Inorganic‐organic Microporous Solid of Wells‐Dawson Type Polyoxometalate: Synthesis,Characterization, and Electrochemical Properties

An inorganic‐organic hybrid solid (H_6/5bppy)₅[P₂W₁₈O₆₂]·4.5H₂O ( 1 ) (bppy = 4‐(5‐(4‐bromophenyl)pyridin‐2‐yl)pyridine) was hydrothermally synthesized by using pre‐constructed Wells‐Dawson type salt α‐K₆P₂W₁₈O₆₂·15H₂O as inorganic moiety. The crystal structure keeps integrated and steady under the interactions together of aryl packing, hydrogen bonding and halogen bonding. X‐ray single crystal structure analysis reveals that compound 1 contains cavities with the sizes of about 6 × 8Å, in which H₂O molecules are captured. The hybrid was used as a solid bulk modifier to fabricate a three‐dimensional bulk‐modified carbon paste electrode ( 1 ‐CPE) by direct mixing. The electrochemical and electrocatalytic behavior of the 1 ‐CPE has been studied in detail. The results exhibit that the redox ability of the Wells‐Dawson polyanions can be maintained in the hybrid solid, which has a good electrocatalytic activity toward the reduction of bromate and hydrogen peroxide. A hydrodynamic voltammetric experiment was performed to characterize the electrode as an amperometric sensor for the determination of hydrogen peroxide. The 1 ‐CPE showed long‐term stability and excellent reproducibility of surface renewal.     

A Nanosized Gly‐Decorated Praseodymium‐Stabilized Selenotungstate Cluster: Synthesis,Structure, and Oxidation Catalysis

A flexible one‐pot strategy with pyramidal Se^IV heteroatoms was employed for the assembly of the praseodymium‐containing gly‐decorated polyoxotungstate [{Pr₃(H₂O)₁₀[Se₂W₂₂O₇₆(gly)₂]}₂(Se₂W₇O₃₀H₂)]¹⁸⁻ ( 1 a ), which is constructed from one {Se₂W₇O₃₀H₂} unit and two identical {Pr₃(H₂O)₁₀[Se₂W₂₂O₇₆(gly)₂]} units. Furthermore, the catalytic performance of Cs₂Na₄H₁₂[{Pr₃(H₂O)₁₀[Se₂W₂₂O₇₆(gly)₂]}₂(Se₂W₇O₃₀H₂)] ⋅ 25 H₂O ( 1 ) for alkene epoxidation with hydrogen peroxide was investigated under mild reaction conditions, and the experimental results suggested that compound 1 exhibits good catalytic performance for the epoxidation of cyclooctene.     

Fabrication and Electrochemical Behavior of Vanadium‐Substituted Keggin‐Type Polyoxometalates Multilayer Films on 4‐Aminobenzoic Acid Modified Glassy Carbon Electrodes

Two Vanadium‐substituted Keggin‐type polyoxometalates, K₃H₂[α‐SiVW₁₁O₄₀]?6H₂O (SiVW₁₁) and K₄H₂[γ(1, 2)‐SiV₂W₁₀O₄₀]?4H₂O (SiV₂W₁₀) were first successfully immobilized on 4‐aminobenzoic acid modified glass carbon electrodes respectively by layer‐by‐layer assembly with poly (ethylenimine) (PEI) as counterions. The regular growth processes were monitored by cyclic voltammetry (CV), and it was proved that the multilayer films were uniform and stable. The cyclic voltammetry results indicated that the electrochemical behavior of two multilayer films was similar, and their redox couples are pH‐ and scan rate‐dependent. The multilayer films show favorable electrocatalytic active toward the reduction of NO₂^?, IO₃^? and H₂O₂.     

