A Lacunary Polyoxovanadate Precursor and Transition‐Metal‐Sandwiched Derivatives for Catalytic Oxidation of Sulfides
Rong Wan, Peipei He, Zhen Liu, Xinyi Ma, Pengtao Ma, Vikram Singh, Chao Zhang, Jingyang Niu, Jingping Wang
Abstract
Abstract A SeO 3 ‐centered lacunary Keggin‐type heteropolyoxovanadate (hetero‐POV) K 6 H 2 [SeV 10 O 28 (SeO 3 ) 3 ] ⋅ 14 H 2 O ( 1 ) was isolated by one‐pot reaction of KVO 3 and SeO 2 under acidic conditions. X‐ray studies revealed that it comprised a single {VO 5 }‐capped trivacant B‐α‐type Keggin ion [SeV 9 O 33 (VO)] 14− with its lacunary sites decorated by three {SeO 3 } pyramids. Interestingly, this new basic hetero‐POV building block was further used as a precursor to assemble with different transition‐metal (TM) ions, yielding a series of TM‐sandwiched POVs K 6 H 8 [(SeV 10 O 28 (SeO 3 ) 3 ) 2 (M(H 2 O) 4 )] ⋅ 24 H 2 O (M 2+ =Mn 2+ ( 2 ), Co 2+ ( 3 ), Zn 2+ ( 4 )). All four compounds were characterized by single‐crystal X‐ray structure analysis, IR, X‐ray photoelectron spectroscopy (XPS), EPR, and 51 V NMR spectroscopy. Importantly, three TM‐sandwiched derivatives exhibited effective catalytic activity for the heterogeneous oxidative desulfurization of sulfides at room temperature.