Catalytic mOF-Cloth Formed via Directed Supramolecular Assembly of UiO-66-NH2 Crystals on Atomic Layer Deposition-Coated Textiles for Rapid Degradation of Chemical Warfare Agent Simulants

Article abstract of DOI:10.1021/acs.chemmater.7b00949

Highly tunable metal-organic framework (MOF) materials, including, for example, UiO-66-NH₂, are known to be effective catalysts to degrade chemical warfare agents (CWAs) with half-lives near 1 min. Therefore, many researchers have been actively working on producing supported MOF materials to improve application effectiveness by using relatively slow solvothermal synthesis or repetitious stepwise layer-by-layer methods. Herein, we demonstrate a facile route to rapidly assemble presynthesized UiO-66-NH₂ crystals onto nonwoven polypropylene (PP) fibrous mats at ambient temperature. Crystal assembly is chemically directed using β-cyclodextrin (β-CD) and cetyltrimethylammonium bromide (CTAB) as surfactant assembly agents, where the agents quickly (within 5 min) self-assemble on the crystal surface and promote physically robust chemical surface attachment while simultaneously impeding solution-phase crystal agglomeration. Furthermore, we find that when the PP is preconditioned using conformal metal oxide thin films, including Al₂O₃, TiO₂, or ZnO formed via atomic layer deposition (ALD), the hydrophilic metal oxide surface further helps improve assembly uniformity and MOF mass loading, producing MOF crystal loading as high as 40 wt % and an overall BET surface area exceeding 200 m²/g_(MOF+Fiber). Using these surface-assembled MOFs, we observe catalytic degradation of dimethyl 4-nitrophenyl phosphate (DMNP), a CWA simulant, with a half-life of less than 5 min.

Full text of DOI:10.1021/acs.chemmater.7b00949

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Article
A Catalytic "MOF-Cloth" Formed via Directed Supramolecular
2
Assembly of UiO-66-NH Crystals on ALD-coated Textiles for
Rapid Degradation of Chemical Warfare Agent Simulants
Dennis T. Lee, Junjie Zhao, Gregory W. Peterson, and Gregory N Parsons
Chem. Mater., Just Accepted Manuscript • Publication Date (Web): 12 May 2017
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Chemistry of Materials
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A Catalytic "MOF-Cloth" Formed via Directed Supramolecular
Assembly of UiO-66-NH2 Crystals on ALD-coated Textiles for
Rapid Degradation of Chemical Warfare Agent Simulants
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Dennis T. Lee,† Junjie Zhao,† Gregory W. Peterson,‡ and Gregory N. Parsons,⁎ †
,
†Department of Chemical & Biomolecular Engineering, North Carolina State University, 911 Partners Way, Raleigh,
NC 27695, United States
‡Edgewood Chemical Biological Center, 5183 Blackhawk Road, Aberdeen Proving Ground, MD 21010, United States
ABSTRACT: Highly tunable metal-organic framework (MOF) materials, including for example UiO-66-NH2, are known to
be effective catalysts to degrade chemical warfare agents (CWAs) with half-lives near 1 minute. Therefore, many researchers
have been actively working on producing supported MOF materials to improve application effectiveness by using relatively
slow solvothermal synthesis or repetitious step-wise layer-by-layer methods. Herein, we demonstrate a facile route to rap-
idly assemble pre-synthesized UiO-66-NH2 crystals onto nonwoven polypropylene (PP) fibrous mats at ambient tempera-
ture. Crystal assembly is chemically directed using β-cyclodextrin (β-CD) and cetyltrimethylammonium bromide (CTAB)
as surfactant assembly agents, where the agents quickly (within 5 minutes) self-assemble on the crystal surface and promote
physically robust chemical surface attachment while simultaneously impeding solution-phase crystal agglomeration. Fur-
thermore, we find that when the PP is pre-conditioned using conformal metal oxide thin films, including Al2O3, TiO2, or
ZnO formed via atomic layer deposition (ALD), the hydrophilic metal oxide surface further helps improve assembly uni-
formity and MOF mass loading, producing MOF crystal loading as high as 40 wt.% and an overall BET surface area exceed-
ing 200 m2/g(MOF+Fiber). Using these surface-assembled MOFs, we observe catalytic degradation of dimethyl 4-nitrophenyl
phosphate (DMNP), a CWA simulant, with a half-life of less than 5 minutes.
which require high temperatures or relatively long pro-
INTRODUCTION
cessing times. Unless care is taken to prepare the sur-
face to promote MOF crystal nucleation,20,
these
Metal-organic frameworks (MOFs) are porous and
highly crystalline materials assembled by bridging na-
noscale metal ions or clusters with multifunctional or-
ganic linkers.1 Since MOFs can exhibit tunable porous
structures, exceptionally high surface area and good
chemical, hydrolytic, and thermal stability,2 they have
been explored for a range of applications, such as gas
storage and separation,3 catalysis,4 light harvesting and
energy conversion,5 selective adsorption of anions from
aqueous solutions,6 and recently degrading chemical
warfare agents (CWAs).7, 8 However, MOF batch synthe-
sis methods often require both high reaction tempera-
tures and long reaction time and result in powders that
require further handling and processing for further ap-
plications.9
21
methods commonly lead to poor coverage of MOFs and
low MOF mass fraction on the substrate. Poor surface
coverage results from relatively rapid nucleation in the
solution phase, thereby depleting reactants available for
slower surface nucleation and growth.
