Surface Nitridation of Molybdenum by Laser-promoted Reaction

l.IntroductionowingtotheirpromisingproPertiesandPOtentialapplications,transitionmetalni-trideshavedrawngreatattentionandthepreparationandinvestigationofthesecom-poundshavebeenasubjectbothofscientificandoftechnologicalinterest.Transitionmetalnitridescombineadvantagesofexce1lenthardness,highmeltingPOint,goodchemi-calstabilityandhigheIectricalconductivity[11,henceoverlaySofthesecompoundshavefoundwideappIicationsinvariousfie1ds.Molybdenumnitrides,inparticular,havealsoemergedasverypromisingcandi…     

Functionalized poly(oxanorbornene)‐block‐copolymers: Preparation via ROMP/click‐methodology

Block copolymers on basis of poly(oxanorbornenes) bearing functional moieties in their side‐chains are prepared via a combination of ROMP‐methods and 1,3‐dipolar‐“click”‐reactions. Starting from N‐substituted‐ω‐bromoalkyl‐oxanorbornenes and alkyl‐/perfluoroalkyl‐oxanorbornenes, block copolymers with molecular weights up to 25,000 g mol^?1 were generated. Subsequent nucleophilic exchange‐reactions yielded the block‐copolymers functionalized with ω‐azidoalkyl‐moieties in one block. The 1,3‐azide/alkine‐“click” reactions with a variety of terminal alkynes in the presence of a catalyst system consisting of tetrakis(acetonitrile)hexafluorophosphate copper(I) and tris(1‐benzyl‐5‐methyl‐1H‐ [1,2,3]triazol‐4‐ylmethyl)‐amine furnished the substituted block copolymers in high yields, as proven by NMR‐spectroscopy. The resulting polymers were investigated via temperature‐dependent SAXS‐methods, revealing their microphase separated structure as well as their temperature‐dependent behavior. The presented method offers the generation of a large set of different block‐copolymers from only a small set of starting materials because of the high versatility of the “click” reaction, thus enabling a simple and complete functionalization after the initial polymerization reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 485–499, 2007     

A high-resolution MAS NMR study on the potential catalysts Mo/HBeta for olefin metathesis: The interaction of Mo species with HBeta zeolite

The interfacial interaction of Mo species with the HBeta zeolite was studied by multinuclear MAS NMR, XRD and N₂ adsorption. As proved by the quantitative ²⁷Al MAS NMR, this interaction is so strong as to dealuminate the framework of HBeta, and leads to a new peak appearing at −14 ppm, which indicates the formation of crystalline Al₂(MoO₄)₃. This can also be detected by XRD measurements when the Mo loading is as high as 9.0 wt.%. The corresponding quantitative ²⁹Si and ¹H MAS NMR spectra show that the amount of silanols and Brønsted acidic sites decrease obviously with increasing Mo loading. This also reveals an interaction between Mo species and HBeta support through an oxygen bridge resulting from condensation with the hydroxyls on the support. At higher Mo loadings, the interaction is so strong that it results in an extraction of aluminum from the zeolite framework, and subsequently appearance of Al₂(MoO₄)₃ and loss of Brønsted acidic sites. These can be correlated to the low catalytic activity of Mo/HBeta in metathesis of ethylene and 2-butylene to propylene.     

Synthesis and characterization of poly(ethylene oxide‐co‐ethylene carbonate) macromonomers and their use in the preparation of crosslinked polymer electrolytes

Methacrylate‐functionalized poly(ethylene oxide‐co‐ethylene carbonate) macromonomers were prepared in two steps by the anionic ring‐opening polymerization of ethylene carbonate at 180 °C, with potassium methoxide as the initiator, followed by the reaction of the terminal hydroxyl groups of the polymers with methacryloyl chloride. The molecular weight of the polymer went through a maximum after approximately 45 min of polymerization, and the content of ethylene carbonate units in the polymer decreased with the reaction time. A polymer having a number‐average molecular weight of 2650 g mol^?1 and an ethylene carbonate content of 28 mol % was selected and used to prepare a macromonomer, which was subsequently polymerized by UV irradiation in the presence of different concentrations of lithium bis(trifluoromethanesulfonyl)imide salt. The resulting self‐supportive crosslinked polymer electrolyte membranes reached ionic conductivities of 6.3 × 10^?6 S cm^?1 at 20 °C. The coordination of the lithium ions by both the ether and carbonate oxygens in the polymer structure was indicated by Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2195–2205, 2006     

