# Robust Functionalized Cotton Fabrics with Zr-Based Tetrahedral Cages for Degrading a Chemical Warfare Agent Simulant

Elise Cape, Pauline Hardy, Rosalia Jreis, Fabrice Bray, Manuela Ferreira, Thierry Loiseau, Christine Campagne, Christophe Volkringer, Alexandre Legrand

► To cite this version:

Elise Cape, Pauline Hardy, Rosalia Jreis, Fabrice Bray, Manuela Ferreira, et al.. Robust Functionalized Cotton Fabrics with Zr-Based Tetrahedral Cages for Degrading a Chemical Warfare Agent Simulant. ACS Applied Materials & Interfaces, 2026, 18 (6), pp.10307-10315. 10.1021/acsami.5c22435. hal-05535050

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Submitted on 3 Mar 2026

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Distributed under a Creative Commons CC BY 4.0 - Attribution - International License
Robust functionalized cotton fabrics with Zr-based
tetrahedral cages for degrading a chemical warfare
agent simulant

Elise Cape,ª Pauline Hardy,ª Rosalia Jreis,ª Fabrice Bray,ᵇ Manuela Ferreira,ᶜ Thierry

Loiseau,ª Christine Campagne,ᶜ Christophe Volkringer,ª and Alexandre Legrand*ª

a. Univ. Lille, CNRS, Centrale Lille, UMR 8181 – UCCS – Unité de Catalyse et Chimie du Solide, Univ. Artois, Lille, F-59000 France.

b. Univ. Lille, CNRS, UAR 3290 – MSAP – Miniaturisation pour l’Analyse, la Synthèse et la Protéomique, Univ. Lille, Lille, F-59000 France.

c. Univ. Lille, Univ. Lille, ENSAIT, ULR 2461–GEMTEX–Génie et Matériaux Textiles, F-59000 Lille, France.

KEYWORDS: metal-organic cages, textile functionalization, composite materials, simulant of
CWA, degradation

ABSTRACT: The resurgence of chemical warfare agents (CWAs) in recent decades underscores the urgent need for efficient and durable personal protective equipment (PPE). Conventional systems employing zeolites or activated carbons provide only passive protection via adsorption
and suffer from limited porosity, low catalytic activity, and weak adhesion to textile substrates. To address these challenges, metal-organic cages (MOCs) offer a promising alternative to metal-organic frameworks (MOFs) due to their solubility, molecular nature, and tunable surface reactivity. In this study, we report the deposition of zirconium-based MOCs (ZrMOCs) onto cotton fabrics using impregnation and in situ growth techniques to develop catalytically active and mechanically robust composites. The resulting MOC-cotton materials were characterized for deposition uniformity and durability under abrasion and ageing tests. Their catalytic performance was evaluated toward the hydrolytic degradation of dimethyl 4-nitrophenyl phosphate (DMNP), a nerve-agent simulant. The in-situ growth method yielded homogeneous coverage and strong interfacial bonding between the ZrMOCs and cellulose fibers, resulting in enhanced resistance to mechanical stress and artificial ageing, while retaining excellent breathability. Despite a moderate loading (6 wt%), the composite exhibited rapid DMNP decomposition ($t_{1/2} < 25$ min) and maintained activity after the abrasion normed test. Although catalytic efficiency decreased after ageing, it remained superior to that of MOF-based cotton composites (UiO-66-NH₂). These results demonstrate the potential of ZrMOC-functionalized textiles as active protective materials for next-generation PPE for CWA decontamination, offering a promising route toward durable and multifunctional fabrics.

## Introduction

For over twenty years, the world has experienced a rise in armed conflicts and terrorist threats.¹ In tandem, the collapse of the international arms control framework and a gradual withdrawal from established agreements have led to the use of both old and new chemical weapons. Recent incidents, such as the Russian Federation's use of tear gas (2-chlorobenzalmalononitrile) in the
Ukrainian conflict and the assassination attempt by a nerve agent (Novichok) on Alexei Navalny in August 2020, have demonstrated that both military and civilian populations can be affected by chemical warfare agents (CWAs).² These agents include nerve agents (Sarin), blister agents (mustard gas), choking agents (phosgene), blood agents (cyanide- or arsenic-based), and riot-control agents (tear gases).

