Detoxification of a Mustard-Gas Simulant by Nanosized Porphyrin

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Detoxification of a Mustard-Gas Simulant by Nanosized Porphyrin-based Metal-Organic Frameworks Carla Pereira, Yangyang Liu, Ashlee J. Howarth, Flavio Figueira, Joao Rocha, Joseph T. Hupp, Omar K. Farha, Joao P. C. Tome, and Filipe A. Almeida Paz ACS Appl. Nano Mater., Just Accepted Manuscript • DOI: 10.1021/acsanm.8b02014 • Publication Date (Web): 16 Nov 2018 Downloaded from http://pubs.acs.org on November 17, 2018

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Detoxification of a Mustard-Gas Simulant by Nano-sized Porphyrinbased Metal-Organic Frameworks. Carla F. Pereira#/, Yangyang Liu+, Ashlee Howarth+, Flávio Figueira#/, João Rocha#, Joseph T. Hupp+*, Omar K. Farha+*, João P. C. Tomé/|*, Filipe A. Almeida Paz#* Department of Chemistry & CICECO–Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal. of Chemistry & QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal. + Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA. | CQE, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. KEYWORDS: Sulfur mustard decontamination; Photo-catalysis; nano Molecular organic Frameworks; Porphyrins. #

/ Department

Supporting Information Placeholder ABSTRACT: Selectivity control of the decomposition of

sulfur mustard (bis(2-chloroethyl)sulfide) under photooxidation conditions using molecular oxygen remains a challenge. In this work, the photo-oxidation of a mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES), was studied using porphyrin-based Metal-Organic Framework (Por-MOFs) catalysts. It is shown that PorMOFs are selective oxidizing agents in the transformation of CEES into 2-chloroethyl ethyl sulfoxide (CEESO) without the formation of the highly toxic sulfone product 2-chloroethyl ethyl sulfone (CEESO2). This method to detoxify mustard-gas is regarded as more realistic, convenient and effective than the other available methods.

The study of Metal–Organic Frameworks (MOFs) remains an intense area of research aiming at applications in gas storage and separation, sensing, catalysis and in environmental issues. Recently, MOFs have found application in photo-catalysis using the energy of sunlight, or artificial light, to promote chemical transformations.1-5 Some of the most efficient photocatalyst MOFs exhibit potential in water splitting, CO2 reduction with photo-generation of free radicals/electrons, and photo-generation of singlet oxygen (1O2) from light-sensitizing MOFs.6-9 Singlet oxygen, a mild, yet efficient, oxidant is a versatile reactive oxygen species with applications in multiple organic transformations, as well as in the degradation of a wide variety of contaminants.10 In this regard, the widespread use of 1O2 as a benign and green agent in several chemical transformations led to its investigation in the detoxification of sulphur mustard gas.11-12 This is one of the most iconic chemical warfare agents (CWA) used in World War I, and even today it is considered

among the most effective chemical weapons. Sulfur mustard has a health toxicity level of 100 ppm, causing severe health effects, namely skin blisters, irritation to the eyes and respiratory tract, while in some cases may even cause death.13 These reasons prompted research into the development of efficient materials and methods capable to catalytically decompose sulfur mustard, so to prevent and avoid human exposure by incorporating them into materials of filtration systems, textiles or even to detoxify sulfur mustard stockpiles.14-21 The most common detoxification routes of sulfur mustard are depicted in Scheme 1, where the most favorable path consists in the partial oxidation of sulfur mustard to bis(2chloroethyl) sulfoxide, since the remaining commonly used degradation approaches (hydrolysis and dehydrohalogenation) are too slow or incomplete to be used as effective decontamination methods.22-25 The full oxidation pathway produces, however, bis(2chloroethyl)sulfone, which is itself also very toxic.26 For this reason, the design of degradation routes allowing only the partial oxidation of sulfur mustard remains a major challenge.27-28 The use of singlet oxygen (1O2) produced by photo-oxidation reactions has already proved successful using several photosensitizers.29-33 The use of MOFs based on porphyrins for this purpose has been investigated by Hupp and coworkers, showing that it is possible to decompose selectively CEES to the