Herein, we report a facile and rapid strategy for inte-
gration of MOFs onto polymeric fibrous mats at ambi-
ent temperature using solvent-suspended pre-synthe-
sized MOF crystals. To demonstrate this strategy, we
use UiO-66-NH2, and provide new insight to allow di-
rect assembly and achieve high MOF mass fraction on
polypropylene (PP) nonwoven mats. We examine UiO-
66-NH2 because it is a highly stable Zr-based MOF
known to be effective for catalytic destruction of organ-
ophosphorus nerve-agents and related simulants, such
To overcome the problem of MOF processing, many
approaches have been reported to integrate MOFs into
polymeric,10 organic-inorganic fibrous mats,11 and poly-
mer matrices.12-14 To date, however, these approaches
are limited to demonstrations using MOF precursor so-
as dimethyl 4-nitrophenyl phosphate (DMNP).22, 23
A
challenge for MOF assembly on polypropylene is that
the polymer surface displays only methyl groups, which
cannot form covalent bonds with UiO-66-NH2 crystals
due to polar amine functional groups.24 To promote the
interaction between the MOF and the substrate, we in-
troduced atomic layer deposition (ALD) of metal oxides
lutions to form crystals via methods including in-situ
16
solvothermal synthesis,15,
layer-by-layer growth,17
counter-diffusion,18 or microwave irradiation,19 many of
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to impart surface hydroxyl groups onto the inert PP.25 A
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dosed with another 30 s of N2 purge. We chose 200 cy-
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supramolecular complex comprised of β-cyclodextrin
(β-CD) and cetyltrimethylammonium bromide (CTAB)
was used as a self-assembly agent. The hydroxyl units
on the cylindrical β-CD and cationic head groups on the
linear CTAB molecules lead to a host-guest self-assem-
bly interaction and bind to polar surfaces (including
both the MOF and the modified PP) via van der Waals,
electrostatic interactions, and hydrogen bonding.26-28
The modified surfaces then readily bind to each other at
room temperature, leading to dense MOF assembly on
the PP. Furthermore, the β-CD and CTAB surface as-
sembly agents work to minimize MOF crystal agglom-
eration in solution, thereby enabling high mass-loading,
conformal coverage and physically robust surface-at-
tachment of UiO-66-NH2 crystals. To the best of our
knowledge, this is the first demonstration of chemical
assembly of pre-synthesized MOF crystals with high
mass loading on textiles utilizing surface assembly
agents. We also substantiate that the assembled MOFs
retain their functional surface area and catalytic activ-
ity, and show that the PP/ALD/MOF composites pro-
mote rapid catalytic degradation of DMNP CWA simu-
lant with a half-life of less than 5 minutes.
cles of ALD Al2O3 as a standard coating thickness.21, 25, 30
ALD ZnO and TiO2 were performed in the same lab-
made hot-wall viscous-flow vacuum reactor as that used
for ALD Al2O3. The deposition pressures were both ~1
Torr, and the temperatures were kept at 90 °C. In an
ALD TiO2 cycle, precursors of both TiCl4 and H2O were
dosed alternatively to the reaction chamber for 1 s, with
40 s of N2 purge between dose steps. We deposited 300
cycles of ALD TiO2 onto the fiber mats resulting in 20
nm of coating thickness, as determined by ellipsometry
on monitor wafers coated simultaneously in the ALD re-
actor. In an ALD ZnO cycle, the substrate (i.e., PP) was
exposed to 2 s of di-ethyl zinc (DEZ) and 2 s of deionized
water alternatively, with 60 s of N2 purge between dose
steps. We used 110 cycles of ALD ZnO as a standard coat-
ing thickness.20, 31, 32
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Synthesis of UiO-66-NH2 in the form of powder.
20 mL glass scintillation vial was loaded with 0.080 g,
0.343 mmol of ZrCl4 followed by being dissolved in 20
mL of N,N-dimethylformamide (DMF), then sonicated
for at least 1 minute until fully dissolved. After that, 20
μL of deionized water and 0.062 g, 0.343 mmol of 2-ami-
noterephthalic acid were added to the prepared solu-
tion. This as-prepared mixture was heated at 85 °C for
24 h. The resulting solid was then collected by filtering
out unreacted precursors and residual DMF using a fil-
tration system. Then the collected solid was rinsed with
80 mL of DMF and ethanol in a sequential manner in
the filtration system. Eventually, the final solid was
stored under vacuum in a desiccator until being used for
assembly experiment.
EXPERIMENTAL SECTION
All reagents were purchased from commercial sources
and used without further purification. Zirconium(IV)
chloride (ZrCl4, Alfa Aesar, ≥99.5%), 2-aminotereph-
thalic acid (Acros Organics, 99%), N,N-dimethylforma-
mide (DMF), deionized water, Ethanol, β-cyclodextrin
(β-CD, Sigma-Aldrich, ≥97%), cetyltrimethylammo-
nium bromide (CTAB, Sigma-Aldrich, ≥98%), N-ethyl-
morpholine (Sigma-Aldrich, ≥97%), and dimethyl 4-ni-
trophenyl phosphate (DMNP, Sigma-Aldrich)
Assembly of UiO-66-NH2 crystals on fibers. 0.24 g
of as-prepared UiO-66-NH2 solid was dispersed in 40
mL of DMF then sonicated for 5 minutes until fully dis-
persed (Solution A), and 0.254 g of β-cyclodextrin (β-
CD) and 0.04 g of cetyltrimethylammonium bromide
(CTAB) were simultaneously dissolved in 40 mL of DMF
for an hour to form supramolecular complex (Solution
B). Solution for assembly was prepared by slowly pour-
ing solution B to solution A, and then keeping the mix-
ture stirred for 30 minutes.
