NU-
0
3
−1
602 exhibited N2 uptakes of 1133 and 1531 cm g ,
respectively at 77 K and P/P = 0.95. The pore size distributions
0
of NU-1601 and NU-1602 based on DFT models from the N2
adsorption isotherms revealed main pores centered at 1.4 and
1
.7 nm, respectively, which agree with the sizes of the diamond
channels. Similar to NU-1600, the extra mesoporesi.e., 2.2
and 2.7 nmcan be attributed to missing-linker defects. The
apparent BET areas of NU-1601 and NU-1602 were estimated
Figure 4. (A) Hydrolysis reaction of DMNP. (B) Hydrolysis profiles of
DMNP with NU-160X (X = 0, 1, 2) using 6 mol % catalyst loadings in
the presence of different bases: N-ethylmorpholine and linear PEI. (C)
First 10 min of the hydrolysis profile shown in (B) for clarity. Solid lines
are used as guides. (D) Conversion vs time data for NU-1600 and NU-
1600/PEI for the hydrolysis of soman. Dotted lines correspond to first-
order fits.
2
−1
to be 3970 and 4500 m g , respectively, after the four BET
consistency criteria were satisfied with correlation coefficients
52
higher than 0.995 (Figures S15 and S16 and Table S4).
Zr-MOFs have been widely evaluated for the hydrolysis of
dimethyl 4-nitrophenyl phosphonate (DMNP), a nerve agent
simulant mimicking the reactivity of organophosphonate-based
nerve agents, on account of Lewis acidic sites on the Zr
MOFs with similar Zr nodes and pore sizes ranging from
micropore to mesopore are still limited. Herein, taking
6
6
4
,53−58
nodes.
However, systematic studies of isoreticular
D
DOI: 10.1021/jacs.9b06179
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Journal of the American Chemical Society
Communication
advantage of the missing-linker defects in NU-160X (X = 0, 1,
Crystallographic data for NU-1600 (CIF)
2
), which expose the Lewis acidic sites on the Zr nodes, we
Crystallographic data for NU-1601 (CIF)
Crystallographic data for NU-1602 (CIF)
explored the hydrolysis of DMNP using microsized (1−4 μm)
crystals of NU-160X (X = 0, 1, 2) (Figures S11−S13) in the
presence of liquid N-ethylmorpholine and solid linear
polyethylenimine (PEI) (Figures 4, S17, and S18). The initial
half-life of DMNP in the presence of N-ethylmorpholine with
NU-1600 (6 mol % catalyst loading) was quite short (t ≈ 1
min), with a turnover frequency (TOF) of 0.21 s . Under the
same conditions, the hydrolysis of DMNP exhibited similar
TOFs, namely, 0.22 and 0.15 s− for catalyst loadings of 3 and
AUTHOR INFORMATION
Corresponding Author
*o-farha@northwestern.edu
ORCID
Zhijie Chen: 0000-0001-9232-7382
Penghao Li: 0000-0002-1517-5845
Xingjie Wang: 0000-0002-5802-9944
Ken-ichi Otake: 0000-0002-7904-5003
Xuan Zhang: 0000-0001-8214-7265
Lee Robison: 0000-0002-7419-4499
Timur Islamoglu: 0000-0003-3688-9158
Gregory W. Peterson: 0000-0003-3467-5295
J. Fraser Stoddart: 0000-0003-3161-3697
Omar K. Farha: 0000-0002-9904-9845
■
1
/2
−
1
1
1
.5 mol %, respectively (Tables S6 and S7).
Moreover, NU-1600 can efficiently hydrolyze DMNP in the
presence of a solid basei.e., linear PEIwith t ≈ 3 min and
1
/2
−
1
TOF = 0.05 s . After washing with water, the NU-1600/PEI
composite displays similar reactivity, confirming the heteroge-
neous nature of the PEI base (Figure S19), which is more
practical for protective suit and mask applications. NU-1601
and NU-1602 show similar performance as NU-1600 toward the
54
hydrolysis of DMNP, but the hydrolysis is slightly slower (t1/2
≈
3
.2 and 2.5 min, respectively). These data suggest that the higher
degree of missing-linker defects in NU-1600 compared with
either NU-1601 or NU-1602, as illustrated by thermogravi-
metric analysis (TGA) under air flow (Figures S8−S10 and
Table S3), induces a larger number of Lewis acidic Zr catalytic
sites for the hydrolysis to occur, since the particle sizes of these
isostructural materials are similar.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
O.K.F. gratefully acknowledges support from the Defense
Threat Reduction Agency (HDTRA1-18-1-0003 for catalysis
and HDTRA1-19-1-0007 for MOF synthesis). This work made
use of the EPIC facility of Northwestern University’s NUANCE
Center, which has received support from the Soft and Hybrid
Nanotechnology Experimental (SHyNE) Resource (NSF
NNCI-1542205); the MRSEC program (NSF DMR-
The NU-1600/PEI composite enhances the hydrolysis rate of
an actual nerve agent, soman (GD), compared with NU-1600.
The conversion of GD to the nontoxic pinacolyl methylphos-
phonic acid (PMPA) as a function of time is shown in Figure 4D,
3
1
and P NMR spectra show the conversion of PMPA (Figures
S20−S22). The enhanced reactivity arising from the solid-phase
PEI base is clear, with 50% of GD reacting in the presence of
NU-1600/PEI sample in under 12 min, compared with only
1
720139) at the Materials Research Center; the International
Institute for Nanotechnology (IIN); the Keck Foundation; and
the State of Illinois through the IIN. This work made use of the
IMSERC at Northwestern University, which has received
support from the NSF (CHE-1048773 and DMR0521267);
the SHyNE Resource (NSF NNCI-1542205); the State of
Illinois, and the IIN. P.L. and J.F.S. acknowledge the Joint
Center of Excellence in Integrated Nano-Systems (JCIN) at
King Abdulaziz City for Science and Technology (KACST) and
Northwestern University (NU). G.W.P. and M.H. gratefully
acknowledge support from the Defense Threat Reduction
Agency under Grant CB3934 for the hydrolysis of GD. We
thanks Margaret E. Schott for the proofreading of this paper.
2
0% of GD reacting on baseline NU-1600 after 400 min. The
rate constants calculated from a first-order kinetic model are 6.2
×
−
4
−2
−1
10 and 5.4 × 10 min for NU-1600 and NU-1600/PEI,
respectively. These results demonstrated that the NU-1600/PEI
composite can efficiently detoxify the chemical warfare agent.
In conclusion, we have rationally designed and synthesized a
series of missing Zr-MOFs, the NU-160X series (X = 0, 1, 2),
with the edge-transitive 6,12-c alb topology. The highly
connected alb net provides a blueprint for programmable
noncatenated MOF structures with tunable surface areas and
tailorable porosities ranging from microporous to mesoporous.
These structurally defective Zr-MOFs display notable activities
toward the efficient destruction of a nerve agent as well as its
simulant in the presence of liquid and solid bases. This research
illustrates the power of reticular chemistry for the rational design
and synthesis of functional highly connected materials and paves
the way for correlating unique material properties with desired
functionalities.
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*
S
Supporting Information
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