Confronted with these threats, the development of civil or military protection involves the use of filtering respiratory devices, ideally capable of capturing toxic agents using microporous materials such as zeolites and activated carbons.³ While the gas mask's function in protecting against CBRN (Chemical, Biological, Radiological, Nuclear) risks is clear, it primarily safeguards the respiratory system. It must be complemented with a suit that covers the entire body to avoid penetration of CWAs through the skin. Civilian or military personal protective equipment (PPE) developed to date is made from synthetic or natural fibers (polyester, cotton, etc.) that respect the individual's physiological parameters, such as temperature and hydration. The function of trapping and degrading toxic molecules is achieved by a catalyst deposited on the textile fiber's surface. As with gas masks, catalysts are typically microporous materials.⁴

Among relatively recent porous solids, metal-organic frameworks (MOFs) are hybrid materials formed by the coordination of a metal ion to an organic ligand. The resulting porous frameworks have pore diameters of several nanometres and specific surface areas up to 5000 m²/g. Their high porosity, catalytic activity, and chemical versatility make MOFs excellent candidates for protecting individuals against CBRN risks. ⁵,⁶,⁷ Recent scientific advances in integrating MOFs into textiles highlight several manufacturing techniques.⁴,⁸ Common methods for integrating
MOFs onto textiles include interfacial synthesis via in situ growth or covalent modification, which have the advantage of being synthetically straightforward and enabling strong interfacial interaction between the MOF and the fabric. However, increasing the precursor concentration leads to amorphous materials, making upscaling difficult.⁹ MOF formation on metal-coated fibers produces uniform, robust MOF-coated fibers.¹⁰ Nevertheless, this method depends on the metal used and thus cannot be applied broadly to many types of MOFs, and it requires costly equipment, such as atomic layer deposition. Finally, electrospinning and hot pressing are processes that enable the production of functionalized textiles on a large scale; however, they result in low MOF loading on the fabric and limited mechanical stability due to the lack of a strong chemical bond between the MOFs and the support.¹¹,¹²

Like activated carbons and zeolites, MOFs are insoluble, and shaping them (e.g., grafting nanoparticles onto the fiber surface) for industrial applications remains difficult. Indeed, the limited dispersibility and interfacial incompatibility of porous materials with the fiber substrate cause defects, uneven distribution of the porous material, and brittle composites.

In contrast, metal-organic cages (MOCs) offer an interesting alternative to MOFs, mainly due to their solubility, discrete molecular nature, and surface reactivity.¹³ They are formed through a coordination reaction between organic ligands and metal ions, yielding discrete molecular cages (0D) with well-defined geometries.¹⁴ Regarding properties, MOCs possess permanent porosity derived from the inner cage cavity and the extrinsic voids between cage packing structures.¹⁵ MOCs have been employed as hosts to accommodate numerous species (gases, liquids, vapors) and have demonstrated promising applications in catalysis,¹⁶ adsorption and separation,¹⁷ and biology.¹⁸ Due to their ease of processing in solution, MOCs have been assembled into films,¹⁹ membranes,²⁰ or colloidal gels²¹ and deposited on various supports such as carbon paper or metal
foil.²² Recently, research groups reported the potential of Zr-based MOCs for the degradation of chemical warfare agent simulants.²³ The molecular nature of MOCs and their surface reactivity were used to form a long-range ordered structure generating extrinsic porosity for the improved diffusion of simulant and its degradation.²⁴ Another group reported that cages could form a self-supporting gel via a disassembly-reassembly process with good catalytic activity for nerve agent simulant degradation and high adsorption capacity for blister agent simulants, coupled with robust stability and hierarchical porosity.²⁵ However, no literature reports the deposition of MOCs onto textile fibers to develop active PPE against CWA.

Here, we examine the deposition of ZrMOCs on cotton fibers using impregnation and in situ growth methods (Figure 1). Advanced characterization techniques were used to evaluate the properties and uniformity of the composite textile for each method, along with standard resistance tests. Each approach was tested for the capture and degradation of dimethyl-4-nitrophenyl phosphate (DMNP), a simulant of organophosphorus nerve agents. The decontamination efficiency of artificially aged samples and those subjected to abrasion tests is also assessed.
<figure><img src="image_2.png" /></figure>

**Figure 1.** Schematic of our strategy for functionalizing cotton fabric with ZrT-2 using either (i) impregnation from pre-synthesized cages or (ii) in situ synthesis of the cages. The composite textile was tested for the degradation of a nerve agent simulant (DMNP). The resistance of the composite to abrasion and ageing, as well as its impact on decontamination efficiency, was also assessed.