Polymeric Fibrous Materials. Non-woven polypro-
pylene (PP) was received from Nonwovens Cooperative
Research Center (NCRC), North Carolina State Univer-
sity. Non-woven PP fiber mats are 0.30 mm thick, with
fiber diameter ranging from 0.6 μm to 9.0 μm.
Atomic layer deposition (ALD). ALD was used to
create thin conformal inorganic Al2O3, TiO2 and ZnO
coatings on the PP fiber mats. These samples are re-
ferred to as PP/Al2O3, PP/TiO2 and PP/ZnO, respec-
tively. The PP/Al2O3, TiO2, and ZnO were deposited di-
rectly on the PP. The fiber coating and analysis proce-
dures follow methods developed previously for ALD
modification of polymers and textile media.29
Assembly of UiO-66-NH2 crystals onto fiber sub-
strates was performed by immersing PP fiber mats (4 ×
2.5 cm) into as-prepared solution with a mild stirring for
20 h at room temperature.
The resulting PP fiber mats with assembled UiO-66-
NH2 crystals were rinsed first with DMF (3 × 80 mL)
then with ethanol (4 × 80 mL). After that, the ultimate
products were dried in air for 1 hour and stored under
vacuum in a desiccator before being used for further
characterization.
The ALD Al2O3 was deposited onto PP using a lab-
made hot-wall viscous-flow vacuum reactor.21 Deposi-
tion pressure was kept at ~1 Torr, and the temperature
was 90 °C. In a general ALD Al2O3 cycle, tri-methyl alu-
minum (TMA) was first dosed to the reaction chamber
for 1 s, followed with 30 s of N2 purge between doses.
After TMA dose and N2 purge, deionized water was
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Chemistry of Materials
Hydrolysis of dimethyl 4-nitrophenyl phosphate
and then stored under vacuum in a desiccator for fur-
ther characterization.
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(DMNP). Hydrolysis for UiO-66-NH2 powder was im-
plemented at room temperature. UiO-66-NH2 powder
(three respective runs: 1) 1.5 mg, 0.0009 mmol, 2) 2.6 mg,
0.0015 mmol, and 3) 5.6 mg, 0.0032 mmol) was added to
an aqueous solution of N-ethylmorpholine (1 mL, 0.45
M) in a 1.5 mL Eppendorf vial (room temperature). The
resulting mixture was stirred for 30 min until finely dis-
persing the UiO-66-NH2. DMNP (~6.2 mg, 0.025 mmol)
was then added to the suspension. Stirring for each re-
action was fixed at 1100 rpm.
Material characterization. Scanning electron mi-
croscopic (SEM) images were taken using an FEI Verios
460 L field emission SEM. A thin layer of Au-Pd (5~10
nm) was sputter-coated onto all samples before SEM
imaging. X-ray diffraction (XRD) was carried out with a
Rigaku SmartLab X-ray diffraction tool (Cu Kα X-ray
source) for crystalline phase analysis. Both MOF powder
(UiO-66-NH2) and fabric with assembled MOF crystals
(PP/ZnO + Assembly) diffraction patterns were also
simulated using Mercury 3.0 software and the crystallo-
graphic information file from Cambridge Crystallo-
graphic Data Centre (CCDC 837796 for UiO-66). A
Quantachrome Autosorb-1C surface area and pore size
analyzer was used for measuring N2 isotherm at 77 K.
Samples were dried in vacuum (~1 × 10-5 Torr) at room
temperature for 1 hour, at 80 °C for 6 h, 90 °C for 1 hour,
100 °C for 1 hour, and 110 °C for 12 h in a sequential fash-
ion, before N2 adsorption measurement. BET surface
area was calculated based on the N2 adsorption data
within a relative pressure range of P/P0 = 0.02 ~ 0.08.33,
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For periodic monitoring prior to UV/Vis measure-
ment, we disposed of a 20 μL aliquot from the reaction
mixture and diluting it with an aqueous solution of N-
ethylmorpholine (10 mL, 0.45 M). Reaction progress was
measured by observing the 4-nitrophenoxide absorb-
ance at 407 nm. Solution for background was identical
to reaction solution except for absence of catalyst.
Hydrolysis for fabric with assembled UiO-66-NH2 was
carried out the same as that for UiO-66-NH2 powder.
Instead of adding the powder sample, we chopped up
PP/ZnO + Assembly (two respective runs: 1) 10 mg, 1.8
mg of UiO-66-NH2 on the fabric, 2) 17.6 mg, 3.2 mg of
UiO-66-NH2 on the fabric; mass fraction of UiO-66-NH2
on the fabric was about 30.7 %) into six pieces and
added them into solution for proper hydrolysis reaction
with DMNP while being stirred at 1100 rpm.
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A Thermo Scientific Nicolet 6700 Fourier transform
infrared spectrometer was used for analyzing MOF
growth on IR silicon wafers. A progressive change in ab-
sorbance intensity during hydrolysis reaction was mon-
itored by a Thermo Scientific Evolution 300 UV/Vis
spectrophotometer.
For monitoring reaction progress, prior to UV/Vis
measurement, we disposed of a 20 μL aliquot from the
reaction mixture and diluting it with an aqueous solu-
tion of N-ethylmorpholine (10 mL, 0.45 M). Reaction
progress was measured the same way of UiO-66-NH2
powder. Solution for background was identical to reac-
tion solution except for absence of catalyst.
