Thermal Behaviour of Some New Polyoxometalate Complexes of Ciprofloxacin with Keggin-type Heteropoly Acids

Four polyoxometalate complexes, (CPFX·HCl)_3H_4SiW_~12 O_~40 , (CPFX·HCl)_3H_3PW_~12 O_~40 , (CPFX·HCl)_3H_3PMo_~12 O_~40 and (CPFX·HCl)_4H_4SiMo_~12 O_~40 , were prepared from ciprofloxacin hydrochloride(CPFX·HCl) reacting with H_nXM_~12 O_~40 ·nH_2O(X=P,Si; M=W,Mo) in an aqueous solution, and characterized by elemental analysis, IR spectrometry and TG-DTA. The IR spectrum confirms the presence of Keggin-type anions of heteropoly acids and the characteristic functional groups of ciprofloxacin. The TG/DTA curves show that their thermal decomposition is a multi-step process including simultaneous collapse of the Keggin-type structure. At first, these compounds had a mass loss of water molecules, then several other mass losses occured due to the decomposition of ciprofloxacin hydrochloride and its fragments with the degradation of Keggin anions. The end product of decomposition is the mixture of WO_3(or MoO_3) and SiO_2(or P_2O_5), identified by X-ray diffraction and IR spectroscopy. The possible thermal decomposition mechanisms of these complexes are proposed. This study exemplified that the thermal stability of the complexes containing tungsten is much better than that of the complexes containing molybdenum.

Synthesis and Properties of Heteropoly Complexes LnHSiW_(12)O_(40)·xH_2O

The present paper covers seven rare earth-containing tungstosilicate heteropoly complexes LnHSiW_(12)O_(40)·xH_2O with Keggin structure(Ln=La,Ce,Pr,Nd,Sm,Eu and Gd)snythesized by double decomposition reaction.The synthesized heteropoly complexes were characterized by ICP,^(29)Si-NMR,XPS, XRD,IR,UV,polarogram,CV and TG-DTA.The relationship between the structure of the synthesized heteropoly complexes and their properties is discussed.

A Study of Heteropoly Complexes of Rare Earths as Catalyst Promoter in the Synthesis of Ethyl Acetate

The capability of the synthesized heteropoly complexes of rare earths {K10 [(O39W11Si) Ln(Gly)3Ln(SiW11O39)]?H2O (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy)} as the catalyst promoter in the synthesis of the ethyl acetate was studied. The results showed that the quantity of H2SO4 used for synthesizing the ethyl acetate can be reduced by 75% and the yield reached 98% at the optional condition.

HYDROXYLATION OF BENZENE BY HETEROPOLY ACIDS(SALTS)CONTAINING VANADIUM

Direct hydroxylation of benzene catalyzed by vanadium-con- taining heteropoly compounds with Keggin or Dawson structure has been investigated.The effects of several factors upon the hydroxylation reaction have also been examined.It is indicated that the highest yield of phenol reached 76%(based on H_2O_(?))with 99.4～100% selectivity.

SUIDIES ON SOME PROPERTIES AND CATALYSIS OF RARE EARTH HETEROPOLY ACIDS

INTRODUCTIONThough potassium salts of rare earth substituted silicotungsticacids were synthesized early in 1971 by R.D.Peacock etc.,sofar the reports about the application of the corresponding acidshave not been found.We prepared fourteen rare earth substitutedsilicotungstic acids and determined their thermal stability,IRabsorption Spectra and x-ray diffraction spectra.Furthermore,thecatalytic activities of the fourteen heteropoly acids in acid cata-lytic reaction were investigated.Our experimental results demonstrated rare earth substituted silico-tungstic acids have very high catalytic activity in the reaction of

Highly efficient synthesis of 2,3-dihydroquinazolin-4(1H)-ones catalyzed by heteropoly acids in water

Heteropoly acids efficiently catalyzed the cyclocondensation reaction of anthranilamide with aldehydes in water at ambient temperature and afforded the corresponding 2,3-dihydro-4（1H）-quinazolinones compounds in good to excellent yields.This method provides mild reaction conditions and clean reaction profiles,using a small quantity of catalyst and a simple workup procedure.

Toluene Alkylation with Methanol to p-Xylene over Heteropoly Acids Supported by Clay

The alkylation of toluene with methanol for the selective formation of p-xylene was systematically studied. Very few studies have been reported on the use of superacids such as heteropolyacids on cheap supports, such as clay. This article deals with the use of different heteropoly acids （HPAs）, viz, Dodeca-Tungstophosphoric acid [H3PO4.12WO3.xH2O] （TPA）, Dodeca-Molyhdo phosphoric acid ammonium salt hydrate [H12Mo12N3O40P＋aq] （DMAA）, Dodeca-Molyhdo Phosphoric acid （PMA） on clay （MontmoriUonite, K-10） and as such plain clay. This comparative study reveals that 20%PMA/Clay shows 62% toluene conversion and 100% selectivity toward p-xylene.