## Experimental

**Materials.** zirconium cyclopentadienyl (ZrCp₂Cl₂), benzene-1,4-dicarboxylic acid (BDC), benzene-1,3,5-tricarboxylic acid (BTC), biphenyl-4,4'-dicarboxylic acid (BPDC), n-ethylmorpholine (NEM), dimethyl 4-nitrophenyl phosphate (DMNP), and dimethylacetamide (DMA) were purchased from commercially available sources and used as received. Cotton fabric was provided by the GEMTEX team of ENSAIT (Roubaix, France).

## Characterizations.
**X-Ray diffraction (XRD).** Powder XRD data were recorded on a Bruker D8 Advance A25 diffractometer with Bragg-Brentano geometry using Cu Kα radiation, from 3° to 50°, with a step size of 0.02° and a counting time of 0.5 s/step.

**UV-visible spectroscopy.** UV/Visible Shimadzu UV1800 spectrometer

**Scanning electron microscope (SEM).** Samples were observed using a field-emission SEM coupled with energy dispersive X-ray spectroscopy (EDX) on a Hitachi SU5000 with an acceleration voltage of 5 keV. Samples were coated with a thickness of 100 to 150 Å of metallic chromium.

**¹H liquid state NMR.** ¹H NMR spectra were recorded on a Bruker Biospin DRX-600 (300 MHz) spectrometer. For ¹H-NMR analysis, 5–10 mg of the cage sample was solubilized in DMSO-*d*6 (750 µl).

**Gas sorption.** Kr (77 K) gas sorption isotherms of the fabric composite were recorded using an ASAP 2020 volumetric adsorption instrument from Micromeritics. Before gas sorption measurements, the samples were activated at 60 °C for 6 hours. The specific surface area was determined using the BET method within the P/P₀ range of 0.065-0.2 for Kr.

**Mass spectrometry.** MALDI-FTICR-MS and ESI-FTICR-MS measurement was realized on a Bruker 9.4 Tesla SolariX XR FTICR mass spectrometer (Bruker Daltonics, Bremen, Germany).

The ESI voltage was set to 4.1 kV in positive mode, the drying gas temperature was set to 200.0 °C, and the spray shield was set to -500.0 V. The acquisition was set at 4 M, with a mass range of 300-3000 m/z, and 32 scans were accumulated.
For MALDI-FTICR-MS, a piece of tissue was deposited on double-sided copper tape attached to a large MALDI plate (Bruker Daltonics, Bremen, Germany). Five microliters of dichloromethane are deposited on the tissue, followed by 10 µL of the HCCA matrix (10 mg/mL in 70% acetonitrile, 30% H₂O and 0.1% formic acid). A Bruker Smartbeam-II Laser System was used for irradiation at a frequency of 1000 Hz, utilizing the “20 µm” predefined shot pattern. MALDI-FTICR spectra were generated from 700 laser shots in the *m/z* range from 693.00 to 5000 with 1 M data points (i.e., transient length of 2.5166 s) and 50% of laser power. Ten spectra were averaged. The transfer time of the ICR cell was set to 1.2 ms, and the quadrupole mass filter operating in RF-only mode was set at *m/z* 500. The time of flight was set to 1.1 ms and the frequency to 4 MHz for the transfer optics.

**Abrasion tests.** The abrasion resistance of the composite fabrics was tested using a Martindale SDL Atlas, in accordance with the ISO 12947-3:1999 standard. It involves measuring the weight loss after a specified number of abrasion cycles. A 3.8 cm diameter sample was placed against a 14 cm diameter wool abrasive textile, with a pressure of 9 kPa, and subjected to 3750 cycles of circular friction at a steady pace (52 cycles/min). A sample was deemed stable (not damaged) when the weight loss was less than or equal to 2%.

**Artificial ageing.** Artificial ageing was conducted in Xenotest 440 (Atlas Material Testing Technology GmbH, Linsengericht, Germany) using xenon-arc radiation. The spectral distribution of sunlight is simulated in the ultraviolet (UV) and visible wavelength ranges by using appropriate filters (for daylight and daylight behind window glass). The sample holders rotate around the lamp with one side facing the lamp continuously. The device is equipped with xenon lamps and operated under the following conditions: 50 W/m² and a black panel temperature of 44 °C. The room temperature and humidity were maintained at approximately 30 ± 1 °C and 60%, respectively,
throughout the experiment. The properties of the samples were evaluated after 24 hours of artificial accelerated ageing.