RESULTS AND DISCUSSION
We prepared UiO-66-NH2 crystals through solvother-
mal synthesis as described previously.35, 36 The quality of
the as-prepared UiO-66-NH2 crystals was confirmed via
N2 adsorption isotherms and powder X-ray diffraction
(PXRD). In Figure 1, The N2 adsorption/desorption iso-
therms show a Brunauer-Emmett-Teller surface area
(BET SA) of 956 ± 81 m2/g and total pore volume of 0.57
cm3/g, equivalent to 16 mmol/g, and the PXRD results
Physical adhesion test for UiO-66-NH2 onto fab-
ric. Physical adhesion test was conducted by immersing
fabric with assembled UiO-66-NH2 (PP/ZnO + Assem-
bly) in ethanol with vigorous stirring at 500 rpm for 24
h. After the stirring step, the sample was dried in air for
1 hour, and dried under vacuum at 110 °C overnight.
Then, weight of the sample after vacuum drying was
measured and compared with that before physical ad-
hesion test.
Regeneration of UiO-66-NH2 (post-catalysis).
Slurry of UiO-66-NH2 after being used for DMNP hy-
drolysis experiment was collected and poured onto an
AnodiscTM filter membrane in a glass microanalysis vac-
uum filter apparatus equipped with a graduated cylin-
der. Once the sample was dried, 80 mL of deionized wa-
ter was filtered through the membrane two times. After
that, 80 mL of ethanol was passed through the mem-
brane two times. Finally, UiO-66-NH2 solid was col-
lected out of the membrane after being fully dried in air,
Figure 1. (a) The N2 adsorption (□) and desorption (○) iso-
therm for the UiO-66-NH2 powder prepared through sol-
vothermal synthesis at 85 °C for 24 h. Inset indicates SEM im-
age of UiO-66-NH2 crystals used for the assembly method.
BET surface area of the powder is 956 ± 81 m2/g with total pore
volume of 16 mmol/g calculated at a relative pressure (P/Po) of
0.95. (b) PXRD data for the UiO-66-NH2 powder used.
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Figure 2. SEM images of samples: (a) PP + Assembly, (b) PP/Al2O3 + Assembly, (c) PP/TiO2 + Assembly, (d) PP/ZnO + Assembly,
and magnified images in dotted circular area of individual images: (e), (f), (g), and (h), respectively. Assembly solution contains
as-synthesized UiO-66-NH2 crystals + β-CD + CTAB.
directly matched the simulated UiO-66 pattern, indi-
cating good quality starting MOF powder. To imple-
ment the assembly method, we prepared a solution con-
taining UiO-66-NH2 crystals, β-CD, and CTAB in DMF,
along with a similar solution with only the MOF and
DMF solvent. For initial experiments, PP substrates
with and without ALD coating were immersed in each
solution for prolonged periods (up to 20 h) with 500
rpm stirring at ambient temperature. Figure 2 shows
SEM images of the uncoated and ALD coated PP after
20 h of assembly in the solution containing β-CD and
CTAB. For the uncoated PP, the β-CD/CTAB assembly
process leads to homogeneous MOF crystal only in the
void regions between the fibers (Figure 2a and e), which
we ascribe to crystal entrapment and aggregation dur-
ing stirring. For the ALD coated PP, we see well dis-
persed MOF assembly on Al2O3 (Figure 2b and f) and
TiO2 (Figure 2c and d), with somewhat higher surface
density on the TiO2. For the fibers coated with ALD ZnO
(Figure 2d, h, and S1c), the UiO-66-NH2 crystals sur-
round and uniformly encase the PP micro-fibers in a
highly packed layer. In some regions, the assembled
crystal layer extends between fibers, which was not ob-
served in previous reports for MOFs formed by direct
solvothermal synthesis onto fibers.37 Using ALD-coated
PP without the supramolecular complex present, SEM
images (Figure S1d) show that after 20 h in solution, the
MOF crystals become trapped and agglomerate within
the fabric voids, similar to that in Figure 2a and e for the
uncoated PP.38
agents are illustrated in Figure 3. For these tests, the
molar ratio of β-CD to CTAB was maintained at the stoi-
chiometric ratio of 2 to 1 to maximize the assembly.26
We speculate that ALD ZnO surface deposited on PP fi-
brous scaffolds can hold hydroxyl groups of β-CD via
hydrogen bonding with Zn-OH (Figure 3a). In addition,
hydroxyl groups in the outer region of β-CD or cationic
heads of CTAB can adhere to electron-rich amine func-
tional groups of outer MOF surface by means of hydro-
gen- or electrostatic bonding, respectively.26, 28 There-
fore, MOF crystals surrounded by the assembly agents
(β-CD + CTAB) can be bridged or connected through
hydrogen bonding between β-CDs or through van der
Waals attractive forces between CTAB tail groups (Fig-
ure 3b).
These results show that combining ALD surface prep-
aration with β-CD/CTAB molecular assembly promot-
ers enables well controlled assembly of UiO-66-NH2
crystals on the surface of flexible fiber webs. Further-
more, we see that the molecular assembly agents or sur-
factants tend to prevent agglomeration UiO-66-NH2
crystals in the solution phase, while facilitating assem-
bly on the fiber surface.
Considering these results, we performed more de-
tailed experiments to confirm that the assembled MOFs
retained the good crystallinity, surface area and cata-
lytic activity of the original MOF powders. We also
sought to better understand the mechanistic reasons for
the observed differences in MOF adhesion on the vari-
ous ALD metal oxides studied, and to characterize the
adhesion and stability of the MOFs on the fibers after
assembly.
