A Lacunary Polyoxovanadate Precursor and Transition‐Metal‐Sandwiched Derivatives for Catalytic Oxidation of Sulfides

Abstract

A SeO3‐centered lacunary Keggin‐type heteropolyoxovanadate (hetero‐POV) K6H2[SeV10O28(SeO3)3]⋅14 H2O (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 [SeV9O33(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 K6H8[(SeV10O28(SeO3)3)2(M(H2O)4)]⋅24 H2O (M2+=Mn2+ (2), Co2+ (3), Zn2+ (4)). All four compounds were characterized by single‐crystal X‐ray structure analysis, IR, X‐ray photoelectron spectroscopy (XPS), EPR, and 51V NMR spectroscopy. Importantly, three TM‐sandwiched derivatives exhibited effective catalytic activity for the heterogeneous oxidative desulfurization of sulfides at room temperature.

Decavanadate‐based Transition Metal Hybrids as Bifunctional Catalysts for Sulfide Oxidation and C—C Bond Construction

“…The Co—O terminal bond distances are in the range of 2.102(3)—2.142(3) Å, which are similar to those of reported Co hybrids K 6 H 8 [(SeV 10 O 28 (SeO 3 ) 3 ) 2 (Co(H 2 O) 4 )]·24H 2 O. [ 24 ]…”

Two Polymorphic Polyoxometalate-Based Metal–Organic Frameworks for the Efficient Synthesis of Functionalized Sulfoxides and Detoxification of Mustard Gas Simulants

“…To realize catalyst reusability, one of the feasible strategies for constructing POM-based heterogeneous catalysts is to choose a proper carrier (e.g., metal oxides, COFs, graphene, nitrides, and MOFs) and immobilize the POMs. ,,− Although the loading method can produce recyclable catalysts with better sulfoxide selectivity, it will suffer from ill-defined structures, leaching and inactivation of active sites, and low loading efficiency. Recently, some research studies have proved that the construction of crystalline pure inorganic high-nuclear clusters or simple organic–inorganic hybrid complexes is also a selectable route for POM heterogeneity, whereas the catalytic activities are usually restricted by the low specific surface area and the low exposure of active sites. , …”

“…Recently, some research studies have proved that the construction of crystalline pure inorganic high-nuclear clusters or simple organic−inorganic hybrid complexes is also a selectable route for POM heterogeneity, whereas the catalytic activities are usually restricted by the low specific surface area and the low exposure of active sites. 23,24 Taking these into account, the rational design and synthesis of crystalline POM-based MOFs (POMOFs), which can achieve the good dispersion of POMs at the molecular level and expose more accessible active sites, have been developed as an efficient strategy for optimizing and stabilizing traditional POM fragments. Meanwhile, the ordered porous structures in POMOFs facilitate the accessibility of substrate molecules to active POM fragments, actualizing the maximum benefit of POMs and the homogeneity of the heterogeneous catalysis.…”

Lacunary {Se4V10} Heteropolyoxovanadate Precursor with Monometal, Metal-Richer-Sandwiched Derivatives {Se8V20M} and {Se8V20M3}: Correlations between the Synthesis, Structure, and Catalytic Property

“… In fact, the 51 V NMR spectrum of diamagnetic Se 8 V 20 Zn 3 closely parallels those of precursors Se 4 V 10 and Se 8 V 20 Zn just because of the presence of the closely related {Se 4 V 10 } building blocks (Figure S6). , …”

“…Delightfully, we have lately developed a novel lacunary hetero-POV precursor, K 6 H 2 [SeV 10 O 28 (SeO 3 ) 3 ]•14H 2 O (abbreviated as Se 4 V 10 ; Figure 1a), using a straightforward synthesis approach with a fair yield. 22 This {VO 5 }-capped trivacant B-α-Keggin precursor could further react with TM 2+ ions, allowing the formation of a group of mononuclear sandwiched hetero-POVs, K 6 H 8 [(SeV 10 O 28 (SeO 3 ) 3 ) 2 (M-(H 2 O) 4 )]•26H 2 O (Se 8 V 20 M, where M = Mn 2+ , Co 2+ , and Zn 2+ ; Figure 1b). 22 Moreover, these three TM-sandwiched hetero-POVs have displayed good catalytic performances in the oxidative desulfurization of sulfides.…”