Catalysis by heteropolyacids—VIII. Immobilization of keggin-type heteropolyacids on poly(4-vinylpyridine)

Anchoring of a Keggin-type heteropolyacid (HPA) to a polymeric support and the effect of heterogenization on the HPA catalysis of the oxidation of a primary diol have been studied. A coloured HPA such as H₆[Co(II)W₁₂O₄₀] (blue green), H₄[SiMo₁₂O₄₀] (yellow) or H₃[PMo₁₂O₄₀] (yellow), as the Keggin-type HPA and poly(4-vinylpyridine) as a polymeric support have been used. The anchoring of H₆[Co(II)W₁₂O₄₀] has led to a markedly increased stability of the oxidation catalyst.     

The Catalytic Performance of Preyssler's Anion, [NaP5W30O110]14−, in the Oxidation of Benzyl Alcohols

Under mild conditions, monosubstituted benzyl alcohols were oxidized to benzaldehydes and benzoic acids in the presence of sodium 30-tungstopentaphosphate (Preyssler's anion), [NaP₅W₃₀O₁₂₀]^14? , and hydrogen peroxide as an oxidant. This polyanion with high hydrolytic stability (pH = 0–12), high thermal stability, and high acidic strength shows good activities. The effects of various parameters on the yield of the products, including a catalyst type, a nature of the substitutents, and temperature, were studied. Comparison between Keggin's heteropolyacids, H₃[PW₁₂O₄₀], H₃[PMo₁₂O₄₀], H₄[SiW₁₂O₄₀], and H₄[SiMo₁₂O₄₀], and Preyssler's anion shows that this polyanion reacts similar to Keggin's acids whitout any degradation of the structure.     

Preparation and Electrochemistry Properties of a New Polyoxometalate‐Based Supramolecular Assembly

A polyoxometalate‐based supramolecular assembly with the formula (Hcpy)₆H₂[PMo₁₂O₄₀] ( 1 ) [cpy = 4‐(5‐chloropyridin‐2‐yl)pyridine] was prepared and characterized. Noncovalent intermolecular interactions including hydrogen bonds (N–H ··· O–Mo, N–H ··· H–N, and C–H ··· O–Mo), halogen (C–Cl ··· O–Mo), and face‐to‐face π packing coexist in crystal 1 , which serves the insolubility of 1 in aqueous solution. Compound 1 was used as a solid material to fabricate a bulk‐modified carbon paste electrode by direct mixing. Electrochemistry results indicated that 1 is possessed of electrocatalytic activities toward the reduction reactions of chlorate, hydrogen peroxide, and nitrite.     

Facile preparation of an α-Keggin-type [H3W12O40] complex: Does it exist in aqueous solution?

The formation processes of α-Keggin-type [H₂W₁₂O₄₀]⁶⁻ and [H₃W₁₂O₄₀]⁵⁻ complexes were investigated in aqueous W^VI (0.05–0.50 M) solutions. The formation of [H₂W₁₂O₄₀]⁶⁻ was ascertained by the appearance of a ¹⁸³W NMR line at −117 ppm, but no evidence was found for the existence of [H₃W₁₂O₄₀]⁵⁻ in the solution at the accessible pH range. The addition of (CH₃)₄N⁺ (Me₄N⁺) to the W^VI solution directly precipitated the (Me₄N)₆[H₂W₁₂O₄₀] salt. On the other hand, the addition of the larger Bu₄N⁺ cation precipitates the (Bu₄N)_4.5H_0.5[H₃W₁₂O₄₀] salt, because a naked proton formed during the crystallization process or in the solid state may enter into the Keggin shell to produce [H₃W₁₂O₄₀]⁵⁻. This explanation is based on the fact that [H₂W₁₂O₄₀]⁶⁻ is not spontaneously converted into [H₃W₁₂O₄₀]⁵⁻ in acidified aqueous solution. On the basis of their voltammetric properties, a simple diagnostic criterion was developed to distinguish between [H₂W₁₂O₄₀]⁶⁻ and [H₃W₁₂O₄₀]⁵⁻.     