Synthesis of d,l-α-Tocopherol Catalyzed by Heteropoly Acids

,d,l-a-Tocopherol (vitamin E) isfound to be synthesized by condensingtrimethylhydroquinone with isophytol catalyzed by heteropoly acids (HPA) H3:PW12O40 andH3PMo12O40 at room temperature. These HPA are efficient catalysts for the synthesis of d l-a-Tocopherol and can easily be separated from the reaction mixture and roused,

Synthesis, Characterization and Inhibition Effects of Vanadium Substituted Dawson-type Heteropoly Acids(Mo, P)

Four new vanadium substituted Dawson-type heteropoly acids H7[P2Mo17VO62]·39H2O（1）, H8[P2Mo16V2O62]·41H2O（2）, H9[P2Mo15V3O62]·51H2O（3） and H8[P2Mo14V4O62H2]·45H2O（4） were prepared respec-tively. Their structures were determined by IR and ICP. The inhibition effects of vanadium substituted Dawson-type heteropoly acids（Mo, P） on free radical polymerization of methyl methacrylate（MMA） were investigated by dilatometry. The results show that the rate of the polymerization of MMA decreases and the inhibition effects of the four heteropoly acids reach the inhibitor performance of hydroquinone at a certain ratio.

Synthesis and proton conductibility of ternary germanic heteropoly acids

The ternary germanic heteropoly acids H_5GeW_(11)O_(40) centre dot 22H_2O andH_5GeMo_(11)VO_(40) centre dot 24H_2O were synthesized for the first time by the stepwiseacidification and the stepwise addition of solution of the component elements. The products werecharacterized by ICP, IR, UV, XRD and TG-DTA. The proton conductibility and the activation energy ofproton conduction of the heteropoly acids were investigated.

Synthesis and Characterization of Heteropoly Complexes of Indium with Metal－centred Undecatungstate Ligan

New indium heteropoly undecatungstometalate complexes of general formula K_n In( H_2O) MW_(11)O_(39) .xH_2O (M = Cr(Ⅲ) , Fe( Ⅲ ), Co(Ⅱ) or Zn( Ⅱ) ) were prepared by the stepwise acidification and the stepwise addition of materials. The products were characterized by elemental analysis, ion-exchange, IRspectra, UV spectra, X-ray powder diffraction and thermal analysis. The results show that the structure ofthe products derives from the Keggin structure. Their themial stability is higher than that of the homolo-gous dedecatungstometalates .

Synthesis and Characterization of Heteropolytungstosilicate Complexes with the Lanthanide Elements

Lanthanide heteropoly compounds K15[Ln(HSiW9O34)2]·28H2O(Ln = La, Ce, Nd), denoted as Ln(SiW9)2, were synthesized and characterized by element analysis, TG-DTA, IR, UV, XPS and XRD. The results show that partial oxygen in Ln(SiW9)2 was coordinated with Ln3- , where Ln-3 was in the inner side of the heteropoly anions, while the fundamental structure of SiW9 had little change. The result was supported by ion exchange experiment.

Voltammetric Studies on Heteropoly Phosphotungstovanadate Anions Across the Liquid/Liquid Interface

Electrochemical transfer behavior of V ⅤW 11 -V Ⅴ 3W 9 heteropoly anions on the water/nitrobenzene interface was investigated by means of cyclic voltammetry. The effect of the solution acidity on the transfer behavior and the stable pH range for the heteropoly anions were studied. The stability of mixed tungstovanadate decreases with increasing the number of vanadium atoms. The main transfer species within the potential window have the negative charges of 4 and the transfer process is diffusion controlled. The apparent transfer potential Δ w o Ψ 0 and the free energy Δ G 0 w→o tr for the heteropoly anions can be obtained from the experimental data. For the different anions, the Δ w o Ψ 1/2 pH relationship can be expressed as: Δ w o Ψ 1/2 =constant-53pH.

Synthesis and Properties of Heteropoly Tungstovanadogermanic Complexes with Rare Earths

Ten tungstovanadogermanic complexes K 13 H 2[Ln(GeW 10 VO 39 ) 2]· n H 2O (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Yb) were synthesized for the first time. Their structures were characterized by IR, UV, ESR, XPS, XRD and magnetic susceptibility. Their redox properties were studied by means of cyclic voctammetry and polargraphy. The results show that the complexes undergo three step reduction, the first step is the double electronic reversible, while the second and the third steps are irreversible. Their thermal stability studied by TG DTA, IR and XRD at various temperature shows that the range of pyrolysis temperature is 450～500 ℃. The complex stability in solution investigated by the acid alkali titration indicates that the range of pH in which the heteropoly anions can exist stably is pH=3 3～7 6 at room temperature.