Air‐stable and recoverable catalyst for copper‐catalyzed controlled/living radical polymerization of styrene; In situ generation of Cu(I) species via electron transfer reaction

Copper‐catalyzed controlled/living radical polymerization (LRP) of styrene (St) was conducted using the silica gel‐supported CuCl₂/N,N,N′,N′,N″‐pentamethyldiethylenetriamine (SG‐CuCl₂/PMDETA) complex as catalyst at 110 °C in the presence of a definite amount of air. This novel approach is based on in situ generation and regeneration of Cu(I) via electron transfer reaction between phenols and Cu(II). Sodium phenoxide or p‐methoxyphenol was used as a reducing agent of Cu(II) complexes in LRP. The number–average molecular weight, M_n,GPC, increases linearly with monomer conversion and agrees well with the theoretical values up to 85% conversion The molecular weight distribution, M_w/M_n, decreases as the conversion increases and reaches values below 1.2. The catalyst was recovered in aerobic condition and reused in copper‐catalyzed LRP of St. For the second run, the number–average molecular weights increased with monomer conversion and the polydispersities decreased as the polymerization proceeded and reached to the value <1.3 at 81% conversion. The recycled catalyst retained 90% of its original activity in the subsequent polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 77–87, 2006     

Thermochemically induced binding of methyl orange to polycations containing primary amine groups

The thermochemical transformation of electrostatically formed complexes of methyl orange (MO) with polycations containing primary amine groups such as ammonium salts afforded new polymers with a high concentration of covalently bound 4‐N,N‐dimethylaminoazobenzene groups in the side chain. Poly(allylamine hydrochloride) and poly(β‐aminoethylene acrylamide hydrochloride) were employed as support polycations for MO. The transformation of sulfonate–ammonium ion pairs into sulfonamide bonds, via heating at an elevated temperature, was supported by the polymer properties before and after the thermal treatment. The polymer structure changes were monitored with elemental analysis, Fourier transform infrared, ¹H NMR, and ultraviolet–visible absorption spectroscopy, and thermogravimetric analysis. The spacer length between the backbone and azobenzene structures used as side chains strongly influenced the polymer properties before and after the heat‐induced reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5898–5908, 2006     

Lithographic design of photosensitive polyarylates based on reaction development patterning

The factors affecting pattern‐forming properties in reaction development patterning were examined with polyarylates with various bisphenol moieties. The developability of the photosensitive polyarylates was dependent on the properties of the subtituent (R) in the bisphenol moieties. The development time decreased in the following order: R?C(CH₃)₂ > fluorenyl unit ? phenolphthalein unit > C(CF₃)₂ > SO₂. This order agreed with that of the reactivity between the polyarylates and ethanolamine, and these orders can be explained by pK_a of the bisphenol used to prepare the polyarylates. The development with NH₂? R′? OH resulted in successful positive‐tone pattern formation. However, pattern formation with the developers containing NH₂? R′? OCH₃ was unsuccessful. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2694–2706, 2006     

Nd掺杂的Bi4Ti3O12变温X射线衍射分析

利用变温X射线衍射技术，在预烧过程中分析了Nd掺杂Bi4Ti3O12后生成Bi3.15Nd0.85Ti3O12（BNT）相的形成过程以及微结构的变化．实验观察到以30℃／min的升温速率，BNT相在700℃时开始形成，其衍射峰强度随温度的继续升高而增强，衍射峰半高宽随烧结时间延长而减小．X射线衍射分析结果表明，在900℃恒温条件下，烧结约2h，可形成单一的BNT相．     

Activity evaluation of carbon paste electrodes loaded with pt nanoparticles prepared in different radiolytic conditions

Three Pt-based catalysts prepared in different radiolytic conditions and supported on graphite powder were packed into a carbon paste electrode configuration. They were compared to each other, to the commercial (Pt) deposited on activated carbon powder (Johnson Matthey) and to pure Vulcan XC-72 for their respective abilities toward the hydrogen evolution reaction (HER). The Tafel parameters were determined for all these electrodes. From the I–V curves and their quantitative treatment, the following order of activity emerged unambiguously and reads: (PtCO)₂ (fcc structure) > (PtCO)₁ (Chini cluster) > (Pt)_neat > (Pt)_JM (Johnson Matthey) ≫ (Vulcan XC-72). As expected, all the Pt-loaded electrodes were more efficient than Vulcan XC-72. The classification appears to be linked with the mean nanoparticle size, and for comparable sizes, with the surface morphology of the materials. The results and the stability of the electrodes suggest that the small particle sizes and the good dispersity on the carbon support were maintained during the HER.