Hydrothermal synthesis and structural characterization of novel alpha-Keggin unit-supported Cu(II)- and Mn(II)-bipyridine complexes from a tri-lacunary precursor

Blue [{Cu(2,2'-bipy)(2)}(2){alpha-SiW12O40}] (bipy = bipyridyl) (1) and pale yellow [Mn(2,2'-bipy)(3)](2)[alpha-SiW12O40] (2) have been synthesized hydrothermally and characterized by IR spectroscopy and single crystal X-ray structure analysis. In 1, the [alpha-SiW12O40](4-) ion acts as a bridge between the two [{Cu(2,2'-bipy)(2)](2+) moieties via coordination through the terminal oxygen atoms, while in 2, the [Mn(2,2'-bipy)(3)](2+) ion balances the charge on the polyoxo anion without forming any covalent bond. To the best of our knowledge, this is the first example of transition metal-mediated transformation of [alpha-SiW9O34](10-) to [alpha-SiW12O40](4-).

Study on the hydrolysis/precipitation behavior of Keggin Al-13 and Al-30 polymers in polyaluminum solutions

The hydrolysis/precipitation behaviors of Al3+, Al-13 and Al-30 under conditions typical for flocculation in water treatment were investigated by studying the particulates' size development, charge characteristics, chemical species and speciation transformation of coagulant hydrolysis precipitates. The optimal pH conditions for hydrolysis precipitates formation for AlCl3, PAC(A113) and PAC(A130) were 6.5-7.5, 8.5-9.5, and 7.5-9.5, respectively. The precipitates' formation rate increased with the increase in dosage, and the relative rates were AlCl3 >> PAC(A130) > PACA113. The precipitates' size increased when the dosage increased from 50 mu M to 200 mu M, but it decreased when the dosage increased to 800 AM. The Zeta potential of coagulant hydrolysis precipitates decreased with the increase in pH for the three coagulants. The isoelectric points of the freshly formed precipitates for AlCl3, PAC(A113) and PAC(A130) were 7.3, 9.6 and 9.2, respectively. The Zeta potentials of AlCl3 hydrolysis precipitates were lower than those of PAC(A113) and PAC(A130) when pH > 5.0. The Zeta potential of PAC(A130) hydrolysis precipitates was higher than that of PACA113 at the acidic side, but lower at the alkaline side. The dosage had no obvious effect on the Zeta potential of hydrolysis precipitates under fixed pH conditions. The increase in Zeta potential with the increase in dosage under uncontrolled pH conditions was due to the pH depression caused by coagulant addition. Al-Ferron research indicated that the hydrolysis precipitates of AlCl3 were composed of amorphous AI(OH)3 precipitates, but those of PACA113 and PACA130 were composed of aggregates of Al-13 and Al-30, respectively. Al3+ was the most un-stable species in coagulants, and its hydrolysis was remarkably influenced by solution pH. Al-13 and Al-30 species were very stable, and solution pH and aging had little effect on the chemical species of their hydrolysis products. The research method involving coagulant hydrolysis precipitates based on Al-Ferron reaction kinetics was studied in detail. The Al species classification based on complex reaction kinetic of hydrolysis precipitates and Ferron reagent was different from that measured in a conventional coagulant assay using the Al--Ferron method. The chemical composition of Al-a, Al-b and Al-c depended on coagulant and solution pH. The Al-b measured in the current case was different from Keggin Al-13, and the high Alb content in the AlCl3 hydrolysis precipitates could not used as testimony that most of the Al3+ Was converted to highly charged Al-13 species during AlCl3 coagulation.

On the acid-base stability of Keggin Al-13 and Al-30 polymers in polyaluminum coagulants

