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MOFabric: Electrospun Nanofiber Mats from PVDF/ UiO-66-NH2 for Chemical Protection and Decontamination Annie Xi Lu, Monica McEntee, Matthew A Browe, Morgan Hall, Jared B. DeCoste, and Gregory W. Peterson ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b01621 • Publication Date (Web): 29 Mar 2017 Downloaded from http://pubs.acs.org on March 30, 2017

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ACS Applied Materials & Interfaces

MOFabric: Electrospun Nanofiber Mats from PVDF/UiO-66-NH2 for Chemical Protection and Decontamination Annie Xi Lu1,2*, Monica McEntee2, Matthew A. Browe2, Morgan G. Hall2, Jared B. DeCoste2, and Gregory W. Peterson2* 1

2

Defense Threat Reduction Agency, 2800 Bush River Road, Aberdeen Proving Ground, MD 21010 USA Edgewood Chemical Biological Center, 5183 Blackhawk Road, Aberdeen Proving Ground, MD 21010 USA

E-mail: [email protected], [email protected] Keywords: chemical warfare agents, composites, electrospinning, metal-organic frameworks, nanofibers, PVDF Abstract: Textiles capable of capture and detoxification of toxic chemicals, such as chemical-warfare agents (CWAs), are of high interest. Some metal-organic frameworks (MOFs) exhibit superior reactivity toward CWAs. However, it remains a challenge to integrate powder MOFs into engineered materials like textiles, while retaining functionalities like crystallinity, adsorptivity, and reactivity. Here, we present a simple method of electrospinning UiO-66-NH2, a zirconium MOF, with polyvinylidene fluoride (PVDF). The electrospun composite, which we refer to as “MOFabric”, exhibits comparable crystal patterns, surface area, chlorine uptake and simulant hydrolysis to powder UiO-66-NH2. The MOFabric is also capable of breaking down GD faster than powder UiO-66-NH2. Half-life of GD monitored by solid state NMR for MOFabric is 131 min versus 315 min on powder UiO-66-NH2.

1. Introduction

synthetic exchange16 make MOFs ideal for emerging environmental and defense applications. In particular, the zirconium-based MOF, UiO-66-NH2, has many potentials for CWA applications due to its ability to act as a catalyst in the hydrolysis of organophosphates.17 Therefore, recent efforts have focused on integrating this MOF in free-standing substrates or textiles, which could lend possibilities not available to primitive MOF powders. A major advantage for engineering MOF powders onto pliable polymeric substrates, such as films or fibers, is to give these nonreactive polymeric materials an additional dimension of functionality. Electrospinning is a scalable process18 that produces nonwoven nanofibers that can be used in textile applications. Integrating MOFs with polymer fibers through electrospinning would be beneficial since electrospun fabrics already exhibit desirable properties, such as fast moisture vapor transport rates and particulate filtration.9, 19 Electrospinning fabric materials with MOFs would provide fabrics with additional porosity and reactivity toward target chemicals. However, one of the most challenging aspects of engineering MOFs onto substrates is finding a suitable polymer/MOF pair, where the interactions between the MOF and polymer are strong enough to avoid interstitial gaps but also allow access to the MOF’s reactive surface and pores.20 PVDF has previously been used as a low-surface-energy binder to increase stability of a moisture-sensitive MOF, HKUST-1,13, 21 and as a particulate filter with UiO-66-NH2.22 With that in mind, we postulate that UiO-66-NH2 electrospun with PVDF would maintain its porosity and CWA reactivity in the engineered form. We term our MOF-PVDF matrix, “MOFabric”, with the envisioned CWA protection applications illustrated in Figure 1. Our engineered product has potential application as textiles for protection against chlorine gas and detoxification of liquid nerve agent. Previous reports have shown reactive textiles used for reaction against CWA simulants, with one recent report by Parsons et al. studying the nerve agent O-pinacolyl methylphosphonofluoridae (soman, GD) in a buffered solution.8 To our knowledge, this is the first report of a