Synthesis, structures and properties of new hybrid solids containing ruthenium complexes and polyoxometalates

Two new organic-inorganic hybrid solids containing Keggin ions and ruthenium complexes have been synthesized and characterized by FT-IR, UV-vis, luminescence, X-ray, and TG analysis. In KNa[Ru(bpy)₃]₂[H₂W₁₂O₄₀]·8H₂O (1), the [Ru(bpy)₃]²⁺ (bpy=2,2′-bipyridine) complex ions are located in between the infinite one-dimensional double-chains formed by adjacent Keggin anions [H₂W₁₂O₄₀]⁶⁻ linked through {KO₇} and {NaO₆} polyhedra, while in K₆[Ru(pzc)₃]₂[SiW₁₂O₄₀]•12H₂O (2), the [Ru(pzc)₃]⁻ (pzc=pyrazine-2-carboxylate) complex anions are confined by layered networks of the [SiW₁₂O₄₀]⁴⁻ clusters connected by potassium ions. Both compounds exhibit three-dimensional frameworks through noncovalent interactions such as hydrogen bonds and anion?π interactions. Additionally, compound 1 shows strong luminescence at 604 nm in solid state at room temperature.     

Electrocatalytic Activity of Nanohybrids Based on Carbon Nanomaterials and MFe2O4 (M=Co,Mn) towards the Reduction of Hydrogen Peroxide

We report the advantages of hybrid nanomaterials prepared with electrogenerated ferrites (MFe₂O₄; M: Co, Mn) and multi‐walled carbon nanotubes (MWCNTs) or thermally reduced graphene oxide (TRGO) on the electro‐reduction of hydrogen peroxide. Glassy carbon electrodes (GCE) modified with these hybrid nanomaterials dispersed in Nafion/isopropanol demonstrated a clear synergism on the catalytic reduction of reduction of hydrogen peroxide at pH 13.00. The intimate interaction between MFe₂O₄ and carbon nanomaterials allowed a better electronic transfer and a facilitated regeneration of M²⁺ at the carbon nanomaterials, reducing the charge transfer resistances for hydrogen peroxide reduction and increasing the sensitivities of the amperometric response.     

A novel preparation of keggin-type dodecatungstocobaltate(II) using [Co(ox)3]3− and hydrogen peroxide as starting materials

A novel rapid route for the preparation of the Keggin-type [Co(II)W₁₂O₄₀]⁶⁻ heteropolyanion was found by using the [Co(ox)₃]³⁻ complex and 30% aqueous hydrogen peroxide. The intermediate dicobalt species [Co(II)Co(II)W₁₁O₄₀H₂]⁸⁻ was directly isolated in high yield and the final product was easily and rapidly derived from it.     

Synthesis, characterization and performance of vanadium hexacyanoferrate as electrocatalyst of H2O2

The present work reports for the first time on the synthesis, characterization and performance of vanadium hexacyanoferrate (VHCF) as electrocatalyst of hydrogen peroxide. VHCF was synthesized by mixing V₂O₅ · nH₂O xerogel with ascorbic acid and K₄[Fe(CN)₆] in double distilled water. X-ray powder diffraction, energy dispersive spectroscopy, scanning electron microscopy, and IR-spectroscopy data suggest the formation of nanocrystalline (mean crystal size 11 nm) compound with a tentative molecular formula K₂(VO)₃[Fe(CN)₆]₂. Composite films of VHCF with poly(vinyl alcohol) were developed over a glassy carbon electrode, and then covered with different (neutral, positively or negatively charged) membranes. The effect of each membrane on the working stability of the resultant sensors was evaluated. Cyclic voltammetry experiments showed that composite films exhibit a pair of reversible redox peaks, and a remarkable low potential electrocatalysis on both the reduction and oxidation of hydrogen peroxide. A linear calibration curve over the concentration range 0.01–3.0 mM H₂O₂ was constructed. Limit of detection (S/N = 3) of 4 μM H₂O₂ was calculated. The proposed transducer is quite selective to hydrogen peroxide. No response was observed in the presence of 10 mM ascorbic acid.     

