Molybdosphoric Acid Mixed with Titania Used as a Catalyst to Synthesize Diphenyl Carbonate via Transesterification of Dimethyl Carbonate and Phenol

The 12-molybdosphoric acid mixed with titania (MPA-TiO2) was found to be a novel and efficient catalyst for the synthesis of diphenyl carbonate (DPC) via transesterification of dimethyl carbonate (DMC) and phenol. The X-ray diffraction (XRD) and infrared (IR) techniques were employed to characterize the prepared catalysts. The effect of the weight ratio of the 12-molybdosphoric acid to titania on the transesterification was investigated. A 13.1% yield of DPC and an 11.6% yield of methyl phenyl carbonate (MPC) were obtained over MPA-TiO2 with the weight ratio of MPA to TiO2 as 5:1.     

Promotion of Ionic Liquid to Dimethyl Carbonate Synthesis from Methanol and Carbcn Dioxide

Promotion of ionic liquid, 1-ethyl-3-methylimidazolium bromide (emimBr), to the synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide in the presence of potassium carbonate and less amount of methyl iodide under mild conditions was investigated. The results showed that the high selectivity and raised yield of DMC was achieved due to the addition of emimBr in the reaction system. And effect of several reaction conditions such as temperature, pressure and amount of emimBr was discussed.     

Moderately concentrated electrolyte enabling high-performance lithium metal batteries with a wide working temperature range

The electrolyte integrated with lithium metal anodes is subjected to the issues of interfacial compatibility and stability, which strongly influence the performances of high-energy lithium metal batteries. Here, we report a new electrolyte recipe viz. a moderately concentrated electrolyte comprising of 2.4 M lithium bis(fluorosulfonyl)imide(LiFSI) in a cosolvent mixture of fluorinated ethylene carbonate(FEC) and dimethyl carbonate(DMC) with relatively high ion conductivity. Owing to the preferen...     

Fabrication of Tubular Structure Agglomerates of Calcium Carbonate by Using Collodion Film

A novel and simple method for preparing tubular structure agglomerates of calcium carbonate (CC-tube) is described. Calcium chloride and sodium carbonate aqueous solutions were used as reactants separated by a collodion film (a nitrocellulose material) in aqueous solution. The effects of the concentrations of calcium chloride and sodium carbonate aqueous solutions on the morphology and phase structure of the as-obtained samples were investigated. The CC-tube growth was prevented with the increase of reactant concentration from 0.5 to 1.0 mol•L－1. Compared with Na2CO3 aqueous solution, it is favourable to grow calcite crystals in CaCl2 aqueous solution. The products were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron- microscopy.     

INVESTIGATIONS ON VINYLENE CARBONATE Ⅰ. PREPARATION AND PROPERTIES OF POLY-(VINYLENEC ARBONATE)

Bulk polymerization of vinylene carbonate using t-butylperoxypivalate at 40℃gave colourless, high molecular weight poly(vinylene carbonate) (PVCA). Solutions of PVCA in acetone and DMF are not stable at 25℃and this degradation was studied. From measurements in DMF with unfractionated PVCA a Mark-Houwink equation was obtained:     

Electrocatalytic Synthesis of Propylene Carbonate from CO_2 and Propylene Oxide

The electrocatalytic synthesis of propylene carbonate(PC) from CO2 and propylene oxide(PO) was studied under mild conditions(PCO2=1.01×105 Pa, t=25 ℃). Influences of solvents, supporting electrolytes, the passed charge, the nature of electrodes and the current density(j) on the yield of PC were investigated to optimize the electrolytic conditions, with the maximal yield to be 46.2%, the selectivity of propylene carbonate is 100%. The reduction of propylene oxide in the absence and presence of CO2 was examin...     

Synthesis of propylene carbonate from urea and 1,2-propanediol

The production of propylene carbonate(PC)from urea and 1,2-propanediol(PG)was investigated in a batch process.The catalytic performances of zinc chloride and magnesium chloride were investigated for this reaction system.The influences of various operation conditions on the PC yield were explored.In this work,MgCl_2 and ZnCl_2 showed the excellent catalytic activity toward PC synthesis,and the yields of propylene carbonate reached 96.5%and 92.4%,respectively.The optimum reaction conditions were as follows...     

An unusual isotopic fractionation of boron in synthetic calcium carbonate precipitated from seawater and saline water