**Air permeability test.** A standard test method for air permeability of textiles was carried out using an analyzer from Eni Development, following the ISO EN 9237:1995 norm for industrial fabrics. Typically, a circular piece of fabric (20 cm²) is submitted to an air pressure of 200 Pa at 20.4°C with a relative humidity of 64.1%. Each sample (pristine fabric or composites) was measured four times; the results are presented in Table S1.

**ICP analysis.** Inductively coupled plasma-optical emission spectrometry (ICP-OES) was used to determine cage loading in the composite. Samples of 1 × 1 cm² dimension were weighted and digested in concentrated H₂SO₄ before diluting them to 0.5 M (V = 10 mL) for the analysis.

Mass loadings (MLs) of the cages on the fibers were calculated using the following equation:

$$ (1) ML = C_{Zr} * \frac{0.01}{m * W_{Zr}} $$

where CZr is the measured concentration of Zr (in mg/mL) from ICP; m is the mass of the composite, and WZr is the mass percentage of Zr in pristine ZrT-2.

**Degradation of Paraoxon-Methyl (DMNP).** The protocol used was similar to the one previously developed by Farha et al.²⁶ A 1 x 1 cm² composite sample was weighed, cut into smaller pieces, and dispersed in an aqueous solution of 1 mL of N-ethylmorpholine (NEM) at 0.45 M in a 2 mL vial. After 20 minutes of stirring, 4 µL of DMNP (25 µmol) was added to the solution. Conversion of DMNP was monitored by following the formation of 4-nitrophenol, a DMNP degradation product with a typical absorbance at 407 nm, by using a UV/Visible Shimadzu UV1800 spectrometer. A 10 µL aliquot was taken at determined intervals and diluted in 5 mL of 0.45 M
NEM. Concentration of 4-nitrophenol was then calculated using the Beer-Lambert equation, the molar absorptivity coefficient ε of 4-nitrophenol being 18330 M⁻¹·cm⁻¹.²⁷

The degradation tests were performed at least three times for each composite. The concatenated data were fitted with an exponential function. The confidence interval and prediction interval are also shown. Both were obtained from the non-linear curve fitting (exponential) of the concatenated data.

## Synthesis.

The Zr-based cages were synthesized according to a previously reported method.²⁸

**Synthesis of ZrT-1.** In a typical synthesis, 1 g of zirconium cyclopentadienyl (ZrCp₂Cl₂, 3 mmol) is mixed with 281.2 mg of benzene-1,4-dicarboxylic acid (BDC, 2 mmol) in 5 mL of N,N-dimethylacetamide (DMA) and 1 mL of distilled water. The solution was heated at 65 °C for 8 hours. The white precipitate was isolated by centrifugation and washed with DMA (3x 20 mL) and the solvent was exchanged with dichloromethane (3x 20 mL). The solid was then isolated by centrifugation and activated in a vacuum oven at 65 °C for 12 hours.

**Synthesis of ZrT-2.** In a typical synthesis, 1 g of zirconium cyclopentadienyl (ZrCp₂Cl₂, 3 mmol) is mixed with 450.6 mg of benzene-1,3,5-tricarboxylic acid (BTC, 2 mmol) in 5 mL of N,N-dimethylacetamide (DMA) and 1 mL of distilled water. The solution was heated at 65 °C for 8 hours. The white precipitate was isolated by centrifugation and washed with DMA (3x 20 mL) and the solvent was exchanged with dichloromethane (3x 20 mL). The solid was then isolated by centrifugation and activated in a vacuum oven at 65 °C for 12 hours.

**Synthesis of ZrT-3.** In a typical synthesis, 1 g of zirconium cyclopentadienyl (ZrCp₂Cl₂, 3 mmol) is mixed with 500.6 mg of biphenyl-4,4'-dicarboxylic acid (BPDC, 2 mmol) in 5 mL of N,N-
dimethylacetamide (DMA) and 1 mL of distilled water. The solution was heated at 65 °C for 8
hours. The white precipitate was isolated by centrifugation and washed with DMA (3x 20 mL) and
the solvent was exchanged with dichloromethane (3x 20 mL). The solid was then isolated by
centrifugation and activated in a vacuum oven at 65 °C for 12 hours.

**Results and discussion**

Zr-based cages were synthesized following the reported literature.²⁹ The synthesis protocol
involves mixing bis(cyclopentadienyl)zirconium(IV) dichloride (ZrCp₂Cl₂) with benzene-1,4-
dicarboxylic acid (BDC), benzene-1,3,5-tricarboxylic acid (BTC), or biphenyl-4,4'-dicarboxylic
acid (BPDC) in dimethylacetamide (DMA) and water, yielding the tetrahedral cages ZrT-1, ZrT-
2 and ZrT-3, respectively.

