40Ni-Added Poly(polyoxometalate) Assembled by {Ni₆GeW₉} and {Ni₈(GeW₉)₂} Units: Structure, Magnetic, and Heterogeneous Catalysis Properties

Abstract

A novel 40Ni-added germanotungstate, Cs8K14Na3H3{[Ni6(OH)3(H2O)6(B-α-GeW9O34)]2[Ni8(μ6–O)­(μ2–OH)2 (μ3–OH)2(H2O)­B2O3(OH)2(B-α-GeW9O34)2]}2·84H2O (1), was made by the reaction of the trivacant [A-α-GeW9O34]10– ({GeW9}) precursor with Ni2+ cations and B5O8 –, and systematically investigated by Fourier-transform infrared spectroscopy, elemental analysis, thermogravimetric analysis, and powder X-ray diffraction. Single crystal X-ray analysis indicates that the polyoxoanion of 1 is a novel octamer constructed by {Ni6GeW9} and {Ni8(GeW9)2} structural building units via Ni–OW linkages. The magnetic behavior shows the existence of overall ferromagnetic interactions among the Ni2+ centers in compound 1. Photocatalytic H2 production studies have implied that 1 can work as a heterogeneous catalyst for hydrogen production with decent robustness and recyclability.

Highly efficient photoelectrocatalytic oxidation of arsenic(iii) with a polyoxometalate-thiacalix[4]arene-based metal–organic complex-modified bismuth vanadate photoanode

“…Recently, MOC- and POM-based photocatalysts have gained significant attention owing to their potential photocatalytic performances. 40–47 POM-based metal–organic complexes (PMOCs) with the combined advantages of both POMs and MOCs have received growing interest due to their unique properties and prospective applications. 48,49 Recent studies have proved that PMOCs are efficient photocatalyst candidates for organic synthesis, CO 2 reduction, H 2 production, pollutant removal, etc .…”

High-Nuclear Co-Added Polyoxometalate-Based Chain: Electrocatalytic Oxygen Production

“…Polyoxometalates (POMs) have attracted great interest due to their advantages of high negative charges, variable shape tunability, remarkable redox capability, and accessible organic grafting. − They have been widely applied in areas of catalysis, medicine, magnetism, electrochemistry, etc. − Lacunary POMs can be considered inorganic multidentate ligands that are capable of clustering multinuclear metal–oxygen fragments at vacant sites and generating transition-metal-added POMs (TMAPs). , A large amount of such intriguing assemblies have been reported, particularly these high-nuclear TMAPs, exhibiting distinct physical and chemical properties arising from their diverse hyper-nuclear cores. − In the past few decades, the outburst of high-nuclear TMAPs has been witnessed by the observation of Zr 24 , Fe 14 , Fe 48 , Ni 20 , Ni 28 , Ni 40 , Co 16 , Co 21 , Mn 19 , Cu 16 , etc.…”

A wheel-shaped Zr-substituted phosphotungstate [{Zr(C2O4)2}3 (PO4)(P6W39O150)]39− with tunable proton conduction properties

“…1–8 In the realm of POMs, transition-metal substituted POMs (TMSPs) represent a prominent branch due to their varied structures and remarkable catalytic and magnetic properties. 9–12 In contrast to other TMSPs, the chemistry of zirconium-substituted polyoxometalates (ZrSPs) remains underexplored, primarily owing to the large ionic radius and high valence state of the Zr 4+ ion, leading to pronounced oxyphilicity in aqueous environments. Consequently, the design and synthesis of novel ZrSPs present formidable challenges, yet intriguing opportunities.…”