Catalytic effect of lucunary heteropolyanion containing molybdenum and tungsten atoms on decolorization of direct blue 71

In this research,a lucunary Keggin structure,[PMo₂W₉O₃₉]^7- was selected as an efficient homogenous catalyst for degradation of an azo dye（direct blue 71） and a simple method was developed for degradation of DB71.The method is based on the oxidation of azo dye in the presence of a lucunary Keggin form of polyoxometalates,K₇[PMo₂W₉O₃₉]? 19H₂O,as a homogenous catalyst at room temperature.The reaction is monitored spectrophotometrically by measuring the absorbance of dye atλ=585 nm.Some parameters including concentration of catalyst,concentration of H₂O₂,pH and reaction time were investigated and optimized. Results show that K₇[PMo₂W₉O₃₉]? 19H₂O is more efficient in the presence of hydrogen peroxide.Degradation of dye in the presence of the catalyst and H₂O₂ could lead to the disappearance approximately 65%of dye after 60 min.But degradation for the same experiment performed in the absence of catalyst or in the absence of H₂O₂ was 22%or 5%respectively.Approximately 87% azo dyes has been eliminated after 90 min in the presence of catalyst,H₂O₂ and optimize conditions(0.6 g/L of K₇[PMo_2- W₉O₃₉H₉H₂O,0.08 mol/L hydrogen peroxide and room temperature).     

MWCNT-Organoimido Polyoxomolybdate Hybrid Material: Analytical Applications for Amperometric Sensing of Hydrogen Peroxide

We report a hybrid material obtained by dispersing the polyoxometalate n-[Bu₄-N]₂[Mo₆O₁₈NC₁₃H₉] functionalized with 2-aminofluorene (POMAF) and multi-walled carbon nanotubes (MWCNTs) in 1,3-dioxolane (MWCNT- POMAF). We demonstrate the peroxidase-like activity of the hybrid material and its application for the amperometric quantification of hydrogen peroxide at −0.450 V previous drop-coating at glassy carbon electrodes, with a linear range between 1.0 μM and 6.0 μM and a detection limit of 330 nM. The reproducibility was 2.2 % using one MWCNTs-POMAF dispersion, and 3.9 % using 4 different dispersions. The sensor was successfully used for the quantification of hydrogen peroxide in enriched milk samples.     

Direct Electrochemistry of Hemoglobin Immobilized on Carbon‐Coated Iron Nanoparticles for Amperometric Detection of Hydrogen Peroxide

A novel method for preparation of hydrogen peroxide biosensor was presented based on immobilization of hemoglobin (Hb) on carbon‐coated iron nanoparticles (CIN). CIN was firstly dispersed in a chitosan solution and cast onto a glassy carbon electrode to form a CIN/chitosan composite film modified electrode. Hb was then immobilized onto the composite film with the cross‐linking of glutaraldehyde. The immobilized Hb displayed a pair of stable and quasireversible redox peaks and excellent electrocatalytic reduction of hydrogen peroxide (H₂O₂), which leading to an unmediated biosensor for H₂O₂. The electrocatalytic response exhibited a linear dependence on H₂O₂ concentration in a wide range from 3.1 μM to 4.0 mM with a detection limit of 1.2 μM (S/N=3). The designed biosensor exhibited acceptable stability, long‐term life and good reproducibility.     

