A Lacunary Polyoxovanadate Precursor and Transition‐Metal‐Sandwiched Derivatives for Catalytic Oxidation of Sulfides. Issue 40 (8th May 2020)

• Record Type: Journal Article
• Authors: Wan, Rong; He, Peipei; Liu, Zhen; Ma, Xinyi; Ma, Pengtao; Singh, Vikram; Zhang, Chao; Niu, Jingyang; Wang, Jingping
• Is Part Of: Chemistry. Volume 26:Issue 40(2020)
• Page Start: 8760
• Page End: 8766
• Publication Date: 2020-05-08
• Subjects: heterogeneous catalysts -- Keggin -- oxidation -- polyoxovanadates -- sulfides -- vanadoselenite; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201905741
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A SeO3 ‐centered lacunary Keggin‐type heteropolyoxovanadate (hetero‐POV) K6 H2 [SeV10 O28 (SeO3 )3 ]⋅ 14 H2 O (1 ) was isolated by one‐pot reaction of KVO3 and SeO2 under acidic conditions. X‐ray studies revealed that it comprised a single {VO5 }‐capped trivacant B‐α‐type Keggin ion [SeV9 O33 (VO)] 14− with its lacunary sites decorated by three {SeO3 } 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 K6 H8 [(SeV10 O28 (SeO3 )3 )2 (M(H2 O)4 )]⋅ 24 H2 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. Abstract : New topology of polyoxovanadates : A rare example of lacunary Keggin‐type vanadoselenite [SeV10 O28 (SeO3 )3 ] 8− ({Se4 V10 }) was readily obtained, which shows sufficient reactivity with divalent transition metals (TMs) to form a new series of TM‐sandwiched complexes {(Se4 V10 )2 M } (M=Mn, Co, Zn). Such new TM derivatives can efficiently catalyze the heterogeneous oxidation of sulfides in high conversion and selectivity under mild conditions.