Using the ZnO-coated PP, we also examined assembly
using only the individual β-CD or CTAB assembly pro-
moters in the MOF solution. While some MOF loading
was observed, the mass uptake with the β-CD or CTAB
alone was less than observed for the combined β-CD +
CTAB (Figure S2 and S3). Possible interactions between
MOF crystals by means of β-CD + CTAB assembly
Figure 4a presents the simulated X-ray diffraction
patterns of UiO-66-NH2 powder, the PP substrate, and
the MOF-coated PP/ALD fiber mats. The intensity of
the primary UiO-66-NH2 peaks at 7.2° and 8.3° in 2-
theta are strongest for PP/ZnO, consistent with larger
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Figure 3. The proposed mechanism of interactions (a) between MOF crystals and ALD ZnO surfaces and (b) MOF crystals them-
selves by means of β-CD + CTAB structures.
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mass loading.10 This sample also shows peaks at 28° to
40° also assigned to UiO-66-NH2 which are not readily
seen in the other experimental patterns. Photographic
images of uncoated PP and PP/ZnO fiber mats after
MOF assembly are shown in Figure 4b. The yellowish
color in the upper image demonstrates the uniform cov-
erage of UiO-66-NH2 crystals.
all BET surface area of 211 m2/g for the PP/ZnO + Assem-
bly. This value for BET surface area is slightly less than
287 ± 24 m2/g expected from the value measured for the
pure powder (956 ± 81 m2/g) and the estimated fraction
of MOF mass loading on the fibers. This reduced value
may reflect uncertainty in the mass loading analysis,
and/or some partial pore blocking of the surface-an-
chored MOF crystals by the β-CD + CTAB assembly
agents.39
The trend in mass loading and surface area with ALD
coating composition demonstrates discrepant interac-
tions between the ALD layer and the supramolecular
complex (β-CD + CTAB) surrounding the UiO-66-NH2
crystals. Previous measurements reported the different
isoelectric points (IEP) for ALD coatings (i.e., Al2O3,
TiO2, or ZnO) and of untreated PP.31 The surface sites
on ZnO and Al2O3 (e.g. hydroxyls and bridging oxygens)
have predominantly Brønsted basic character, whereas
the surfaces of untreated PP and TiO2 are more acidic.
The basic surface sites promote stronger interaction
with the assembly agents (β-CD + CTAB), thus promot-
ing MOF attachment. In addition, surface roughness of
fiber after the ALD coating may also increase the surface
area available for MOF attachment.20
Figure 4. (a) XRD spectra of (from bottom to top) UiO-66-
NH2 powder, polypropylene as a substrate, and samples:
PP/Al2O3 + Assembly, PP/TiO2 + Assembly, and PP/ZnO + As-
sembly. (b) Photographs of a virgin PP swatch (bottom) and
actual PP/ZnO swatch after “Assembly method” (top). Assem-
bly solution contains as-synthesized UiO-66-NH2 crystals + β-
CD + CTAB.
Next, we studied mass fraction and overall BET SA of
UiO-66-NH2 crystals assembled onto different ALD lay-
ers (Figure 5). In Figure 5a, PP/ZnO + β-CD + CTAB +
MOF (referred to as "PP/ZnO + Assembly") shows
higher BET SA of 211 m2/g compared to that of PP/Al2O3
+ Assembly (79 m2/g) and PP/TiO2 + Assembly (90
m2/g). This is consistent with the result that the highest
MOF mass fraction of 30.7% was obtained by PP/ZnO +
Assembly. In comparison with overall BET SA of the
control samples (i.e., untreated PP fiber mat, 1 m2/g; PP
coated with ALD ZnO, PP/ZnO, 1 m2/g; and PP + Assem-
bly, 15 m2/g) the results in Figure 5b depicts a large over-
Figure 5. (a) Mass fraction of MOFs on ALD-treated PP + As-
sembly (left y-axis and blank columns) and overall BET surface
area for ALD-treated PP + Assembly (right y-axis and filled
columns). (b) Overall BET surface area for PP, PP/ZnO, PP +
Assembly, and PP/ZnO + Assembly. Overall BET surface area
means BET surface area of (MOF + Fiber). Assembly solution
contains UiO-66-NH2 + β-CD + CTAB.
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As shown in Figure 2a and e, and Figure S1, the MOF This strong adhesion of the assembled MOFs on fibers
1
assembly on the uncoated PP (PP + Assembly) leads to
agglomeration of UiO-66-NH2 crystals within the void
regions on the fiber mat substrates. In addition, XRD
analysis of MOFs formed within the PP fiber matrix
without ALD coating (Figure S4) shows appreciably
smaller MOF loading with poor dispersion. We antici-
pate that these agglomerated crystals do not chemically
interact with untreated PP surface, and therefore
smaller amount of MOF crystals are randomly loaded
on the fabric. This ultimately leads to relatively small
surface area per unit mass (MOF + Fiber). We conclude
therefore, that for the self-assembled MOF on fiber sys-
tem, high overall BET SA requires a procedure that pro-
duces both uniform MOF surface distribution and high
surface loading.
is in distinct contrast to samples prepared without ALD
coating or without the β-CD + CTAB complex, where
MOFs present on the surface readily fell off with under
gentle shaking or handling. To examine the MOF as-
sembly mechanism in more detail, we used Fourier
transform infrared spectroscopy (FTIR) to investigate
changes in the vibrational modes present in each type
of prepared sample (Figure 7). Sample substrates were
IR transparent silicon with thin native oxide solution-
coated with either CTAB, β-CD, or β-CD + CTAB. Direct
IR analysis of the PP fabric was not feasible because of
absorbance by the relatively thick polymer fiber. Other
silicon samples were coated with thin layers (20 nm) of
ALD metal oxides (Al2O3, TiO2, or ZnO) followed by as-
sembly (UiO-66-NH2 crystals + β-CD + CTAB in DMF)
with mild stirring for 20 h. As a further control, we also
analyzed silicon wafers coated with ALD TiO2 followed
by solvothermal MOF growth (85 °C for 24 h). All the
samples were completely dried in air for 3 h before char-
acterization. This allowed us to carefully trace changes
in intrinsic chemical functionalities of the MOF upon
assembly, and observe differences between assembled
and directly-grown crystals.