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Scheme 1: Common catalytic degradation routes of sulphur mustard.

corresponding 2-chloroethyl ethyl sulfoxide (CEESO) equivalent to the non-toxic bis(2-chloroethyl)sulfoxide in a fairly simple fashion.16 Porphyrin-based MOFs (PorMOFs) materials constitute a highly interesting branch of MOFs, which despite being in its infancy has received much attention in the past decade.34 Porphyrins are structurally functional robust molecules with terminal pendant functional groups that can be easily tuned, while exhibiting a relatively rigid geometry and high thermal stability as well as multiple applications.35-38 Herein, we report the first examples of phosphonic acid porphyrinbased nano-MOFs, namely [La(H9TPPA)(H2O)x]Cl2·yH2O (1), [Yb(H9TPPA)(H2O)x]Cl2·yH2O (2) and [Y(H9TPPA)(H2O)x]Cl2·yH2O (3) (where x+y = 7), employed as photo-catalysts in the detoxification of sulfur mustard.16, 28, 39-40 The nano-MOFs are obtained combining 5,10,15,20tetrakis(p-phenylphosphonic acid)porphyrin (H10TPPA) and the correspondent chloride lanthanide salts, under hydrothermal conditions using a recently published procedure (Scheme 2).41 These materials provide a reasonably good sensitization and production of 1O2.41 STEM and dynamic light scattering (DLS) analysis of 1-3 (Figure S1) confirm their nanometric size (ca. 180, 140 and 100 nm). The porosity of these materials was assessed with N2 adsorption/desorption isotherms.

NH N (HO)2OP

PO(OH)2

N HN

La

HCl H2O

(HO)2OP

1

+

3

1

2

3

2 Scheme 2: Hydrothermal synthesis of nano-MOFs 1-3 and STEM images of materials of the prepared materials.

We concluded that the materials have a very limited porosity. The experimentally determined values of the BET surface area were 91, 33 and 25 m2/g for materials 1, 2 and 3, respectively, clearly showing that most likely these are dense coordination polymers (Figure S2). The oxidation of CEES was performed using a method recently reported, where the simulant CEES was selectively oxidized to CEESO without formation of CEESO2.16 This simulant is deemed as exhibiting an oxidation behavior similar to mustard gas, while being much less toxic and safer to manipulate.39, 42 Interestingly, some differences between CEES and sulfur mustard are observed in this kind of photo-oxidation reaction. The lesser solubility of sulfur mustard in methanol contrasts with the higher CEES solubility, delaying the reaction by a few minutes as described previously by Hupp and coworkers. Nonetheless, oxidation reactions mediated by 1O2 offer several advantages, being the most important the prevention of the complete oxidation of CEES to CEESO2. Mechanistically, on the basis of highlevel ab initio performed by Jensen and coworkers it was established that an S-hydroperoxysulfonium ylide intermediate can be formed which can be rearranged with a reasonably low energy barrier (∼12 kcal/mol) to either an R-hydroperoxide or to a protonated sulfone ylide structure, leading to the sulfone product via a keto-enol rearrangement.43 As a consequence, intramolecular

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sulfone formation should not be observed (or should at least be reduced) when products corresponding to oxidation of the R-carbon are observed. The use of stronger oxidizing agents, such as hydrogen peroxide or tert-butyl hydroperoxide, usually yields fulloxidized CEESO2.44-46 For this reason, the use of molecular oxygen combined with light and Por-MOFs is particulary convenient as these conditions facilitate the production of 1O2 which, in turn, leads to a single oxidation, instead of full oxidation of the substrate. In a typical experiment, 2% mol of the catalyst (1, 2 or 3) were dispersed in methanol in a sealed glass tube. After purging with O2 for 20 min, CEES was added using a micro-syringe and the reaction was monitored by GCFID, and products identified by GC-MS. The main absorption bands of 1, 2 and 3 are centred at 420 nm, which is consistent with absorption of porphyrin cores at the Soret Band region (Figure S8). As a result, a blue UV LED (λmax = 400-500 nm, Figure S9) was chosen for the generation of singlet oxygen from porphyrins. Each blue LED (and two were used at all the times) has a power density of 325 mW/cm2. Under blue LED irradiation the singlet oxygen generated by the materials selectively oxidized CEES to CEESO, with only trace amounts of 1-(ethylsulfinyl)-2-methoxyethane, a nontoxic side product of the reaction obtained from methanolysis (Figure S3). 28 The CEES photo-oxidation kinetic profiles using catalysts 1, 2 and 3 are shown in figure 1.