Engineered materials capable of capture and removal of chemical warfare agents (CWA) and toxic industrial chemicals (TICs) are highly desirable for protective textile applications. Current individual protection garments for CWAs are carbon-based air-permeable suits which offer physical adsorption for nerve and vesicant agents, or impermeable protective barriers such as Teflon-based suits, which require built-in breathing units as air supply.1, 2 Neither system is capable of self-detoxification of CWAs. Recently, several groups have developed processes with successful integration of reactive materials onto textiles,3-6 some with specific applications for protection against CWAs.7-12 Of these reactive composites, those incorporating metal-organic frameworks (MOFs) have shown remarkable ability as sorbents and catalysts for neutralizing nerve agents and TICs.8, 10, 12, 13 MOFs are porous materials composed of inorganic metal nodes connected by organic linkers to form crystalline structures.14 The high surface area15 and tailorability of properties through both de novo synthesis and post-

Figure 1. Illustration of MOFabric and its application. Illustration of electrospun nanofiber mats with UiO-66-NH2. MOFabric, can be used for protection against toxic industrial chemicals (TICs) and chemical warfare agents (CWAs).

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Figure 2. SEM (top) and optical (bottom) images of MoFabric with different mass loading of UIO-66-NH2. (a) 20 wt% PVDF control; (b) 9.1 wt% UiO-66-NH2 in 20 wt% PVDF solution; (c) 16.7 wt% UiO-66-NH2 in 20 wt% PVDF solution; (d) 23.1 wt% UiO-66-NH2 in 20 wt% PVDF solution; (e) 41.2 wt% UiO-66-NH2 in 18 wt% PVDF solution.

MOF/textile composite neutralizing GD droplets in a solvent free environment.

crystallinity due to the arrangement of the hydrogen and fluorine atoms on the polymer carbon chain.23 Each of the MOFabric swatches show a clear diffraction peak at 2θ = 20.5°, indicative of the PVDF β phase, while the lower MOF loading samples, MOFabric7.0% and MOFabric-13% also exhibit a diffraction peaks at 2θ = 18.9°, indicative of the PVDF γ phase. At higher MOF loadings, the peak for the β phase comes less apparent, suggesting that the crystalline structure of the γ and β phases of PVDF can be interrupted through the incorporation of solid particles.24-26 Presence of these phases are further confirmed by DRIFTS and peak assignments are shown in SI Table S2. A key benefit of MOFs is their high surface area, which is useful for applications in gas adsorption and separations. N2 physisorption measurements at 77K (Figure 3c) were used to determine the BET surface area of each sample. The BET surface area of the baseline UiO-66-NH2 powder is 726 m2g-1, whereas the BET surface areas of MOFabric-7.0, -13, -19, and -33% are 30, 89, 111, and 225 m2g-1, respectively. These values scale well with the actual MOF loading determined by TGA, indicating that the pores of the MOFs are accessible to nitrogen in the MOFabric matrix . Due to the low surface energy of fluorinated polymers, it is unlikely that new bonds are formed between UiO-66-NH2 and PVDF. Therefore, the reactive moieties like –NH2 and –OH on the UiO-66NH2, which are necessary to drive a number of CWA reactions,27-31

2. Results and Discussion Various concentrations of PVDF in solvent consisting of 1:1 weight ratio of N,N-dimethylformamide (DMF) and acetone were tested to determine the optimal conditions for electrospinning. SEM images, Supplemental Information (SI) Figure S1, showed that a 10 wt % PVDF solution created bead-on-string structures, while a 15 wt % PVDF solution created fibers with visible nodes. A 20 wt % PVDF (Figure 2a) created stable nanofibers when spun at 15.5 kV. Subsequent polymer solutions based on 20 wt % PVDF containing different weight loadings of UiO-66-NH2 were prepared according to the masses listed in SI Table S1. SEM images and photographs of MOFabric swatches bearing nominal weight loadings of 9.1, 16, 23, and 41% UiO-66-NH2 are shown in Figure 2 (b-e). As shown in the SEM images, the clusters of UiO-66-NH2 are randomly dispersed throughout the field of view, with the exception of the highest-mass-loading sample. However, in the macroscopic pictures, it is apparent that the nanofiber mats increasingly exhibit the characteristic yellow color of UiO-66-NH2. Thermogravimetric analysis (TGA) (Figure 3a) was used to analyze the actual MOF mass fraction in the samples, as MOF particles can settle out of solution during the electrospinning process. The calculated MOF mass fraction for each sample is determined to be 7.0, 13, 19, and 33 wt% for 9.1, 17, 23, and 41 wt% MoFabric swatches, respectively (calculations shown in SI). As the calculated values represent the percent of MOF successfully incorporated into each sample, samples will be referred to as MOFabric-x% throughout the manuscript (e.g. the first sample will be referred to as MOFabric7.0%) The crystal structures of the UiO-66-NH2 in the MOFabric swatches were confirmed by PXRD (Figure 3b). PVDF has intrinsic