Inorganic calcium carbonate precipitation from natural seawater and saline water at various pH values was carried out experimentally. The results show the clear positive relationships between boron concentration and δ11B of inorganic calcium carbonate with the pH of natural seawater and saline water. However, the variations of boron isotopic fractionation between inorganic calcite and seawater/saline water with pH are inconsistent with the hypothesis that B(OH)4- is the dominant spe-cies incorporated into the biogenic calcite structure. The isotopic fractionation factors α between synthetic calcium carbonate precipitate and parent solutions increase systematically as pH increases, from 0.9884 at pH 7.60 to 1.0072 at pH 8.60 for seawater and from 0.9826 at pH 7.60 to 1.0178 at pH 8.75 for saline water. An unusual boron isotopic fractionation factor of larger than 1 in synthetic calcium carbonate precipitated from seawater/saline water at higher pH is observed, which implies that a substantial amount of the isotopically heavier B(OH)3 species must be incorporated preferentially into synthetic inorganic carbonate. The results propose that the incorporation of B(OH)3 is attributed to the formation of Mg(OH)2 at higher pH of calcifying microenvironment during the synthetic calcium carbonate precipitation. The preliminary experiment of Mg(OH)2 precipitated from artificial seawater shows that heavier 11B is enriched in Mg(OH)2 precipitation, which suggests that isotopically heavier B(OH)3 species incorporated preferentially into Mg(OH)2 precipitation. This result cannot be applied to explain the boron isotopic fractionation of marine bio-carbonate because of the possibility that the unusual environment in this study appears in formation of marine bio-carbonate is infinitesimal. We, however, must pay more attention to this phenomenon observed in this study, which accidentally appears in especially natural environment.     

Protic ionic liquid-promoted synthesis of dimethyl carbonate from ethylene carbonate and methanol

In this work,the protic ionic liquid[DBUH][Im](1,8-diazabicyclo[5.4.0]-7-undeceniumimidazolide)was developed as an efficient catalyst for the transesterification of ethylene carbonate with methanol to produce dimethyl carbonate.At 70℃,up to 97%conversion of ethylene carbonate and 91%yield of dimethyl ca rbonate were obtained with 1 mol%[DBUH][Im](relative to ethylene carbonate)as catalyst in 2 h.Even at room temperature,the conversion of ethylene carbonate can reach 94%and the yield of dimethyl carbonate can approach 81%for 6 h.Catalytic mechanism investigation showed the high catalytic efficiency of this ionic liquid results from the synergistic activation effect,wherein the cation can activate ethylene carbonate and the anion can activate methanol through hydrogen bond formatio n.Although the reusability of the ionic liquid need to be further improved,high efficiency and comme rcial availability of[DBUH][Im]render it a promising catalyst for the preparation of dimethyl carbonate.     

An in situ infrared study of dimethyl carbonate synthesis from carbon dioxide and methanol over well-shaped CeO2

The mechanism of dimethyl carbonate(DMC) formation from CO_2 and methanol is investigated using three well-shaped CeO_2 catalysts, nanorod, nanocube and octahedron, which are packed with different crystal planes. In situ Fourier Transform Infrared Spectroscopy(FTIR) is employed to probe each reaction step in the DMC synthesis. The number of –OH groups and the species of CO_2 adsorptions on ceria surface have significant influence on the activity of ceria with different morphologies. Rod-ceria has favorable catalytic activity because of the large amount of –OH groups and the formation of bidentate carbonate species.     

A Novel [OSSO]-Type Chromium(III) Complex as a Versatile Catalyst for Copolymerization of Carbon Dioxide with Epoxides

A new chromium(III) complex, bearing a bis-thioether-diphenolate [OSSO]-type ligand, was found to be an efficient catalyst in the copolymerization of CO₂ and epoxides to achieve poly(propylene carbonate), poly(cyclohexene carbonate), poly(hexene carbonate) and poly(styrene carbonate), as well as poly(propylene carbonate)(cyclohexene carbonate) and poly(propylene carbonate)(hexene carbonate) terpolymers.     

Radiation Chemistry of Neptunium Ions in Aqueous Carbonate and Bicarbonate Solutions*

The radiolytic reactions of neptunium ions in aqueous carbonate, alkaline carbonate, and bicarbonate solutions were examined. It was found that Np(VI) is not oxidized to Np(VII) in carbonate and bicarbonate solutions saturated with nitrous oxide, whereas this oxidation process takes place in alkaline carbonate solutions, in which Np(VI) occurs as a hydroxo complex. It was also found that Np(V) is a radiation-stable neptunium species in carbonate solutions, whereas Np(VI) is stable in bicarbonate solutions.     

Regulation of Microstructure of Calcium Carbonate Crystals by Egg White Protein

Crystal growth of calcium carbonate in biological simulation was investigated via egg white protein with different volume fractions,during which calcium carbonate was synthesized by calcium chloride an...     

On the structure of amorphous calcium carbonate--a detailed study by solid-state NMR spectroscopy

The calcium carbonate phases calcite, aragonite, vaterite, monohydrocalcite (calcium carbonate monohydrate), and ikaite (calcium carbonate hexahydrate) were studied by solid-state NMR spectroscopy ( (1)H and (13)C). Further model compounds were sodium hydrogencarbonate, potassium hydrogencarbonate, and calcium hydroxide. With the help of these data, the structure of synthetically prepared additive-free amorphous calcium carbonate (ACC) was analyzed. ACC contains molecular water (as H 2O), a small amount of mobile hydroxide, and no hydrogencarbonate. This supports the concept of ACC as a transient precursor in the formation of calcium carbonate biominerals.     

