Polyoxometalate-mediated syntheses of three structurally new silver clusters.

Three structurally new polyoxometalate-templated silver clusters, homometallic [(SiW9O34)@Ag24(iPrS)11(DPPP)6Cl]2(SiW12O40) (Ag24), heterometallic [(SiW9O34)@Ag22Cu(iPrS)11(DPPP)6Cl](SbF6)2 (Ag22Cu) and {Ag16(iPrS)6(DPPP)8(CH3COO)4[Co4(OH)3(H2O)SiW9O33]2}·(CH3CN)4 (Ag16Co8) (iPrS- = isopropanethiolate, DPPP = 1,3-bis(diphenylphosphino)propane, SbF6- = hexafluoroantimonate) have been successfully synthesized using a facile solvothermal approach. The introduction of copper and cobalt ions can induce obvious changes in the molecular configuration of the obtained clusters, leading to distinct temperature-dependent photoluminescence and photothermal conversion properties.

Transition metal-substituted polyoxometalate-ionic liquids with remarkable flame retardancy performance.

The development of effective and novel flame retardants has been attracting considerable attention in extenuating the fire threat of flammable polymer materials including the widely-used epoxy resins. In this work, we pioneeringly report the construction of transition-metal-substituted polyoxometalate-ionic liquids (tmsPOM-ILs) as effective flame retardants, which consist of tetra-metal-containing POMs ([M4(H2O)2(PW9O34)2]10-, M4P2, M = Ni, Cu) anions and tetra-n-heptylammonium [(n-C7H15)4N+, THPA] cations. The resulting tmsPOM-ILs exhibited remarkably improved fire-safety of the epoxy resin (EP) matrix and even at a loading amount of as low as 3 wt%, the flame retardancy efficiency was even higher than that of commercial flame retardants (aluminum hydroxide (ATH), triphenyl phosphate (TPP), and decabromodiphenyl ethane (DBDPE)). Physicochemical and mechanistic studies revealed that the remarkable flame retardancy performance of the tmsPOM-ILs reported is due to their excellent epoxy matrix compatibility and remarkable catalytic charring ability. This work opens up a brand-new research direction of developing next-generation compatible and effective tmsPOM-based molecular flame retardants at the molecular level.

Atomically Precise Silver Clusters Stabilized by Lacunary Polyoxometalates with Photocatalytic CO2 Reduction Activity.

The syntheses of atomically precise silver (Ag) clusters stabilized by multidentate lacunary polyoxometalate (POM) ligands have been emerging as a promising but challenging research direction, the combination of redox-active POM ligands and silver clusters will render them unexpected geometric structures and catalytic properties. Herein, we report the successful construction of two structurally-new lacunary POM-stabilized Ag clusters, TBA6 H14 Ag14 (DPPB)4 (CH3 CN)9 [Ag24 (Si2 W18 O66 )3 ] ⋅ 10CH3 CN ⋅ 9H2 O ({Ag24 (Si2 W18 O66 )3 }, TBA=tetra-n-butylammonium, DPPB=1,4-Bis(diphenylphosphino)butane) and TBA14 H6 Ag9 Na2 (H2 O)9 [Ag27 (Si2 W18 O66 )3 ] ⋅ 8CH3 CN ⋅ 10H2 O ({Ag27 (Si2 W18 O66 )3 }), using a facile one-pot solvothermal approach. Under otherwise identical synthetic conditions, the molecular structures of two POM-stabilized Ag clusters could be readily tuned by the addition of different organic ligands. In both compounds, the central trefoil-propeller-shaped {Ag24 }14+ and {Ag27 }17+ clusters bearing 10 delocalized valence electrons are stabilized by three C-shaped {Si2 W18 O66 } units. The femtosecond/nanosecond transient absorption spectroscopy revealed the rapid charge transfer between {Ag24 }14+ core and {Si2 W18 O66 } ligands. Both compounds have been pioneeringly investigated as catalysts for photocatalytic CO2 reduction to HCOOH with a high selectivity.

Structurally-New Hexadecanuclear Ni-Containing Silicotungstate with Catalytic Hydrogen Generation Activity.

A structurally-new, carbon-free hexadecanuclear Ni-containing silicotungstate, [Ni16(H2O)15(OH)9(PO4)4(SiW9O34)3]19-, has been facilely synthesized using a one-pot, solution-based synthetic method systematically characterized by single-crystal X-ray diffraction and several other techniques. The resulting complex works as a noble-metal-free catalyst for visible-light-driven catalytic generation of hydrogen, by coupling with a [Ir(coumarin)2(dtbbpy)][PF6] photosensitizer and a triethanolamine (TEOA) sacrificial electron donor. Under minimally optimized conditions, a turnover number (TON) of 842 was achieved for TBA-Ni16P4(SiW9)3-catalyzed hydrogen evolution system. The structural stability of TBA-Ni16P4(SiW9)3 catalyst under photocatalytic conditions was evaluated by the mercury-poisoning test, FT-IR, and DLS measurements. The photocatalytic mechanism was elucidated by both time-solved luminescence decay and static emission quenching measurements.

Metal-Organic Cages with {SiW9 Ni4 } Polyoxotungstate Nodes.

A tritopic, Ni-substituted Keggin cluster, {SiW9 Ni4 }, assembles with rigid dicarboxylate linkers to give rise to a set of discrete, POM2n L3n -type structures (POM={SiW9 Ni4 }) with defined interior voids. The outcome of coordination-driven self-assemblies of these polyhedral cages-from fused dimers to trigonal prisms-was found to be sensitive to bend angles of the ditopic ligands, which vary from 122° to 180°. These polyoxotungstate-based metal-organic polyhedra, when coupled with [Ru(bpy)3 ]Cl2 as a photosensitizer and triethanolamine as the electron donor, serve as highly effective catalysts for CO2 reduction, with turnover numbers up to 328 and CO selectivity as high as 96.2 %. The inner cavities of such cage structures, if functionalized or of sufficient size to encapsulate targeted guest molecules, could present a new strategy towards functional materials for potential applications.

Self-template synthesis of hollow ellipsoid Ni-Mn sulfides for supercapacitors, electrocatalytic oxidation of glucose and water treatment.

In this work, we have successfully developed a simple self-template route for preparation of hollow ellipsoid Ni-Mn sulfides. This route involves the synthesis of solid Ni-Mn ellipsoids via a chemical precipitation method. Then, using thioacetamide (TAA) as the sulfur source, the solid Ni-Mn ellipsoids can be easily converted to hollow ellipsoid Ni-Mn sulfides in ethanol via sulfidation reaction. The as-synthesized hollow ellipsoid Ni-Mn sulfides possess large specific surface areas and porous structures. Benefiting from these structural and compositional advantages, the electrochemical performance of the hollow ellipsoid Ni-Mn sulfides is studied. As expected, the hollow ellipsoid Ni-Mn sulfides show a high specific capacitance of 1636.8 F g-1 at 2.0 A g-1 and good cycling stability (only 4.9% loss after 4000 cycles) as electrode materials for supercapacitors. Furthermore, electrocatalytic oxidation of glucose based on the synthesized hollow ellipsoid Ni-Mn sulfides is also performed. The hollow ellipsoid Ni-Mn sulfides present high sensitivity and selectivity, good stability and a low detection limit (0.02 µM). In addition, the as-synthesized hollow ellipsoid Ni-Mn sulfides exhibit good ability to remove the Congo red dyes from water, which gives them potential application in water treatment. The current work makes a major contribution to the design and preparation of hollow metal sulfide structures, as well as their potential applications in supercapacitors, electrocatalytic oxidation of glucose and water treatment.