The acid-base stabilities of Al-13 and Al-30 in polyaluminum coagulants during aging and after dosing into water were studied systematically using batch and flow-through acid-base titration experiments. The acid decomposition rates of both Al-13 and Al-30 increase rapidly with the decrease in solution pH. The acid decompositions of Al-13 and Al-30 with respect to H+ concentration are composed of two parallel first-order and second-order reactions, and the reaction orders are 1.169 and 1.005, respectively. The acid decomposition rates of Al-13 and Al-30 increase slightly when the temperature increases from 20 to ca. 35 A degrees C, but decrease when the temperature increases further. Al-30 is more stable than Al-13 in acidic solution, and the stability difference increases as the pH decreases. Al-30 is more possible to become the dominant species in polyaluminum coagulants than Al-13. The acid catalyzed decomposition and followed by recrystallization to form bayerite is one of the main processes that are responsible for the decrease of Al-13 and Al-30 in polyaluminum coagulants during storage. The deprotonation and polymerization of Al-13 and Al-30 depend on solution pH. The hydrolysis products are positively charged, and consist mainly of repeated Al-13 and Al-30 units rather than amorphous Al(OH)(3) precipitates. Al-30 is less stable than Al-13 upon alkaline hydrolysis. Al-13 is stable at pH < 5.9, while Al-30 lose one proton at the pH 4.6-5.75. Al-13 and Al-30 lose respective 5 and 10 protons and form [Al-13] (n) and [Al-30] (n) clusters within the pH region of 5.9-6.25 and 5.75-6.65, respectively. This indicates that Al-30 is easier to aggregate than Al-13 at the acidic side, but [Al-13] (n) is much easier to convert to Alsol-gel than [Al-30] (n) . Al-30 possesses better characteristics than Al-13 when used as coagulant because the hydrolysis products of Al-30 possess higher charges than that of Al-13, and [Al-30] (n) clusters exist within a wider pH range.

A new alpha-Keggin type polyoxometalate coordinated to four silver complex moieties: {PW9V3O40[Ag(2,2 '-bipy)](2)[Ag-2(2,2 '-bipy)(3)](2)}

A new polyoxometalate derivative {PW9V3O40[Ag(2,2'-bipy)](2)[Ag-2(2,2'-bipy)(3)](2)} 1 has been hydrothermally synthesized and structurally characterized by the single crystal X-ray diffraction. X-Ray analysis showed that both [Ag(2,2'-bipy)](+) and [Ag-2(2,2'-bipy)(3)](2+) units are supported on the alpha-Keggin polyoxoanion [PW9V3O40](6-) via the surface bridging oxygen atoms. 1 represents the first alpha-Keggin type polyoxoanion coordinated with four transition metal complex moieties, which further acts as a neutral molecular units for the construction of an interesting three-dimensional supramolecular framework.

Modified polyoxometalates: Hydrothermal syntheses and crystal structures of three novel reduced and capped Keggin derivatives decorated by transition metal complexes

Three novel polyoxometalate derivatives decorated by transition metal complexes have been hydrothermally synthesized. Compound 1 consists of [(PMo6Mo2V8O44)-Mo-VI-V-V-O-IV{CO (2,2'-bipy)(2)(H2O)}(4)](3+) polyoxocations and [(PMo4Mo4V8O44)-Mo-IV-V-V-O-IV{Co(2,2'-bipy)(2)(H2O)}(2)](3-) polyoxoanions, which are both built on mixed-metal tetracapped [PMo8V8O44] subunits covalently bonded to four or two {Co(2,2'-bpy)(2)(H2O)}(2+), clusters via terminal oxo groups of the capping V atoms. Compound 2 is built on [(PMo8V6O42)-V-VI-O-IV{Cu-I(phen)}(2)](5-) clusters constructed from mixed-metal bicapped [(PMo8V6O42)-V-VI-O-IV](7-) subunits covalently bonded to two {Cu(phen)}(+) fragments in the similar way to 1. The structure of 3 is composed of [(PMo9Mo3O40)-Mo-VI-O-V](6-) units capped by two divalent Ni atoms via four bridging oxo groups.

钒取代Keggin型杂多酸的多层组装和电催化性能研究

用层层组装的方法在 4 -氨基苯甲酸预修饰的玻碳电极上交替沉积过渡金属钒取代的杂多酸H3 PW6V6O6- 4 0 (简称 PW6V6)和联吡啶锇取代的聚乙烯吡啶 (QPVP-Os) .用表面等离子体共振 (SPR)技术和循环伏安 (CV)法对多层膜进行了表征 .结果表明 ,多层膜的生长均匀 ,平均厚度为 2 .88nm.还研究了多层膜对亚硝酸根 (NO- 2 )和溴酸根 (Br O- 3 )的催化还原活性.