The cage has the general formula {[Cp₃Zr₃(µ₃-O)(µ₂-OH)₃]₄L₆}⁴⁺ for dicarboxylic acid (L=BDC or BPDC), where the ligands serve as edges, or {[Cp₃Zr₃(µ₃-O)(µ₂-OH)₃]₄L₄}⁴⁺ for tricarboxylic acid ligands (L = BTC), which act as the faces of the tetrahedral cage. Each vertex of these tetrahedra is a Cp-capped zirconium oxocluster with a charge of +1, resulting in a total charge of +4 balanced by chloride anions. Powder X-ray diffraction (PXRD) and ¹H NMR analysis confirmed the formation of the expected cages crystallizing in a cubic space group (Figure S1 and S2).²⁸

The three cages were tested for their catalytic activity in degrading DMNP. For this, 5.8 µmol
of the cages (2.0 µmol relative to Zr₁₂) were added to an aqueous solution of n-ethylmorpholine
(NEM, 0.45 M) as a co-catalyst, and the mixture was stirred for 30 minutes. Then, 25 µmol of
DMNP was added to the solution. Since the degradation product forms 4-nitrophenol, which
absorbs at 407 nm, UV-visible spectroscopy was used to monitor the degradation process by taking
aliquots of the solution at regular intervals (Figure S3). From this, the time needed to convert 50% of DMNP (half-life time, t₁/₂) was determined from the exponential fit of the evolution of the percentage of conversion of DMNP as a function of time. The best catalytic activity was observed for ZrT-2 with a t₁/₂ of 23 minutes (Figure S4), which is in the same order as for Zr-based MOFs (UiO-66 t₁/₂= 25 min, NU-1000 t₁/₂= 15 min, and PCN-222 t₁/₂= 8 min).³⁰ The catalytic activity follows the order ZrT-2 > ZrT-1 > ZrT-3, as expected.²⁴ No correlation is observed between the pore diameter or the window opening of the cages and their catalytic activities. One hypothesis is that the constraint imposed by BTC ligands on the cage structure enhances the accessibility to the surface of the metal nodes, thereby improving catalytic activity. The difference in catalytic activity might also be due to variations in the Lewis acidity of the Zr(IV) catalytic center, as different ligands impact its local electronic environment.³¹

For coating cotton fibers, we focused on the ZrT-2 cage as it exhibits the highest degradation efficiency for DMNP. Two impregnation methods were explored. The first involved a solution of pre-synthesized ZrT-2 cage dispersed in ethanol (15 mL, 4 mg/mL), which was impregnated at 0°C onto a 5 × 5 cm² piece of cotton fabric (PS\_ZrT-2@CF). A low temperature was used to limit nucleation and crystal growth during cage packing, resulting in optimal conditions for producing smaller particles with a homogeneous distribution on the fabric. The second method involved placing the fabric in contact with a DMA solution of the metal precursor (0.11 M) for 17 hours, followed by the addition of the organic ligand (0.06 M), or vice versa. Subsequently, heating the solution at 65°C for 24 hours facilitated the in-situ formation of the cage (IS\_ZrT-2@CF). A one-pot strategy was also tested, in which both reagents were added simultaneously to the solution containing the fabric. The composites were washed with DMA, acetonitrile, and dichloromethane, then dried under air at room temperature.
For all obtained samples, PXRD analysis of the impregnated fabric does not show the characteristic peaks of the ZrT-2 cage (Figure S5). This can be explained by the low loading of cages onto the fabric, which renders MOC reflections invisible on the X-ray diffractogram compared to those of the cotton.<sup>32</sup> Another hypothesis is that, in the guest-free state, the ordered packing of the cages is lost, along with their extrinsic porosity, resulting in an amorphous structure.<sup>28</sup> Therefore, PXRD analysis is not a reliable method for characterizing the composite fabric. Instead, matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) was used to confirm the nature of the compounds impregnated on the fabric. The spectra clearly show the presence of intact tetrahedral cages on the fabric for both PS_ZrT-2@CF and IS_ZrT-2@CF samples (Figure 2a). Specifically, the observed ion peak at m/z of 2968.29839 corresponds to the [M-4Cl-4H]<sup>+</sup> ion. M represents the entire tetrahedral cage ( {[Cp<sub>3</sub>Zr<sub>3</sub>(μ<sub>3</sub>-O)(μ<sub>2-<sup>OH</sup>)<sub>3</sub>}<sub>4</sub>(BTC)<sub>4</sub>·4Cl) losing four Cl<sup>-</sup> and four H<sup>+</sup>. It matches the mass of pristine ZrT-2 used as a reference obtained by electrospray ionization mass spectrometry (ESI-MS) (Figure S6). Additionally, the experimental isotopic distribution patterns for each charge state are in good agreement with the theoretically calculated values based on the chemical composition of ZrT-2 (Figure 2b).
<figure><img src="image_3.png" /><figcaption>**Figure 2.** (a) MALDI-MS spectra of PS-ZrT-2@CF (orange) and IS-ZrT-2@CF (blue), and (b) experimental and calculated isotope patterns of the 1 + peaks at 2968 m/z. M = {[Cp₃Zr₃(µ₃-O)(µ₂-OH)₃]₄(BTC)₄}·4Cl.</figcaption></figure>

