Ion exchange of intercalation compounds from WOP2O7 and intercalation ofn-alkylamines

Ion exchange of Na _x WOP₂O₇ ·nH₂O (x 1.4) prepared from WOP₂O₇ was attempted, using alkaline and alkaline earth ions. The degree of exchange was observed to be >50% at 90° C except for Mg²⁺. The basal spacing of ion-exchanged materials for the hydrated phase were dependent on the number of water molecules in the interlayer spaces, while those for the dehydrated phase increased with the size of ions in the interlayer spaces. The network of water molecules linked by the hydrogen bond in the interlayer spaces seems to determine the basal spacing. By the ion-exchange reaction,n-alkylammonium ions were intercalated into the interlayer spaces of Na _x WOP₂O₇ ·nH₂O (x 1.4) and Sn _x H _y WOP₂O₇ ·nH₂O (2x +y 0.5). In spite of the difference in the charge density of the host layer, a similar arrangement of alkyl chains in the interlayer spaces resulted, and neutral amines were considered to be intercalated as well as ammonium ions. Direct reaction ofn-alkylamine with WOP₂O₇ produced an intercalation compound without reduction of tungsten. The arrangement of the amines in the interlayer spaces is similar to that supposed to the ion-exchanged derivatives when heated at 140° Cin vacuo.     

Polymerization via zwitterion 25. Alternating copolymerizations of cyclic acyl phosphorite and phosphite with vinyl monomers having an electron withdrawing group

Summary Spontaneous copolymerizations of cyclic acyl phosphonite (SPO) and phosphite (SPI) with an electron-deficient vinyl monomer such as methyl acrylate (MA), methyl vinyl ketone (MVK), and acrolein (AL), gave the corresponding alternating copolymers. These copolymerizations took place without added initiator and proceeded through zwitterion intermediates. Copolymer structures 1a, 1b, 2 and 3 have been established, all of which were derived in a regiospecific manner of ambident anions. The scheme of the copolymerizations is presented.     

Cationic ring-opening polymerization of 2-phenyl-1,3,6,2-trioxaphosphocane

Summary The ring-opening polymerization of 2-phenyl-1,3,-6,2-trioxaphosphocane (4), an eight-membered cyclic phosphonite, has been investigated. Cationic initiators of PhCH₂-Cl and MeOTf gave polymers, whereas anionic and radical initiators did not yield polymer. The structure of polymer was examined by IR, ¹H, ³¹P, and ³¹C NMR spectroscopy of polymers and elemental analysis as well as the alkaline hydrolysis products. The polymer consisted of two different units, i.e., the major part is the normal phosphinate structure 5 and the minor part is the isomerized unit 6 in 7% with PhCH₂Cl initiation and in 34% with MeOTf initiator. The difference in nature of propagating species from these two initiators are discussed in connection with their reactivities.On leave from the Institute of Chemistry, Academia Sinica, Beijing, China     

Cationic ring-opening polymerization of 2-phenyl-1,2-oxaphospholane (deoxophostone)

Summary The ring-opening polymerization of deoxophostone 5, a five-membered cyclic phosphinite, has been studied. Some cationic initiators gave polymer whereas anionic and radical initiators as well as metal chloride (Lewis acid) catalysts did not yield polymer. The polymer consisted of a phosphine oxide repeating unit 6. The polymerization proceeded via the Arbuzov-type reaction. The reduction of polymer 6 with a HSiCl₃/Et₃N system gave polyphosphine 7.     

Influence of Metal Ions on the Order-Disorder Transition Temperature of the Ba-M-O (M: La, Y, In, or Ga) System

Preparation of BaLa₂O₄, B_a3,Y₄O₉, B_a,In₂O₅, and Ba₃Ga₂O₆ powders and their sintering were investigated in Ar or air. These sintered bodies with perovskite-related structure were synthesized by reaction sintering, using mixed powders in the atomic ratios of Ba/La = 1, Ba/Y = 0.75, Ba/In = 1, and Ba/Ga = 1.5. The order-disorder transition temperatures of the BaLa₂O₄, Ba₃Y₄O₉, Ba₂In₂O₅, and Ba₃Ga₂O₆ sintered bodies were 270°, 350°, 880°, and 123O^oC, respectively. It was found that the temperatures were influenced by the ionic radius of cations in B sites, and the transition temperatures decreased with increasing ionic radius.     

Adsorption of trypsin onto poly(2-hydroxyethyl methacrylate)/polystyrene composite microspheres and its enzymatic activity

Poly(2-hydroxyethyl methacrylate)/polystyrene (PHEMA/PS) composite microspheres were produced by emulsifier-free seeded emulsion polymerization for styrene in the presence of PHEMA seed particles. Effects of the surface characteristics of the PHEMA/PS composite microspheres on the adsorption immobilization of trypsin and on its enzymatic activity were discussed. Above 5 mol% of HEMA content, trypsin molecules adsorbed had high activity, 65–100% of the activity of free trypsin. The excellence of the composite microspheres as a carrier for trypsin seems to be closely related with the surface heterogeneity consisting of both hydrophilic and hydrophobic parts.     

Effects of functional groups in glow discharge polymerization

Summary Glow discharge polymerizations of allyltrimethylsilane (ATMS) and trimethylvinyloxysilane (TMVOS) were investigated by elemental analysis and infrared spectroscopy. The formed polymers were far different in elemental composition from the starting materials, and possessed high carbon and hydrogen contents. There was less difference in an infrared-spectral sense between the two polymers from ATMS and TMVOS. A polymer-forming process in a discharge state is discussed.     

Design of High-Quality Pt–CeO2 Composite Anodes Supported by Carbon Black for Direct Methanol Fuel Cell Application

A Pt on nano-sized CeO₂ particles that in turn are supported on carbon black (CB) was synthesized using the co-impregnation method. This potential anode material for fuel cell applications was synthesized in a stepwise process. The pure CeO₂ was synthesized using an ammonium carbonate precipitation method, and the Pt particles dispersed on the CeO₂ in such a way that a uniform dispersion with the CB was obtained (Pt–CeO₂/CB). The electrochemical activity of the methanol (CH₃OH) oxidation reaction on the Pt–CeO₂/CB was investigated using cyclic voltammetry and chronoamperometry experimentation. The onset potential of CH₃OH oxidation reaction on the Pt–CeO₂/CB anode was shifted to a lower potential as compared with that on commercially available Pt–Ru/carbon (C) alloy anode. In addition, the activation energy of the Pt–CeO₂/CB anode was much lower than that of the Pt–Ru/C alloy anode. Moreover, the current density of the Pt–CeO₂/CB anode was much higher than that of the Pt–Ru/C alloy anode at temperatures between 28° and 60°C. These results suggest that the anode performance of the Pt–CeO₂/CB anode at the operating temperature of typical fuel cells (80°C) is superior to that of the more usual Pt–Ru/C alloy anode. Importantly, the rare metal, Ru, is not required in the present anode material and the amount of Pt required is also significantly reduced. As a consequence, we report a promising candidate Pt–CeO₂/CB composite anode for application in the development of direct methanol fuel cells.     

Influence of dry operating conditions: observation of oscillations and low temperature CO oxidation over Co3O4 and Au/Co3O4 catalysts

A Sm(III) exchanged NaY zeolite prepared from aqueous SmCl₃ was modified with various amounts of fluorine using NH₄F. These fluorinated zeolites exhibit enhanced catalytic activity for the dealkylation of cumene. The evaluation of acid sites by infrared spectroscopy and pyridine adsorption was correlated with fluorine content.