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To test how well the assembled UiO-66-NH2 crystals
are adhered to ALD ZnO-coated PP, we immersed the
substrates into ethanol, and then vigorously stirred at
500 rpm for 24 h (Figure 6a). From the measured mass
change, we found this procedure produced less than
0.1% mass loss (Figure 6b), indicating very strong
MOF/surface bonding. As a further test of MOF adhe-
sion, we repeatedly sheared a nylon brush across the
UiO-66-NH2 coated PP substrates. After 30 manual
brush strokes, no MOF powder could be visibly detected
on the brush or on surrounding surfaces, and as shown
in Figure S5, the fabric pieces retained their typical yel-
low color, indicating good MOF adhesion in the
brushed regions.
The IR spectra from these samples are shown in Fig-
ure 7b and c. The samples with β-CD or β-CD+CTAB
show broad νsym(OH) signals at 3600-3200 cm-1 associ-
ated with the expected β-CD hydroxyl moieties.40
Figure 6. (a) A schematic of the adhesion test during which
samples are immersed in ethanol with vigorous stirring at 500
rpm for 24 h and (b) a table revealing comparison of mass
change of each sample after the adhesion test. ꢀ is mass after
completion of adhesion test, and ꢀ0 is initial mass before the
adhesion test. [⊥] For comparison with the conventional sol-
vothermal approach in the attachment of MOF crystals, rather
than using “Assembly method”, UiO-66-NH2 is nucleated and
grown on PP/ZnO at 85 °C for 24 h.
Figure 7. (a) Schematic of expected interactions between
MOFs and supramolecular complex (β-CD + CTAB). (b-c)
FTIR spectra of CTAB, β-CD, supramolecular complex (β-CD
+ CTAB) on Si/SiO2, UiO-66-NH2 assembly on ALD-treated
(Al2O3, TiO2, or ZnO) Si/SiO2, and UiO-66-NH2 grown via sol-
o
vothermal synthesis (85 C for 24 h) on Si/SiO2/TiO2. Note
that Si/SiO2 is used as a background for all FTIR patterns.
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Chemistry of Materials
The top-most spectrum in Figure 7b and c were col-
the other metal oxides. One possible difference for as-
sembly on ZnO vs TiO2 and Al2O3 on polypropylene may
relate to the role of the ALD precursors in the surface
modification of the polymer. On polypropylene, some
ALD precursors can readily diffuse into the polymer sur-
face, leading to sub-surface metal oxide nucleation and
surface roughening. The extent of roughening depends
on the polymer, nature of the precursor, the ALD reac-
tant dose times, and the ALD process temperature.46, 47
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lected from the solvothermal MOF films grown on ALD
TiO2 on silicon. The spectrum shows OH-related peaks
at 3666-3635 cm-1 assigned to intrinsic μ3-OH groups in
the Zr6O4(OH)4 MOF secondary building unit (SBU)
clusters. Peaks associated with the organic aromatic
linker (i.e., 2-aminoterephthalic acid) include
νasym(NH2) at 3523-3500 cm-1, νsym(NH2) near 3400 cm-1,
and aromatic C-H stretches, ν(Car-H) at 3100-2850 cm-
1.41 Other MOF-related features in this sample in Figure
7c include δ(NH2) at 1629 cm-1, νasym(COO-) at 1566 cm-1,
aromatic C=C stretch, Car=Car near 1496 cm-1, νsym(COO-
) at 1431 and 1390 cm-1, and ν(Car-N) at 1338 and 1259 cm-
9
Generally, compared to TiO2 and Al2O3, ZnO ALD
tends to produce a roughened surface on PP, whereas
on planar silicon, these ALD films will all show smooth
surface texture.48 Therefore, the increased MOF attach-
ment on the ZnO-coated PP may be also associated with
preferred attachment on roughened polymer sub-
strates.
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.
Figure 7b and c also show three additional spectra
from MOF films formed by β-CD/CTAB assembly on
ALD TiO2, ZnO, and Al2O3 on silicon. As expected, these
spectra show features consistent with the combined
MOF and β-CD + CTAB assembly agents. Careful in-
spection, however, reveals noticeable differences. For
example, the intensity of the NH2 bending mode at 1629
cm-1 is reduced for the assembled MOF relative to the
grown MOF, particularly for MOF assembly on ZnO.