For impregnation with the pre-synthesized cage, different parameters, including impregnation duration (10 minutes or 1 hour) and the number of impregnation cycles (1 or 5 with a 2-second contact time), were examined to optimize the fiber coating. The evaluation criteria included cage loading, specific surface area (S<sub>BET</sub>), coating uniformity, and catalytic activity, which were measured using inductively coupled plasma (ICP) spectroscopy, krypton sorption (77K), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), and degradation tests, respectively. The best results were achieved when increasing the number of impregnation cycles from 1 to 5 while maintaining a short contact time (2 seconds). Specifically, the cage loading
reached 3.2 wt% of ZrT-2, and the SBET increased from 0.3 m²/g for the pristine fabric to 1.4 m²/g for the composite (Table S1 and Figures S7 and S8). SEM images of one impregnation cycle reveal cubic particles approximately 0.8 µm in size, heterogeneously distributed on the fiber surface. Increasing the number of impregnation cycles improved the fiber coverage with more densely packed cubic particles and fused particles (Figure S9). In contrast, increasing the contact time from 10 min to 1 h did not improve cage loading or SBET (1.1 wt% and 0.4 m²/g, respectively). Indeed, SEM images reveal an inhomogeneous distribution of aggregated particles, with no improvement in fiber coverage for either sample.

For the impregnation with in-situ synthesis of the cage, the order in which the reagents were applied to the fabric was examined (metal first IS-M, ligand first IS-L, or one-pot IS-O). Both cage loading and SBET were highest when the fabric was initially impregnated with the metal precursor (5.9 wt% and 1.3 m²/g, Table S1 and Figures S10 and S11). Images obtained by scanning electron microscopy (SEM) for IS-M_ZrT-2@CF appear to show no coverage of the fiber at all (Figure 3a). However, backscattered electron imaging reveals a distribution of bright areas across the fiber, attributed to the heavier zirconium, which deflects incident electrons more strongly than lighter elements. Indeed, elemental mapping of the transverse cut of the fabric using energy-dispersive X-ray spectroscopy (SEM-EDX) reveals a homogeneous distribution of zirconium and chlorine, and thus of the cages (Figure 3b). In contrast, IS-L_ZrT-2@CF and IS-O_ZrT-2@CF form spherical aggregates that cover the fibers heterogeneously (Figure S12). An air permeability test indicates that the deposition of ZrT-2 slightly decreases the breathability of cotton for IS-M_ZrT-2@CF (−14%) and PS-5C_ZrT-2@CF (−4%) composites compared to the pristine fabrics (1333.8 ± 25.5 L/m²/s).
<figure><img src="image_4.png" /><figcaption>**Figure 3.** SEM images of IS-M_ZrT-2@CF with (a) secondary electron (SE) and (b) backscattered electron (BSE) detectors. (c) SEM-EDX analysis on a transverse cut of the fiber, showing the electron image and corresponding elemental mapping of the carbon, zirconium and chlorine elements.</figcaption></figure>

