Polyoxometalate‐Incorporated Cu^I‐Resorcin[4]arene Metal‐Organic Complexes as Heterogeneous Catalysts for Catalytic Oxidation of Mustard Gas Simulant

Abstract

Exploring efficient heterogeneous catalysts for catalytic oxidation of chemical warfare agents (CWAs) is highly desired. As a class of discrete anionic metal oxide clusters, polyoxometalates (POMs) provide abundant catalytic active sites, thus resulting their rich redox properties. Here, a family of known POM‐incorporated CuI‐resorcin[4]arene metal‐organic complexes, namely, [Cu4(TPTR4A)2][PW12O40](OH) ⋅ 0.5DMA ⋅ 5H2O (Cu‐PW), [Cu4(TPTR4 A)2][PMo12O40](OH) ⋅ 2DMA ⋅ H2O (Cu‐PMo) and [Cu4(TPTR4A)2][SiW12O40] ⋅ 2.5DMA (Cu‐SiW) were utilized as catalysts to promote the oxidation of 2‐chloroethyl ethyl sulfide (CEES). Strikingly, compared to the novel compound [Cu3Cl6(TPTR4A)(DMA)] ⋅ CH3CH2OH (defined as Cu‐T), the three complexes exhibited excellent stability, indicating that the integration of POMs and metal–organic units could improve the stability of the compounds. Moreover, Cu‐PMo and Cu‐PW showed higher activities for the catalytic oxidation of CEES to CEESO with selectivities both of 99 %.

Solution Blow Spinning Ultrafine Fiber Sponge-Loaded MOF-808 for Effective Adsorption and Degradation of Mustard Gas

“…In the past decade, metal oxides, − polyoxometalates, − metal hydroxides, − and metal–organic frameworks (MOFs) − have been used to effectively decompose chemical warfare agents into nontoxic or low-toxicity substances. Among them, zirconium-based materials, such as Zr (OH) 4 , and zirconium-based MOFs (MOF-808, UIO-66-NH 2 , NU-1000, etc.)…”

MOF-808 on Polyacrylonitrile Nanofibers for Degradation of Chemical Warfare Agents

“…However, saturation is easily attained via adsorption, which shortens the protection time and causes secondary pollution . In recent years, nanostructured materials (e.g., metal oxides, − polyoxometalates, − metal hydroxides, − and metal–organic frameworks (MOFs) − ) have been developed to catalytically degrade CWAs into nontoxic or less toxic substances.…”