This change, along with the observable differences in
the OH and NH stretching features for the assembled
versus grown MOF films, is indicative of the hydrogen
bonding and electrostatic interactions that influence
the μ3-OH (on the SBUs), electron-rich amines (on the
organic linkers), and the terminal OH groups (on β-CD)
upon MOF/β-CD/CTAB assembly. The expected struc-
ture of the fully-assembled MOF on ALD surface is
shown schematically in Figure 7a.44, 45 The larger change
in the IR for assembly on ZnO is consistent with SEM
(Figure 2), XRD (Figure 4), and BET surface area (Figure
5) showing more extensive assembly on ZnO relative to
To evaluate the functional performance of the fiber-
surface assembled UiO-66-NH2 MOF crystals, we per-
formed experiments using assembled UiO-66-NH2 crys-
tals as catalytic agents for hydrolysis of chemical war-
fare agent simulants.37, 49, 50 Here, we used DMNP and
examined the rate of phosphate ester bond hydrolysis to
simulate hydrolysis of GB (Sarin) or GD (Soman) nerve
agents that each contain labile P-F bond.51 Katz et al.,
have recently found that the DMNP hydrolysis rate us-
ing UiO-66-NH2 is approximately 20 times than that of
UiO-66.52 This noticeable enhancement was probably
by the amino moiety functioning as a Brønsted-base in
UiO-66-NH2, improving proton transfer during the hy-
drolysis. Figure 8a shows a schematic of the hydrolysis
of DMNP by MOF-based catalyst (left) and periodic
monitoring (right) of the hydrolysis reaction using UV-
Vis measurements. As the reaction progresses, the in-
tensity at 407 nm becomes enhanced due to emergence
of the 4-nitrophenoxide hydrolysis product. Conversion
profiles for DMNP hydrolysis in the presence of un-
treated PP, PP/ZnO, PP/ZnO + Assembly and UiO-66-
NH2 MOF powder are plotted, respectively. As shown in
Figure 8b and Table 1, for untreated PP microfibers,
DMNP destruction rate is negligible with the estimated
half-life of around 6 days. With ALD ZnO layers on PP
microfibers (PP/ZnO), it lowers the half-life to less than
20 h (Figure S6). This shows consistency that metal ox-
ides like TiO2 or ZnO can function as catalysts for de-
grading CWAs or their simulants.53, 54 The DMNP hy-
drolysis reaction rates are much faster with PP/ZnO +
Assembly (m(MOF+Fabric) = 10 mg) fabric and (mMOF = 2.6
mg) UiO-66-NH2 powder with the half-life of 6.5 min
for both. The kinetic traces and half-lives of hydrolysis
of DMNP using the fabric and powder samples are close
to each other. We believe this observation is reasonable
considering that mass fraction of UiO-66-NH2 on the
fabric (PP/ZnO + Assembly) was around 30.7%. There-
fore, it is sensible to regard the amount of MOFs on the
fabric as about 3.1 mg, which is similar amount of MOFs
Figure 8. (a) Catalytic hydrolysis reaction for DMNP (top) and
UV-Vis trace of the hydrolysis of DMNP as a function of time
(0 - 120 min) using PP/ZnO + Assembly fiber mats (bottom).
(b) Conversion profiles for the hydrolysis of DMNP in the
presence of PP, PP/ZnO, PP/ZnO + Assembly, and UiO-66-
NH2 powder at room temperature as a function of time. Inset
shows transparent color of solution before hydrolysis reaction
starts remarkably changed into yellowish one after the reac-
tion completes. *UiO-66-NH2 powder used is collected from
remnants of assembly solution. The slight drop in the data at
~30 minutes is within the statistical uncertainty of the results.
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Table 1. Material properties and catalytic performance Scheme 1. Comparison of “Assembly method” at ambi-
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of degrading a CWA simulant, DMNP.
ent temperature between untreated polypropylene
(PP) and ALD-treated PP.
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*UiO-66-NH2 powder used was collected from remnants
of assembly solution. Turn over frequency (TOF) was cal-
culated per Zr6 cluster at t1/2. [a] Amount of catalyst for
fabric samples is corrected based on the actual mass frac-
tion of UiO-66-NH2 assembled on PP/ZnO, which is
about 30.7% as calculated in Figure 5a.
Solution for assembly contains pre-synthesized UiO-66-
NH2 crystals and the supramolecular complex (β-cy-
clodextrin (β-CD) + cetyltrimethylammonium bromide
(CTAB)).
in powder sample (mMOF = 2.6 mg). Furthermore, the
rates for DMNP degradation are similar to those re-
cently reported for UiO-66-NH2 formed on ALD-coated
polymer fibers via direct solvothermal synthesis.36 As for
the hydrolysis reactions catalyzed with the fabric sam-
ples, we cut one piece of fabric into several pieces to well
disperse in the reacting solution. As a control experi-
ment, we kept the total amount of sample (MOF + fiber)
fixed and varied the extent of fabric cutting used to pre-
pare the samples for kinetic analysis. Results in Figure
S7 show we obtained the same DMNP degradation rate
using either a single fabric piece or a sample cut into
small pieces, confirming that sample cutting did not in-
fluence measured reaction kinetics.
UiO-66-NH2 on polymer fabric is a viable means to cre-
ate MOF-cloths for chemical hydrolysis agents simu-
lated by DMNP with half-life less than 5 minutes.
CONCLUSIONS
The results described here clearly demonstrate that
the combining ALD surface modification with solution-
based β-CD + CTAB supramolecular complex adhesion
promotor allows assembly of high density, robust and
functionally active MOF crystal coatings on fiber-based
substrates. The assembly approach is summarized in
Scheme 1. The ALD layer provides a chemically func-
tional attachment layer for the supramolecular β-CD +
CTAB complex, and the complex acts as assembly agent
to well disperse UiO-66-NH2 crystals and allow them to
assemble into dense coatings onto the ALD layers via
electrostatic and hydrogen bonding interactions. We
find that the extent of MOF loading depends on the
composition of the metal oxide ALD coating, with a
larger extent of loading on ZnO vs Al2O3 or TiO2. Infra-
red analysis confirms that assembled layers contain β-
CD, CTAB and the MOF crystals, and analysis of the IR
results suggests that surface composition as well as fiber
surface roughness may be factors in the extent of MOF
loading.
In another set of experiments, we varied the catalyst
loading and found that the initial t1/2 values are dimin-
ished as the amounts of the catalyst loading are in-
creased (Figure S8 and Table 1). These results are anal-
ogous to those with UiO-67 derivatives previously re-
ported.52 We also identified such kinetic traces with fab-
ric (PP/ZnO + Assembly) samples showed similar pro-
pensity (Figure S9 and Table 1).