The catalytic activity of the fabric composites (1 x 1 cm²) was measured under the same conditions as the pristine cage. The half-time to convert 50% of the DMNP was 152.4 ± 58.5 minutes and 164.2 ± 36.7 minutes for the impregnation times of 10 minutes and 1 hour, respectively (Figure S13a and b). The highest activity was observed after five cycles of impregnation, with a t₁/₂ of 42.7 ± 12.6 minutes, compared to more than 360 minutes for a single cycle (Figure S13c and d). Increasing the deposition cycle has a greater impact on the catalytic degradation of DMNP than increasing the impregnation time, because of the higher cage loading in the composites. In the second impregnation method, the shortest t₁/₂ (22.2 ± 1.2 min) was observed for IS-M_ZrT-2@CF, which has the highest cage loading (Figure S14a). It is worth
noting that even IS-L_ZrT-2@CF and IS-O_ZrT-2@CF ($t_{1/2}$ = 35.7 ± 6.1 min and 30.0 ± 8.2 min, respectively) performed better than the best composite prepared from pre-synthesized cages (Figure S14 b and c). Control experiments were performed on pristine cotton and on cotton impregnated with the metal precursor using the same degradation test conditions. A DMNP conversion below 15% was attributed to NEM, the co-catalyst (Figure S14d).

The composites have undergone standard resistance normed tests. The abrasion test involves a contact pressure of 9 kPa and 3600 cycles of circular friction on the fabric surface (ISO 12947-3). For impregnation from pre-synthesized cages, the final weight loss is greater with increasing the number of impregnation cycles (4.5% versus 8.8%) than with extending the impregnation time (5.1% versus 2%) as shown in Figure 4a and Figures S15a and b. The abrasion tests indicated a negligible weight loss of 1% for IS-M_ZrT-2@CF, compared to 3% and 6% for IS-L_ZrT-2@CF and IS-O_ZrT-2@CF, respectively (Figure S15c). These results were supported by ICP and sorption analysis, where all samples, except IS-M_ZrT-2@CF, show a decrease in the cage loading (Figure 4a) and $S_{BET}$ after abrasion tests (Figure S7, S8, S10, and S11).

The minimal weight loss for IS-M_ZrT-2@CF may be due to a stronger interaction between the cage and the fabric when impregnating the fabric with the metal initially, rather than with the organic ligand. Indeed, water is present in DMA for the hydrolysis of $ZrCp_2Cl_2$, which generates Zr–OH species that can strongly coordinate to cellulose hydroxyls (M–O bonds).³³ On the other hand, the interactions for the BTC ligand should be dominated mainly by hydrogen bonding between its –COOH groups and cellulose –OH groups. Nonetheless, the binding remains relatively weak and non-specific compared to coordination chemistry. These observations confirm that impregnating the fabric with the metal precursor first leads to better adherence of ZrT-2 cages. Moreover, SEM-EDX analysis of IS-M_ZrT-2@CF after the abrasion test revealed that the
homogeneous distribution of the cages across the fabric remains intact (Figure 4b). Most importantly, the half-life time for IS-M_ZrT-2@CF remains unchanged after abrasion ($t_{1/2}$ = 23.0 ± 1.2 min), whereas it increases by at least half for all other composites, regardless of the impregnation method (Figure 5, Table S2 and Figure S16).

<figure><img src="image_5.png" /><figcaption>**Figure 4.** (a) Effect of the impregnation methods on the cage loading before (gray) and after (red) the abrasion test, as well as after the ageing test (blue) for PS_ZrT-2@CF and IS_ZrT-2@CF. The total weight loss after 3600 abrasion cycles is shown as black squares for each composite (right y-axis). (b) SEM-EDX analysis on a transverse cut of the IS-M_ZrT-2@CF after abrasion test, showing the electron image and corresponding elemental mapping of the carbon, zirconium and chlorine elements.</figcaption></figure>
A severe artificial ageing test, simulating six days of extreme conditions, was also performed on the best composite, IS-M_ZrT-2@CF. The sample was placed in an exposure chamber under UV irradiation (3456 J/m²), controlled temperature (30 °C), and moisture (relative humidity = 60%) for 24 hours. ICP analysis shows that the cage loading and S<sub>BET</sub> remain unchanged after the ageing test (Figure 4a and Figure S17), indicating strong resistance under the selected conditions. However, its efficiency in degrading DMNP was reduced by a factor of two (t<sub>1/2</sub>= 41.0 ± 5.0 min, Figure 5). Zr-based MOCs are usually stable in both acidic and basic solutions and at high temperatures. However, structural transformation and decomposition should not be ruled out, such as the removal of cyclopentadiene from the metal node or its dimerization under mild conditions.<sup>34</sup>

<figure><img src="image_6.png" /><figcaption>**Figure 5.** Evolution of the half-life time of DMNP degradation before (gray) and after (red) the abrasion test, as well as after the ageing test (blue) for PS_ZrT-2@CF and IS_ZrT-2@CF.</figcaption></figure>

