Selective Photooxidation of a Mustard‐Gas Simulant Catalyzed by a Porphyrinic Metal–Organic Framework

Abstract

The photooxidation of am ustard-gas simulant, 2-chloroethyl ethyl sulfide (CEES), is studied using aporphyrin-based metal-organic framework (MOF) catalyst. At room temperature and neutral pH value,singlet oxygen is generated by PCN-222/MOF-545 using an inexpensive and commercially available light-emitting diode.The singlet oxygen produced by PCN-222/MOF-545 selectively oxidizes CEES to the comparatively nontoxicp roduct 2-chloroethyl ethyl sulfoxide (CEESO) without formation of the highly toxic sulfone product. In comparison to current methods,w hichu tilize hydrogen peroxidea sa no xidizing agent, this is am ore realistic,c onvenient, and effective method for mustard-gas detoxification.

Atomistic Approach toward Selective Photocatalytic Oxidation of a Mustard-Gas Simulant: A Case Study with Heavy-Chalcogen-Containing PCN-57 Analogues

“…26 We have previously reported the use of a porphyrin photosensitizer in a Zr6-based MOF PCN-222/MOF-545, to photocatalyze the oxidation of mustard gas simulant 2-chloroethyl ethyl sulfide (CEES) to 2-chloroethyl ethyl sulfoxide (CEESO) with a blue LED at a half-life (t1/2) of 13 min. 6 The pyrene containing mesoporous MOF, NU-1000, showed catalytic activity for the partial oxidation of CEES itself under UV light (t1/2 = 6 min). 5 The catalytic performance of NU-1000 was further improved (t1/2 = 3.5 min) when fullerene-based photosensitizers were postsynthetically incorporated in the MOF.…”

Elucidating heterogeneous photocatalytic superiority of microporous porphyrin organic cage

“…NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-14831-x ARTICLE Heterogeneous photocatalytic properties of PTC-1(2H). It is well known that the practical application of the molecular porphyrins as heterogeneous photocatalysts has been retarded by the aggregation-induced deactivation 13,15 . The lack of both the intramolecular and intermolecular face-to-face packed porphyrin moieties in the cage-based supramolecular framework as revealed by single crystal X-ray analysis, in combination with the existence of moderately permanent porosity in the PTC-1(2H) framework, therefore inspires our interest toward investigating its heterogeneous photocatalytic performance.…”

“…It has been established that the excited triplet states of some visible light-absorbing molecules are able to initiate the catalytic cycle via photo-induced electron/ energy transfer process [1][2][3][4][5][6] . By virtue of the strong visible light absorption, long triplet lifetime, and high triplet quantum yield, porphyrin derivatives have been extensively utilized as one of the most powerful photocatalysts toward aerobic organic reactions [7][8][9][10][11][12][13][14][15][16][17][18] . Their practical applications have been retarded by aggregation-induced deactivation of photosensitized performance and low-density solar energy 5,15 ; it is therefore of great importance to develop excellent molecular porphyrin photocatalysts with improved absorption and excited states for facilitating photon conversion.…”

Thermal and catalytic methods used for destruction of chemical warfare agents

“…Due to the high toxicity and difficulty in obtaining research permits for pure sulfur mustards, which result from the CWC convention, its simulants are used for research works. One of the simplest simulants of sulfur mustard is dibutyl sulfide; however, the most popular simulant is 2-chloroethyl ethyl sulfide (CEES) (Verma et al 2015(Verma et al , 2016Liu et al 2015;Li et al 2014).…”