Table 1. Chlorine gas loading on MOFabric samples and powder UiO-66-NH2.


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Figure 3 Characterization of MOFabric swatches with various loading of UiO-66-NH2, compared to powder UiO-66-NH2 and electrospun PVDF control: (a) TGA spectra; (b) X-ray diffraction patterns; (c) N2 isotherm.

should remain chemically unbound and theoretically accessible. We used diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to measure the IR absorbance peaks of these reactive moieties on the various MOFabrics and compared their IR absorbance peaks to the native UiO-66-NH2 spectrum. Figure 4 shows the IR spectra of PVDF alone (orange curve), incremental increases of the UiO-66-NH2 wt% on the polymer (blue, red, green and purple curves) and lastly UiO-66-NH2 alone (navy blue curve). The Zr-OH and -NH2 sites of the MOF are assigned to IR peaks at 3679 cm-1 (ν(OH)) and 3477 (νas(NH2)) and 3370 (νs(NH2)) cm-1, respectively.28-30 The other IR bands that increase in the fingerprint region around 1700-1500 cm-1 correspond to the IR modes of UiO66-NH2 as shown in Figure 4. A table of the IR bands and their corresponding assignments for both UiO-66-NH2 and PVDF are shown in the SI Table S2. Indeed, the IR spectra do not contain any new product peaks, and increasing the mass loading of UiO-66-NH2 increases both the –NH2 and –OH IR stretching peaks, as shown in SI Figure S2(b) by integrating the area under the IR band of interest. A lack of any significant IR shifts in either the -OH or -NH2 peaks after

incorporation into the fabric indicates these sites are not chemically bound to the PVDF polymer and theoretically free for reactivity. UiO-66-NH2 is particularly attractive for chlorine adsorption due to electrophilic aromatic substitution of chlorine on the benzene ring of the aminoterephthalic acid (MOF linker).31 Chlorine uptake capacities were measured for each material using microbreakthrough tests at a chlorine concentration of 2000 mg m-3. The results, as seen in Table 1, suggest that the chemisorption of chlorine to UiO-66-NH2 in the MOFabric swatches is possible and scales with the mass loading of UiO-66-NH2 and their respective BET values. Next, we evaluated the ability of MOFabrics to catalytically degrade CWA simulants, following previously published methods.8, 32 The degradation kinetics of dimethyl p-nitrophenylphosphate (DMNP), a simulant for soman, were monitored by tracking the absorbance of the reaction product p-nitrophenoxide at 407 nm in a buffered reaction, with the percent conversion over time shown in SI Figure S3. The concentration of the product is calculated based on Lambert-Beer Law and its natural log is plotted as a function of time in SI Figure S4 to obtain the slope. The half-lives are calculated



composites. SI Figure S5 shows the natural logarithm of the area from NMR 31P doublets at 29 and 34 ppm, corresponding to the decay of GD, as seen in an example SS NMR spectrum found in SI Figure S6. The growth of the peak at 30 ppm between the GD doublets corresponds to growth of pinacolyl methylphosphonic acid (PMPA), the non-toxic hydrolysis product via the P-F bond cleavage of GD. From the slopes of the natural log of the height of GD (SI Figure S5), the half-life is calculated for each sample, shown in Table 2. For MOFabric-7% and -13%, half-lives are over 1000 min, indicating that the MOF is not able to adequately degrade the agent in these materials. At higher MOF loadings, however, GD is removed more effectively, as MOFabric-19 and -33% have half-lives between 2 and 3h, compared to over 5h for the pure UiO-66-NH2 powder. In fact, the composite samples exhibit faster GD removal than pure UiO-66-NH2. It was observed that the concentrated GD droplet did not disperse well throughout the powder, and saturated a small percentage of the material. Thus, GD removal became diffusionlimited and the reaction sites were over-saturated. We hypothesize that the improved performance of the composites is due to the low surface energy of PVDF aiding in the spreading of the GD droplet to UiO-66-NH2 particles. In the composite, although an overall lower amount of MOF is present, the GD is likely able to reach more MOF faster, reducing the overall diffusion rates, thus, the MOF is more efficiently utilized within the composite.