Synthesis of α‐Dawson‐Type Silicotungstate [α‐Si2W18O62]8− and Protonation and Deprotonation Inside the Aperture through Intramolecular Hydrogen Bonds

The design of structurally well‐defined anionic molecular metal–oxygen clusters, polyoxometalates (POMs), leads to inorganic receptors with unique and tunable properties. Herein, an α‐Dawson‐type silicotungstate, TBA₈[α‐Si₂W₁₈O₆₂] ? 3 H₂O ( II ) that possesses a ?8 charge was successfully synthesized by dimerization of a trivacant lacunary α‐Keggin‐type silicotungstate TBA₄H₆[α‐SiW₉O₃₄] ? 2 H₂O ( I ) in an organic solvent. POM II could be reversibly protonated (in the presence of acid) and deprotonated (in the presence of base) inside the aperture by means of intramolecular hydrogen bonds with retention of the POM structure. In contrast, the aperture of phosphorus‐centered POM TBA₆[α‐P₂W₁₈O₆₂]?H₂O ( III ) was not protonated inside the aperture. The density functional theory (DFT) calculations revealed that the basicities and charges of internal μ₃‐oxygen atoms were increased by changing the central heteroatoms from P⁵⁺ to Si⁴⁺, thereby supporting the protonation of II . Additionally, II showed much higher catalytic performance for the Knoevenagel condensation of ethyl cyanoacetate with benzaldehyde than I and III .     

Peroxide derivatives of heteropoly compounds with Keggin anions [PW<Subscript>12</Subscript>O<Subscript>40</Subscript>]<Superscript>3−</Superscript> and [SiW<Subscript>12</Subscript>O<Subscript>40</Subscript>]<Superscript>4−</Superscript>: Synthesis and structure

Peroxide derivatives of heteropoly compounds with Keggin anions [PW₁₂O₄₀]^3? and [SiW₁₂O₄₀]^4? are isolated in an individual state from concentrated hydrogen peroxide solutions and characterized by physicochemical methods. The structure of Ba₂[SiW₁₂O₄₀] · 4H₂O₂ · 11H₂O (I) is solved by X-ray crystallography. Crystals of compound I (H₃₀Ba₂O₅₉Si₁W₁₂, FW = 3483.21) are monoclinic, space group C2/c, a = 24.981(2) Å, b = 12.2103(11) Å, c = 18.7142(17) Å, β = 122.620(2)^o, V = 4808.0(8) ų, Z = 4. The structure contains Keggin anions [SiW₁₂O₄₀]^4?; all hydrogen peroxide molecules are coordinated to Ba²⁺ cations.     

Hydrogen Peroxide Insular Dodecameric and Pentameric Clusters in Peroxosolvate Structures

Peroxosolvates of 2‐aminonicotinic acid ( I ) and lidocaine N ‐oxide ( II ) including the largest insular hydrogen peroxide clusters were isolated and their crystal structures were determined by single‐crystal X‐ray diffraction. An unprecedented dodecameric hydrogen peroxide insular cluster was found in I . An unusual cross‐like pentameric cluster was observed in the structure of II . The topology of the (H₂O₂)₁₂ assembly was never observed for small‐molecule clusters. In I and II new double and triple cross‐orientational disorders of H₂O₂ were found. Cluster II is the first example of a peroxosolvate crystal structure containing H₂O₂ molecules with a homoleptic hydrogen peroxide environment. In II , a hydrogen bond between an H₂O₂ molecule and a peptide group ‐CONH⋅⋅⋅O₂H₂ was observed for the first time.     

New Entangled Coordination Networks Based on Charge‐Tunable Keggin‐Type Polyoxometalates

