A New Hexa‐Ti IV ‐Substituted Sandwich‐Type Polyoxotungstate: Hydrothermal Synthesis, Structure, and Oxidative Decontamination of Chemical Warfare Agent Simulant

A new hexa‐Ti IV ‐substituted sandwich‐type silicotungstate, Na 2 (H 2 enMe) 4 [Ti 6 (µ‐O) 9 (A‐α‐SiW 9 O 34 H 2 ) 2 ] · 16H 2 O ( 1 , enMe = 1,2‐diaminopropane) has been synthesized under mild hydrothermal conditions and characterized by FT‐IR spectroscopy, elemental analysis, thermogravimetric analysis, single‐crystal and powder X‐ray diffraction. Compound 1 contains a dimeric polyoxoanion with two [A‐α‐SiW 9 O 34 ] 10– Keggin moieties sandwiching a trigonal‐prismatic [Ti 6 (µ‐O 9 )] 6+ cluster. The catalytic performance of 1 was evaluated for the oxidative decontamination of chemical warfare agent, i.e. sulfur mustard simulant, 2‐chloroethyl ethyl sulfide (CEES), using H 2 O 2 under ambient conditions, showing that 1 is an excellent catalyst for the rapid and complete transformation from CEES to nontoxic 2‐chloroethyl ethyl sulfoxide (CEESO) with 100 % selectivity. In addition, 1 exhibits good stability and recyclability.