1.8 PVDF MOFabric-7.0% MOFabric-13% MOFabric-19% MOFabric-33% UiO-66-NH2

1.6 1.4

Absorbance

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νs(NH)

1.2

νas(NH)

1.0 0.8

Zr-OH

0.6 0.4 0.2 0.0 4000

3500

3000

2500

2000

1500

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1000

-1

Wavenumber (cm ) Figure 4. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) spectra of the various MOFabric samples, control PVDF, and 100% UiO-66-NH2.

based on first-order kinetics and given in Table 2. The degradation curves and kinetics trend well with the amount of UiO-66-NH2 incorporated into each MOFabric. We postulate that the decreased activity of MOFabric samples compared to powder UiO-66-NH2 is due to clustering of MOF particles in the polymer matrix. While we believe that reaction sites are still accessible based on the data from the increased –OH and –NH2 peaks in the DRIFTS spectra, the clustering effect may present a diffusion barrier for the CWA simulant. For plain PVDF nanofibers, DMNP showed a negligible rate for hydrolysis. With promising results from the simulant DMNP, we then investigated the ability of MOFabric to hydrolyze the nerve agent Opinacolyl methylphosphonofluoridae (soman, GD) without a buffered solution. Using solid state nuclear magnetic resonance (SS-NMR), 2.6 µL of GD was dosed onto 1 cm2 swatches of MOFabric

3. Conclusions In this study, we demonstrated the ability to generate fabric swatches using the electrospinning process. A fluorinated polymer PVDF and Zr-based UiO-66-NH2 were chosen as a model polymer-MOF pair for creating the MOFabric swatches. We also demonstrated that electrospun UiO-66-NH2 in PVDF maintained characteristics of MOFs such as porosity and crystallinity in the electrospun state. We explored the compatibility of this polymer-MOF pair through DRIFTS and confirmed that there is no covalent interactions or new bonds formed between the polymer and MOF, thereby not blocking accessibility to the MOF. The electrospun MOFabric swatches were used to hydrolyze chemical warfare simulant DMNP and chemical warfare agent GD. In summary, we have demonstrated that MOFabric is a promising textile for chemical protection and decontamination against TICs and CWAs.

Table 2. Hydrolysis of methyl paraoxon (DMNP) of MoFabric swatches with various mass loading of UiO-66-NH2, powder UiO-66-NH2, and plain electrospun PVDF swatch as control in 0.4 M N-ethylmorpholine stirred reaction; calculated half-lives of methyl paraoxon in solution with MoFabric; Hydrolysis of the nerve agent O-pinacolyl methylphosphonofluoridae (soman, GD) without a buffered solution. Rate of product formation is measured by the integrated area under the solid state nuclear mangetic resonance (ssNMR) spectra of the hydrolysis product. Calculated half-lives of GD in MoFabric samples with different mass loading of UiO-66-NH2 and powder UiO-66-NH2.

ASSOCIATED CONTENT Supporting Information Experimental details, calculations of MOF content through TGA data; Figures S1-6, Table S1 and S2

AUTHOR INFORMATION Sample

DMNP t1/2(min)

GD t1/2(min)

MOFabric-7%

210

1616

MOFabric-13%

75

1155

MOFabric-19%

36

161

MOFabric-33%

12

131

UiO-66-NH2

4.4

315

PVDF

1155

N/A

Corresponding Author [email protected] [email protected]

Acknowledgements: We would like to thank Oak Ridge Associated Univeristies for providing M.L.M. with an ORISE fellowship. J. B. D., G. W. P., A.X.L., M.B., and M.G.H., also thank the Joint Science and Technology Office for Chemical Biological Defense for funding under project number CB3934/BA13PHM210.


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