Concerning verified high mechanical and hydrostabil-
ity of UiO-66-NH2, XRD and SEM confirmed that UiO-
66-NH2 is fairly intact under our hydrolysis condition
(Figure S10). Moreover, we confirmed that the micro-
structure of the UiO-66-NH2 is retained after assembly,
as determined by overall BET SA of the MOFs. The sur-
face area of 817 m2/g after assembly is very close to 956
± 81 m2/g measured for similarly-prepared UiO-66-NH2
crystals. This difference probably reflects the extra mass
of the supramolecular complex, or perhaps partial
blocking of the accessibly MOF pores.39 Even so, the
BET surface area remains similar to values ca. 830 m2/g
reported for some pristine UiO-66-NH2 powders.22 Con-
sidering all results collectively, chemical assembly of
We also verified that the crystals assembled on PP fi-
brous mats retain their effectiveness for rapid catalytic
degradation of hazardous chemical simulants, with
rates in line with those observed for the same reactions
on UiO-66-NH2 MOFs in free-powder form. The results
clearly show that chemically assembling a relatively
small amount of MOF crystals on a fiber surface can be
beneficial to overcome difficulties in deployment of
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Chemistry of Materials
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Li, J. R.; Kuppler, R. J.; Zhou, H. C., Selective gas
MOF powders. Moreover, the assembly process pro-
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adsorption and separation in metal-organic frameworks. Chem.
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(10)
The Example of UiO-66/Polyurethane. ACS Appl. Mater.
Interfaces 2013, 5, 2360-2363.
ceeds readily at room temperature and therefore can be
considered for extending to a wide range of substrate
materials at large scale.
Pinto, M. L.; Dias, S.; Pires, J., Composite MOF Foams:
ASSOCIATED CONTENT
Supporting Information.
The Supporting Information is available free of charge on the
http://pubs.acs.org.
Additional information pertaining to SEM, MOF adhesion
tests, kinetic studies, and XRD.
(11)
Liu, C.; Wu, Y. N.; Morlay, C.; Gu, Y. F.; Gebremariam,
B.; Yuan, X.; Li, F. T., General Deposition of Metal-Organic
Frameworks on Highly Adaptive Organic-Inorganic Hybrid
Electrospun Fibrous Substrates. ACS Appl. Mater. Interfaces 2016,
8, 2552-2561.
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Fan, L. L.; Xue, M.; Kang, Z. X.; Li, H.; Qiu, S. L.,
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Electrospinning technology applied in zeolitic imidazolate
framework membrane synthesis. J. Mater. Chem. 2012, 22, 25272-
25276.
AUTHOR INFORMATION
Corresponding Author
(13)
Li, Y. B.; Wee, L. H.; Volodin, A.; Martens, J. A.;
Vankelecom, I. F. J., Polymer supported ZIF-8 membranes
prepared via an interfacial synthesis method. Chem. Commun.
2015, 51, 918-920.
(14)
from fundamentals to applications. Nanoscale 2015, 7, 7482-7501.
(15) Armstrong, M. R.; Arredondo, K. Y. Y.; Liu, C. Y.;
Stevens, J. E.; Mayhob, A.; Shan, B. H.; Senthilnathan, S.; Balzer,
C. J.; Mu, B., UiO-66 MOF and Poly(vinyl cinnamate) Nanofiber
Composite Membranes Synthesized by a Facile Three-Stage
Process. Ind. Eng. Chem. Res. 2015, 54, 12386-12392.
*(G.N.P.) E-mail: parsons@ncsu.edu
Author Contributions
Li, S.; Huo, F., Metal-organic framework composites:
The manuscript was written through contributions of all au-
thors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
(16)
Guo, H.; Zhu, G.; Hewitt, I. J.; Qiu, S., “Twin Copper
ACKNOWLEDGMENT
Source” Growth of Metal−Organic Framework Membrane:
Cu3(BTC)2 with High Permeability and Selectivity for Recycling
H2. J. Am. Chem. Soc. 2009, 131, 1646-1647.
The authors acknowledge support from ECBC (grant no.
W911SR-07-C-0075) and the Joint Science and Technology Of-
fice (Army Research Office grant no. W911NF-13-1-0173). We
acknowledge the excess of the Analytical Instrumentation Fa-
cility (AIF) at North Carolina State University, supported by
the State of North Carolina and National Science Foundation.
(17)
So, M. C.; Jin, S.; Son, H. J.; Wiederrecht, G. P.; Farha, O.
K.; Hupp, J. T., Layer-by-Layer Fabrication of Oriented Porous
Thin Films Based on Porphyrin-Containing Metal-Organic
Frameworks. J. Am. Chem. Soc. 2013, 135, 15698-15701.
(18)
Yao, J. F.; Dong, D. H.; Li, D.; He, L.; Xu, G. S.; Wang, H.
T., Contra-diffusion synthesis of ZIF-8 films on a polymer
substrate. Chem. Commun. 2011, 47, 2559-2561.
(19)
framework thin films using microwave-induced thermal
deposition. Chem. Commun. 2008, 2441-2443.
(20) Zhao, J.; Losego, M. D.; Lemaire, P. C.; Williams, P. S.;
Gong, B.; Atanasov, S. E.; Blevins, T. M.; Oldham, C. J.; Walls, H.
J.; Shepherd, S. D.; Browe, M. A.; Peterson, G. W.; Parsons, G. N.,
Highly Adsorptive, MOF-Functionalized Nonwoven Fiber Mats
for Hazardous Gas Capture Enabled by Atomic Layer Deposition.
Adv. Mater. Interfaces 2014, 1, 1400040.
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