Synthesis and biodegradation studies of 1,3-propanediol based aliphatic poly(ester carbonate)s

A series of poly(ester carbonate)s were obtained from adipic acid, 1,3-propanediol and diethyl carbonate in the presence of catalyst Ti(OBu)₄ by polycondensation and transestrification process. The amount of monomeric composition was varied in order to get the polymer of different composition. The structure, average molecular weight and physical properties of poly(ester carbonate) were characterized by FT-IR, ¹H NMR, solubility, solution viscosity, gel permeation chromatography, differential scanning calorimetry and XRD analysis. Biodegradability of poly(ester carbonate)s was investigated by hydrolytic (pH 7.2 and 11.5), enzymatic using Rhizopus delemar lipase at 37 °C and soil burial test. The biodegradation rate observed was more for poly(ester carbonate) containing 40% and 10% of diethyl carbonate due to their low crystallinity.     

碳酸钴中钴碳氮的测定与结构表征研究

碳酸钴由于受生产工艺的制约,生产的产品组分复杂,且市售碳酸钴产品的命名也存在多样性.采用X射线荧光光谱仪、电感耦合等离子体发射光谱仪、元素分析仪、X射线多功能粉末衍射仪和红外吸收光谱仪对某碳酸钴产品的成分进行测定和结构表征.结果表明:该碳酸钴产品钴、碳、氮的含量分别为46.53％、8.31％ 和1.48％,相对标准偏差...     

Synthesis and properties of poly(carbonate‐urethane) consisting of alternating carbonate and urethane moieties

Poly(carbonate‐urethane) consisting of alternating carbonate and urethane moieties (poly(HC‐MDI)) was prepared by polyaddition of 4,4′‐diphenylmethane diisocyanate (MDI) and a monocarbonate diol bis(3‐hydroxypropyl)carbonate (HC), prepared by hydrolysis of a six‐membered spiroorthocarbonate 1,5,7,11‐tetraoxa‐spiro[5.5]undecane. The polyaddition proceeds without concomitant side reactions including carbonate exchange reaction and affords the desired poly(carbonate‐urethane). The hydrolysis and thermal behaviors of poly(HC‐MDI) were compared with those of the analogous polyurethane carrying no carbonate structure (poly(ND‐MDI)) prepared from MDI and 1,9‐nonanediol (ND). Although the glass transition behaviors are almost identical, poly(HC‐MDI) is less crystalline than poly(ND‐MDI). Poly(HC‐MDI) is more susceptible to hydrolysis than poly(ND‐MDI) probably due to the higher polarity and the lower crystallinity. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2802–2808, 2006     

Comparative kinetic studies of the copolymerization of cyclohexene oxide and propylene oxide with carbon dioxide in the presence of chromium salen derivatives. In situ FTIR measurements of copolymer vs cyclic carbonate production

The catalysis of the reaction of carbon dioxide with epoxides (cyclohexene oxide or propylene oxide) using the (salen)Cr(III)Cl complex as catalyst, where H(2)salen = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexenediimine (1), to provide copolymer and cyclic carbonate has been investigated by in situ infrared spectroscopy. As previously demonstrated for the cyclohexene oxide/CO(2) reaction in the presence of complex 1, coupling of propylene oxide and carbon dioxide was found to occur by way of a pathway first-order in catalyst concentration. Unlike the cyclohexene oxide/carbon dioxide reaction catalyzed by complex 1, which affords completely alternating copolymer and only small quantities of trans-cyclic cyclohexyl carbonate, under similar conditions propylene oxide/carbon dioxide produces mostly cyclic propylene carbonate. Comparative kinetic measurements were performed as a function of reaction temperature to assess the activation barrier for production of cyclic carbonates and polycarbonates for the two different classes of epoxides, i.e., alicyclic (cyclohexene oxide) and aliphatic (propylene oxide). As anticipated in both instances the unimolecular pathway for cyclic carbonate formation has a larger energy of activation than the bimolecular enchainment pathway. That is, the energies of activation determined for cyclic propylene carbonate and poly(propylene carbonate) formation were 100.5 and 67.6 kJ.mol(-1), respectively, compared to the corresponding values for cyclic cyclohexyl carbonate and poly(cyclohexylene carbonate) production of 133 and 46.9 kJ.mol(-1). The small energy difference in the two concurrent reactions for the propylene oxide/CO(2) process (33 kJ.mol(-1)) accounts for the large quantity of cyclic carbonate produced at elevated temperatures in this instance.     

Back-Extraction of Uranium(VI) from Organophosphoric Acid with Hydrazine Carbonate

The back-extraction of uranium(VI) from di(2-ethylhexyl)phosphoric acid (HDEHP) and diisodecylphosphoric acid (DIDPA) was studied by using hydrazine carbonate as back-extractant. U(VI) was back-extracted from n-dodecane solutions of 0.5M HDEHP - 0.2M TBP and 0.5M DIDPA - 0.1M TBP by hydrazine carbonate. The distribution ratios were decreased with an increase of hydrazine carbonate concentration. The back-extraction equilibria were expressed by slope analysis in consideration of neutralization between the extractant (DIDPA, HDEHP) and hydrazine carbonate, which occurred quantitatively during the back-extraction.