Figure 1: Kinetic profiles for oxidation of CEES (23 μL, 0.2 mmol) in the presence of 2% mol of 1, 2 and 3. Lines between experimental points are guides to the eye. (Blue Led: 465-475 nm).

Given the nature of our experiment where we irradiate a powder in a vial, we anticipate that we are only irradiating the porphyrins on the surface of the material. As a result, our actual catalyst loading, in terms of “active” catalyst is likely lower than we report.

CEES detoxification half-lives in the presence of PorMOFs 1, 2, 3 were 19, 18 and 14 minutes, respectively. After complete conversion of CEES (Figure 2), the reusability and stability of the materials were tested by adding more CEES to the system and purging with O2 for 20 min to re-establish the original reaction conditions. In the absence of 1, 2, 3, the conversion of CEES was negligible. These cycles were performed three times for each material and all tests were completed in less than 60 minutes, with full CEES conversion.

Figure 2: Kinetic profiles for CEES oxidation after a second injection of (23 μ L, 0.2 mmol) using 2% mol [Y(H9TPPA)(H2O)x]Cl2·yH2O (3) (where x+y = 7): following the first CEES injection, the simulant was completely converted to non-toxic products. Figure 2 shows the oxidation kinetics of the second cycle for 3, where the catalyst exhibiting the lowest half-life time in the first cycle (see the reaction profile for 1 and 2 in Figures S4 and S5 in the ESI). Illumination of the photosensitizer is required at all times to generate singlet oxygen, which goes on to oxidize CEES. Because there is no other oxidant in our system, reactions without illumination does not provide any conversion of CEES. Inductively coupled plasma-optical emission spectroscopy (ICP-OES) revealed only trace amounts of the metals leached out to the reactive mixture (data not shown). Altogether, these results show that 1, 2 and 3 perform well as heterogeneous catalysts in this reaction, with 3 being the most effective oxidation catalyst with a half-life time (full time of 28 min.) of ca. 14 minutes. We further note that these results, are comparable with those reported for PCN22 whose the oxidation half life time is ca. 13 min.16 The second CEES injection provided a very slightly faster catalytic cycle with a half-life time of ca. 11 min. The reason for the increased a half-life time in the first cycle is due to an induction period after the first CEES injection which delays the reaction.16, 47-49 Powder X-ray diffraction confirms the materials preserve their structural integrity after the second catalytic cycle



(Figure 3, for 3, and Figures S6 and S7 in the ESI, for 1 and 2. Interestingly, the H10TPPA ligand in solution shows a comparable half-life time to the materials (Figure S10). However much of the advantages provided by the heterogeneous catalysts are not obtainable with the homogeneous H10TPPA. For instance, the structure of nano-Por materials 1, 2 and 3 isolates the porphyrin moieties in an ordered array, which should help to enhance the efficiency of singlet oxygen generation, preventing aggregation and photodegradation as well as provide additional recoverability and reuse capabilities.

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increases the photocatalytic capabilities of the materials.50-51 While this is not the case, this report shows that the photocatalytic activity of coordination polymers towards the sulfur mustard simulant seems much more associated with the capability of the photosensitizer to produce singlet oxygen than the actual crystallite size or crystal structure. ASSOCIATED CONTENT Supporting Information. The Supporting Information contents are; Experimental section, Photocatalytic Studies, Stem Images of materials 1 to 3, Chromatogram indicating the products of the photo-catalysis, Reusability tests, PXRD spectra of materials 1 to 3, PXRD spectra of materials 1 to 3 after reusability tests. (PDF)

AUTHOR INFORMATION Corresponding Author

E-mail: [email protected] E-mail: [email protected] E-mail: [email protected] E-mail: [email protected] Funding Sources

Figure 3: Powder X-ray diffractograms of [Y(H9TPPA)(H2O)x]Cl2·yH2O (3) (where x+y = 7) before and after the catalytic cycles.