Electrochemical behavior of alpha-Keggin-type nanoparticles, Co(en)(3)(PMo12O40), in polyethylene glycol

The electrochemical behavior of alpha-Keggin-type nanoparticles, Co(en)(3)(PMo12O40) (abbreviated as PMo12-Co), have been studied in poly(ethylene glycol) for four different molecular weights (PEG, average MW 400, 600, 1000, and 2000 g mol(-1)) and containing LiClO4 (O/Li=100/1) supporting electrolyte. The diffusion coefficients of the PMo12-Co nanoparticles were determined using a microelectrode by chronoamperometry for PEG of different molecular weights that were used to describe the diffusion behavior of PMo12-Co nanoparticles in different phase states. Moreover, the conductivity of the composite system increases upon addition of PMo12-Co nanoparticles, which was measured by an a.c. impedance technique. FT-IR spectra and DSC were used to follow the interactions of PEG-LiClO4-PMo12-Co, and well described the reason that the PMo12-Co nanoparticles could promote the conductivity of the PEG-LiClO4-PMo12-Co system.

[H2N (C2H4)(2)NH2](4) (H3O) [(PMo2Mo6V4O40)-Mo-V-V-VI-O-IV ((VO)-O-IV)(2)] center dot H2O: A new highly reduced, bicapped pseudo-Keggin vanadylpoly-molybdophosphate

A new vandylpolymolybdophosphate, [H2N(C2H4)(2)NH2](4)-(H3O)[(PMo2Mo6V4O40)-Mo-V-V-VI-O-IV((VO)-O-IV)(2)].H2O, was hydrothermally synthesized and structurally characterized by elemental analyses, IR, UV-vis, XPS, ESR spectra, mid singe crystal X-ray diffraction analysis. The compound contains an unusual highly reduced pseudo-Keggin type polyoxoanion with nine negative charges and exhibits an interesting phosphorus-centered alternate layer arrangement of molybdenum and vanadium oxides.

Multilayer assembly of Bis-Keggin-type heteropoly compound on chemically modified glassy carbon electrode and its electrocatalysis

Through layer-by-layer assembly, the bis-Keggin-type heteropolyanion K10H3 [Nd(SiMo7W4O39)(2)] XH2O was successfully immobilized on a glassy carbon electrode surface grafted covalently by 4-aminobenzoic acid. The electrochemical behavior of the heteropolyanion was investigated. Cyclic voltammetry proved the uniform growth of the film. However, the characteristic redox peaks of the heteropolyanion in the film were deformed with increasing of the number of the multilayer film. The effect of pH on the redox behaviors of [Nd(SiMo7W4)(2)](13-) in the film was discussed. The multilayer film electrodes have excellent electrocatalytic activities to the reduction of BrO3-, HNO2 and H2O2.

双-Keggin型四元杂多化合物[Nd(SiMo_7W_4O_(39))_2]~(13-)多层膜在化学修饰玻碳电极上的组装及电催化

报道双－Ｋｅｇｇｉｎ型四元杂多化合物Ｋ１０Ｈ３［Ｎｄ（ＳｉＭｏ７Ｗ４Ｏ３９）２］ＸＨ２Ｏ（简称［Ｎｄ（ＳｉＭｏ７Ｗ４）２］１３－）聚合物的交替组装多层膜在４－氨基苯甲酸修饰玻碳电极上的制备及其电化学特性。各层的循环伏安行为证明膜的均匀增长，峰电流随层数的增加而增加。与溶液中的电化学行为相比，位于多层膜中的杂多化合物的氧化还原特征峰随着多层膜层数的增加，具有一定程度的形变。该电极具有较高的稳定性。并讨论了ｐＨ对其氧化还原行为的影响，考察了该多层膜修饰电极对ＢｒＯ３－、ＨＮＯ２和Ｈ２Ｏ２等的电催化性能。

Ultrathin multilayer films incorporating Keggin-type heteropolyanion clusters

Two new ultrathin multiplayer films have been successfully prepared fi-om Keggin-type heteropoly acids H-4[SiW12O40] and H-3[PMo12O40] with polyelectrolytes PEI, PSS, and PAH, using the electrostatic layer-by-layer self-assembly, technique. The XR results reveal their film thickness at nanoscale (similar to 20 nm). According to the AFM images, it is believed that the surface roughness (rough degree of film surface) of the polyelectrolyte-polyoxometalate film greatly depends on the kind of polyoxometalates.