Magnetic Properties of Heteropoly Complexes α-NamHn[GaW9M3（H2O）3O37]·16H2O （M=Co（Ⅱ）,Mn（Ⅱ）,Cr（Ⅲ））

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A new method for the synthesis of molybdovanadophosphoric heteropoly acids and their catalytic activities

An environmentally benign method for the syn-thesis of heteropoly acids H3+nPMo12–nVnO40·xH2O(PMoVn,n=1–3)was developed by the reaction of an aqueous slurry which contained stoichiometric amounts of MoO3,V2O5 and H3PO4.Characterization of the as-synthesized catalysts with inductively coupled plasma(ICP)elemental analysis,thermogravimetry(TG),X-ray diffraction(XRD)and infra-red(IR)spectroscopy indicated that V ions substituted for Mo ions in Keggin-type phosphomolybdic acid.The as-synthesized samples were found to be an efficient catalyst for the hydroxylation of benzene which was carried out in a mixed solvent of acetonitrile and acetic acid with aqueous hydrogen peroxide as oxidant.PMoV2 exhibited the highest benzene conversion of 34.5%with phenol selectivity of 100%.

Syntheses, Characterizations and Catalytic Activities of Rare Earth Derivatives of Molybdotungstovanado-Phosphoric Heteropoly Acid

Seven new-type pentabasic heteropoly complexes with the general molecular formula K 10H 5[Ln(PMo 5W 4V 2O 39) 2]·nH 2O(Ln=La, Ce, Pr, Nd, Eu, Gd, Dy) were synthesized. The results of IR, UV, 31P, 51V NMR and X-ray powder diffraction pattern demonstrate that the product still maintains Keggin structure. The thermal stability studied by water solubility test, TG-DTA, XRD and IR at various temperature shows that the range of pyrolysis temperature is from 500～550 ℃. The catalytic action varies according to the contents of rare earths which are used to catalyze the decomposition of hydrogen peroxide.

CATIONIC RING-OPENING POLYMERIZATION OF TETRAHYDROFURAN WITH KEGGIN-TYPE HETEROPOLYCOMPOUNDS AS SOLID ACID CATALYSTS

Three Keggin-type heteropolyanions, namely H3PMo12O40-13H2O, （NH4）3PMo12O40·4H2O and H3PW12O40·13H2O were prepared and tested in the ring-opening polymerization reaction of tetrahydrofuran. The effects of the counter-cation （H＋, NH4＋） and the peripheral atoms （Mo, W） on the polymerization were investigated. It has been found that when the protons of H3PMo12O40·13H2O were replaced by the ammonium cations the polymerization rate decreased dramatically. Whereas, when the peripheral atoms （Mo） were replaced by their homologous （W）, the polymerization rate increased twofold. As for the viscosity average molecular weight （My） of polymer products, it was found that the high molecular weight （7930） was obtained by using H3PW12O40·13H2O. The molecular weight （My） obtained by H3PMo12O40·13H2O and （NH4）H3PMo12O40·13H2O was 6470 and 6810, respectively.

Hydroxylation of Benzene with Hydrogen Peroxide over Highly Efficient Molybdovanadophosphoric Heteropoly Acid Catalysts

Keggin 类型 molybdovanadophosphoric heteropoly 酸， H3+nPMo12-nVnO40 (n = 1 3 ) ，被一个新奇环境联盟者准备良性的方法，和他们的催化表演在冰川的醋酸和 acetonitrile 的混合溶剂作为氧化剂与氢过氧化物经由苯的 hydroxylation 被评估到酚。各种各样的反应参数例如反应时间，反应温度，到氢过氧化物的苯的比率，水的氢过氧化物的集中，到在溶剂和催化剂集中的 acetonitrile 的冰川的醋酸的比率，被改变获得最佳的反应条件。H3+nPMo12-nVnO40 (n = 1 3 ) 被揭示是为苯的 hydroxylation 的高度有效的催化剂。在 H5PMo12-nVnO40 的情况下，有 100% 的酚的选择的 34.5% 的苯的变换能以最佳的反应条件被获得。

Preparation and Conductivity of Triheteropoly Tungstozincoaluminic Acid

The ternary undecatungstozincoaluminic heteropoly acid H-7[Al(H2O)ZnW11O39](.)12H(2)O was prepared by the ion exchanging-cooling method. The optimal proportion of solutions of the component elements and the pH of the synthesis reaction were given. The product was characterized by chemical analysis, potentiometric titration, IR, UV, XRD and TG-DTA. AC impedance measurement results show that its proton conductivity is 1.37x10(-4) S/cm at 18 degreesC.