Investigation into a hydrothermal reaction system with transition‐metal (TM) ions, 1,4‐bis(1,2,4‐triazol‐1‐lmethyl)benzene (BBTZ) and various charge‐tunable Keggin‐type polyoxometalates (POMs) led to the preparation of four new entangled coordination networks, [Co^II(HBBTZ)(BBTZ)_2.5][PMo₁₂O₄₀] ( 1 ), [Cu^I(BBTZ)]₅[BW₁₂O₄₀] ? H₂O ( 2 ), [Cu^II(BBTZ)]₃[AsW^V₃W^VI₉O₄₀] ? 10 H₂O ( 3 ), and [Cu^II₅(BBTZ)₇(H₂O)₆][P₂W₂₂Cu₂O₇₇(OH)₂] ? 6 H₂O ( 4 ). All compounds were characterized by using elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. The mixed valence of W centers in compound 3 was further confirmed by using XPS spectroscopy and bond‐valence sum calculations. In the structural analysis, the entangled networks of 1 – 4 demonstrate zipper‐closing packing, 3D polythreading, 3D polycatenation, and 3D self‐penetration, respectively. Moreover, with the enhancement of POM negative charges and the use of different TM types, the number of nodes in the coordination networks of 1 – 4 increased and the basic metal–organic building motifs changed from a 1D zipper‐type chain (in 1 ) to a 2D pseudorotaxane layer (in 2 ) to a 3D diamond‐like framework (in 3 ) and finally to a 3D self‐penetrating framework (in 4 ). The photocatalytic properties of compounds 1 – 4 for the degradation of methylene blue under UV light were also investigated; all compounds showed good catalytic activity and the photocatalytic activity order of Keggin‐type species was initially found to be {XMo₁₂O₄₀}>{XW₁₂O₄₀}>{XW_12?nTM_nO₄₀}.     

A Novel Hydrogen Peroxide Biosensor Based on the PDDA‐GNPs/MWNTs Nanocomposite Matrix

A novel nanocomposite designed by the assembly of the positively charged poly(diallyldimethylammonium chloride) protected gold nanoparticles (PDDA‐GNPs), and the negatively charged multi‐walled carbon nanotubes (MWCNTs) on ITO electrode via electrostatic interaction, was used as a supporting matrix for immobilizing hemoglobin (Hb) to develop a high‐performance hydrogen peroxide (H₂O₂) biosensor. The cyclic voltammetrys of immobilized Hb showed a pair of well‐defined and quasi‐reversible redox peaks with the formal potential of ‐0.205V (vs. SCE) and the peak‐to‐peak potential separation of 44 mV at a scan rate of 100 mV×s^?1 in 0.1 mol×L^?1 pH 7.0 PBS. Under the optimized experimental conditions, a linearity range for determination of H₂O₂ was from 2.0 × 10^?6 to 5.2 × 10^?4 mol×L^?1 with a correlation coefficient of 0.9994 (n = 37) and a detection limit of 8.4 × 10^?7 mol×L^?1. The biosensor displayed excellent electrochemical and electrocatalytic response to the reduction of H₂O₂, high sensitivity, long‐term stability, good bioactivity and selectivity.     

Two New Hybrid Architectures Based on Polyoxometaloborates and Imidazole Fragments

Two new hybrid compounds based on polyoxometaloborates, (HIm)₁₂[MnBW₁₁O₃₉H]₂ · 13H₂O ( 1 ) and (HIm)(Im)[(Im)₄Zn]₂[BW₁₂O₄₀] · 2H₂O ( 2 ) (Im = imidazole), have been synthesized and characterized by elemental analyses, IR, UV, TG, and single‐crystal X‐ray diffraction. Compound 1 is made up of [MnBW₁₁O₃₉H]^6– polyoxoanions, which are coordinatively linked together by terminal oxygen atoms to yield an unprecedented one‐dimensional chain that represents the first example of one‐dimensional assemblies based on polyoxotungstoborates and transition metal cations. Adjacent inorganic chains are further in close contact by imidazole molecules to form a three‐dimensional supramolecular channel framework by strong hydrogen‐bonding interactions. Compound 2 exhibits a three‐dimensional supramolecular architecture constructed from Keggin‐type polyoxoanions [BW₁₂O₄₀]^5– and zinc‐imidazole coordination units by strong hydrogen‐bonding interactions. Furthermore, both compounds exhibit interesting photoluminescence properties at room temperature.