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Current Organic Synthesis


ISSN (Print): 1570-1794
ISSN (Online): 1875-6271

Research Article

Highly Reactive Heterogeneous Nanofibers Catalyst based on [Mo154] Clusters for Green Aerobic Oxidation of Sulfur Mustard Analogues under Ambient Conditions

Author(s): Reza Haddad*

Volume 19, Issue 7, 2022

Published on: 23 May, 2022

Page: [808 - 818] Pages: 11

DOI: 10.2174/1570179419666220301124655

Price: $65


Background: Due to the increasing chemical and biological threats posed by terrorist attacks, there is a need to design and prepare nanofibers (NFs) with the ability to neutralize CWAs. For this purpose polyacrylonitrile NFs and polyoxomolybdate [Mo154] (abbreviated as PAN NFs/[Mo154]) as a heterogeneous catalyst was prepared by electrospinning method with a diameter of about 100nm.

Objective: The PAN NFs/[Mo154] catalyze the selective aerobic oxidation of sulfur mustard stimulants, such as 2-chloroethyl ethyl sulfide (2-CEES) and 2-chloroethyl phenyl sulfide (2-CEPS) under green and “ambient” conditions (25 °C, 1atm O2) in the presence of ethanol with high efficiency and selectivity. 2-CEES was selected as a model reaction to optimize the parameters of the reaction.

Methods: The progress of the reaction was evaluated after different times using GC-FID, GCMS and TLC. The reaction product was also confirmed by 1H-NMR spectroscopy.

Results: The aerobic oxidation results of 2-CEES showed that PAN NFs/[Mo154] have a conversion of 98% to produce only a nontoxic product, 2-CEESO with the selectivity of 100% after 45min. The results were performed using [Mo154] without any PAN NFs for comparison whereas [Mo154] converts only 52% of 2-CEES under identical conditions.

Conclusion: Heterogeneous PAN NFs/[Mo154] catalyst was reused after washing with solvent up to 5 steps without leaching of [Mo154] from PAN NFs and without any loss in efficiency due to the morphology of NFs. In addition to the recovery of PAN NFs/[Mo154] in different cycles, the use of FT-IR, UV-Vis and TEM techniques confirms the stability and morphology of PAN NFs/[Mo154] after the fifth cycle, 2-CEES oxidation. According to our information, this report is the first use of PAN NFs enriched with [Mo154] for aerobic oxidation of sulfur mustard simulants.

Keywords: Sulfur mustard simulants, aerobic oxidation, polyoxomolybdates, polyacrylonitrile nanofiber, sulfoxide, blister agents.

Graphical Abstract
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