Conclusions

In summary, MOC-cotton fabric composites were synthesized using impregnation methods. A comparison was made between impregnation from pre-synthesized cages and in-situ synthesis. The latter approach proved more promising, resulting in effective coverage of the fabrics, as evidenced by uniform deposition of the porous material within the fabric. A stronger interaction
between the fabric and the deposit was observed when the fabric was first impregnated with the metal precursors, likely due to the formation of a coordination bond between the metal and the cellulose hydroxyl groups. This enhances resistance to abrasion and severe ageing conditions. Additionally, the composite retains excellent permeability. Cage loading is the primary parameter influencing the composite's catalytic performance in the degradation of DMNP. In-situ impregnation proved to be the most efficient method to achieve high cage loading and efficient immobilization of the zirconium-based catalyst. The composite IS-M_ZrT2@CF shows the best efficiency in DMNP decomposition (t₁/₂ < 25 min) even after abrasion, despite only a relatively low ZrT-2 loading (6 wt%) in the fabrics. Although catalytic efficiency diminishes after ageing, the composite remains significantly better than UiO-66-NH₂ composites impregnated onto cotton fabric, which showed a much longer half-time (>100 min) and a loss of porosity, indicating lower resistance under similar ageing conditions.³⁵ However, some optimization of our system is still necessary to compete with the catalytic performance of the recent Zr-based MOF/hydrogel (MOF-808) composite (t₁/₂ = 1 min) for which the use of a branched polyethylenimine hydrogel (BPEIH) mediates the microenvironment in MOFs for a more effective reaction with DMNP by providing a high density of amine functional groups that regenerate the catalytic sites, as well as the trapped water in the hydrogel, which facilitates hydrolysis.³⁶

## ASSOCIATED CONTENT

The experimental protocols and data supporting this article have been included as part of the Supplementary Information. The following file is available free of charge.

Materials and methods, synthesis protocols, PXRD diffractograms, ¹HNMR spectra, UV-visible, and ESI-TOF-MS spectra, Kr sorption isotherms, SEM-EDX images, abrasion and degradation tests. (PDF)
# AUTHOR INFORMATION

## Corresponding Author

*Alexandre Legrand. Univ. Lille, CNRS, Centrale Lille, UMR 8181 – UCCS – Unité de Catalyse et Chimie du Solide, Univ. Artois, Lille, F-59000 France. orcid.org/0000-0002-7975-9348; E-mail: alexandre.legrand@univ-lille.fr

## Author Contributions

AL formulated the research goals and aims and managed the planning and execution of the research activity. AL, EC, and CV developed the methodology. EC and PH conducted the research and investigation, specifically performing the experiments (composite synthesis) and characterisations. FB performed mass spectroscopy of the composite. MF and CC performed the abrasion and ageing tests. EC and AL wrote the original draft, and all authors reviewed and commented on the manuscript. AL, CC, TL, and CV verified the overall reproducibility of experiments and research outputs.

## ORCID

Elise Cape: 0009-0008-1372-8267

Rosalia Jreis: 0009-0002-1302-4282

Fabrice Bray: 0000-0002-4723-8206

Manuela Ferreira: 0000-0003-0180-4441

Thierry Loiseau: 0000-0001-8175-3407

Christine Campagne: 0000-0001-5223-0236
## Notes

There are no conflicts of interest to declare.

## ACKNOWLEDGMENT

The authors would like to thank the UCCS for its support. ICP analyses were performed on a << Spectrométrie par torche à plasma >> platform of the Research Federation Michel-Eugène Chevreul hosted by the LASIR laboratory. Financial support from the IR INFRANALYTICS FR2054 for conducting the research is gratefully acknowledged. The SEM national facility in Lille was supported by Conseil Régional des Hauts-de-France, European Regional Development Fund, and CNRS-INSU. The authors also thank Alexandre Fadel for his help in SEM analyses, Laurence Burylo for XRD measurements, and Véronique Alaimo for the ICP analysis. Parts of Figure 1 have been designed using free license icons from Freepik, Ayub Irawan (Flaticon.com), Jatuphol Intaphong, and Oleg Gapeenko (Vecteezy.com).

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<figure><img src="image_7.png" /></figure>
Development of a robust textile composite for the degradation of a nerve agent simulant (DMNP) by functionalizing cotton fabric with Zr-based cages.