Conclusions Under blue LED irradiation, porphyrin based nano-MOFs [La(H9TPPA)(H2O)x]Cl2·yH2O (1) and [Yb(H9TPPA)(H2O)x]Cl2·yH2O (2) and [Y(H9TPPA)(H2O)x]Cl2·yH2O (3) (where x+y = 7) are heterogeneous catalysts for the oxidation of CEES, a mustard gas simulant, to nontoxic products with half-life times of 19, 18 and 14 min, respectively. Furthermore, the present materials exhibit a selectivity control towards the decomposition of sulfur mustard (bis-2chloroethylsulfide) under photo-oxidation conditions using molecular oxygen, avoiding the full oxidized toxic product bis-2-chloroethyl sulfone. We believe these results are associated with the amounts of 1O2 the ligand can produce, meaning that other materials assembled from ligands with even better 1O2 production will most likely lead to better oxidation half-life times. In sum, these results constitute unprecedented results considering the use of nano porphyrin-based MOFs in the photocatalytic degradation of a mustard gas simulant. There is much discussion in the literature about the applicability and behaviour of nano- and micro- sized materials, and there are several reports where the use of nano materials

Fundação para a Ciência e a Tecnologia (FCT, Portugal), the European Union, QREN, FEDER through Programa Operacional Factores de Competitividade (COMPETE), CICECO - Aveiro Institute of Materials (POCI-01-0145FEDER-007679; FCT Ref. UID/CTM/50011/2013), QOPNA (FCT UID/QUI/00062/2013) and CQE (FCT UID/QUI/0100/2013) research units, financed by national funds through the FCT/MEC and when appropriate cofinanced by FEDER under the PT2020 Partnership Agreement.

ACKNOWLEDGMENT We wish to thank Fundação para a Ciência e a Tecnologia (FCT, Portugal), the European Union, QREN, FEDER through Programa Operacional Factores de Competitividade (COMPETE), CICECO - Aveiro Institute of Materials (POCI-01-0145-FEDER-007679; FCT Ref. UID/CTM/50011/2013), QOPNA (FCT UID/QUI/00062/2013) and CQE (FCT UID/QUI/0100/2013) research units, financed by national funds through the FCT/MEC and when appropriate cofinanced by FEDER under the PT2020 Partnership Agreement. Individual Grants and Scholarships: FCT is also gratefully acknowledged for the Ph.D. grant No. SFRH/BD/86303/2012 (to CP). We further wish to acknowledge the project “Smart Green Homes – BOSCH” (POCI-010247-FEDER-007678) for the post-doctoral scholarship (Refs. BPD/CICECO/5508/2017) attributed to FF.

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51. Li, P.; Moon, S.-Y.; Guelta, M. A.; Lin, L.; Gómez-Gualdrón, D. A.; Snurr, R. Q.; Harvey, S. P.; Hupp, J. T.; Farha, O. K., Nanosizing a Metal–Organic Framework Enzyme Carrier for Accelerating Nerve Agent Hydrolysis. ACS Nano 2016, 10 (10), 9174-9182.

The photo-oxidation of a mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES), was studied using porphyrin-based nano Metal-Organic Framework (Por-MOFs) catalysts. The nano-Por-MOFs oxidized selectively the transformation of CEES into 2-chloroethyl ethyl sulfoxide (CEESO) under blue LED irradiation without the formation of the highly toxic sulfone product


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ACS Applied Nano Materials 2-chloroethyl ethyl sulfone (CEESO2). This was achieved in 28 minutes with the formation of trace amounts of 1(ethylsulfinyl)-2-methoxyethane.

2 mol% MOF catalyst

CEES Cl

+

S

1 2 3

Cl

S O

+

O2

H3CO

S O Traceamount


Detoxification of a Mustard-Gas Simulant by Nanosized Porphyrin

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