Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers

Poly(ethylene oxide)-b-polyhedral oligomeric silsesquioxane (PEO–POSS) mixed with lithium bis(trifluoromethanesulfonyl)imide salt is a nanostructured hybrid organic–inorganic block copolymer electrolyte that may enable lithium metal batteries. The synthesis and characteristics of three PEO–POSS block copolymer electrolytes which only differ by their POSS silica cage substituents (ethyl, isobutyl, and isooctyl) is reported. Changing the POSS monomer structure results in differences in both thermodynamics and ion transport. All three neat polymers exhibit lamellar morphologies. Adding salt results in the formation of a disordered window which closes and gives way to lamellae at higher salt concentrations. The width of disordered window decreases with increasing length of the POSS alkyl chain substituent from ethyl to isobutyl and is absent in the isooctyl sample. Rheological measurements demonstrate good mechanical rigidity when compared with similar all-organic block copolymers. While salt diffusion coefficient and current ratio are unaffected by substituent length, ionic conductivity increases as the length of the alkyl chain substituent decreases: the ethyl substituent is optimal for ion transport. This is surprising because conventional wisdom suggests that ion transport occurs primarily in the PEO-rich domains, that is, ion transport should be unaffected by substituent length after accounting for the minor change in conducting phase volume fraction. © 2020 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2020 © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 363–371     

Mesostructure organic‐inorganic hybrid ionic liquids based on heteropoly acids: Effect of linkage on the molecular structure and catalytic activity

The new inorganic–organic hybrids based on SO₃H‐functionalized ionic liquids (ILs) and Keggin‐type heteropoly acids (H₃PW₁₂O₄₀, H₃PMo₁₂O₄₀, and H₄SiW₁₂O₄₀; HPAs) are prepared and characterized by FT‐IR, NMR, XRD, CV, SEM/EDX, ICP‐OES, BJH and UV. Different molecular structures according to the different inorganic part were also proved. Potentiometric titration showed a good relationship between catalytic activity and acidity of the catalysts. Electrochemical aspects showed electron transfer ability of the compounds. For understanding catalytic activities of the HPA‐IL hybrids in N‐formylation reaction, effect of catalyst composition, substrate, and reaction conditions were studied. The best SO₃H‐functionalized ionic liquid catalyst was readily recovered and reused for four runs. Easy preparation of the catalyst, simple and easy work‐up, mild reaction conditions, low cost, excellent yields and short reaction times are the key features of this work.     

Facile synthesis of inorganic–organic Fe2W18Fe4@NiO@CTS hybrid nanocatalyst induced efficient performance in oxidative desulfurization of real fuel

In this work, a new nanocatalyst, Fe₂W₁₈Fe₄@NiO@CTS, was synthesized by the reaction of sandwich‐type polyoxometalate (Fe₂W₁₈Fe₄), nickel oxide (NiO), and chitosan (CTS) via sol–gel method. The assembled nanocatalyst was systematically characterized by FT‐IR, UV–vis, XRD, SEM, and EDX analysis. The catalytic activity of Fe₂W₁₈Fe₄@NiO@CTS was tested on oxidative desulfurization (ODS) of real gasoline and model fuels. The experimental results revealed that the levels of sulfur content and mercaptan compounds of gasoline were lowered with 97% efficiency. Also, the Fe₂W₁₈Fe₄@NiO@CTS nanocatalyst demonstrated an outstanding catalytic performance for the oxidation of dibenzothiophene (DBT) in the model fuel. The major factors that influence the desulfurization efficiency and the kinetic study of the ODS reactions were fully detailed and discussed. The probable ODS pathway was proposed via the electrophilic mechanism on the basis of the electrophilic characteristic of the metal‐oxo‐peroxo intermediates. The prepared nanocatalyst could be reused for 5 successive runs without any appreciable loss in its catalytic activity. As a result, the current study suggested the potential application of the Fe₂W₁₈Fe₄@NiO@CTS hybrid nanocatalyst as an ideal candidate for removal of sulfur compounds from fuel.     

贴牌生产供应链混合渠道构建基础及优化机理研究

研究由制造商和品牌商组成的混合渠道贴牌生产供应链渠道结构优化问题,制造商通过直销和贴牌两条渠道销售产品.通过与单一渠道比较,分别推导出制造商和品牌商选择混合渠道的依据和优越性,进而归纳出双方共同接受混合渠道的制造商生产成本和品牌商品牌溢价优化条件,分析了渠道转移系数对双方构建混合渠道结构条件的影响,得出了制造商生产成本和品牌商品牌溢价作为竞争要素的互动决策改进贴牌供应链整体绩效的优化机理.     

Versatile functional poly(3‐hexylthiophene) for hybrid particles synthesis by the grafting onto technique: Core@shell ZnO nanorods

We demonstrate an efficient strategy to anchor poly(3‐hexylthiophene) (P3HT) onto zinc oxide (ZnO) surfaces. Synthesis of a novel triethoxysilane‐terminated regioregular P3HT is herein reported and supported by thorough characterization. Three triethoxysilane‐terminated P3HTs of different molar masses were prepared via a hydrosilylation reaction from allyl‐terminated P3HT. MALDI‐TOF and ¹H NMR were performed to characterize the polymer and show that around 80% of the chains are end‐functionalized. These polymers were then grafted onto the ZnO nanorods to create a macromolecular self‐assembled monolayer. This versatile technique could be subsequently applied to different metal oxide surfaces, such as silicon, titanium, or indium‐tin oxide, and represents a new one‐pot strategy based on triethoxysilane coupling reaction. Importantly, the influence of the molar mass on the grafting density and the polymer shell thickness was studied via thermo gravimetric analysis and transmission electron microscopy. The optical properties of the hybrid materials were determined by UV–visible absorption and photoluminescence to show a quenching effect of P3HT fluorescence by ZnO when grafted. This electronic transfer associated with an improved miscibility of the ZnO@P3HT, makes these hybrid materials suitable candidates for photovoltaic applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 30–38     

Solvent-free deposition of hybrid halide perovskites onto thin films of copper iodide p-type conductor

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Polymerizable Molecular Silsesquioxane Cage Armored Hybrid Microcapsules with In Situ Shell Functionalization

We prepared core–shell polymer–silsesquioxane hybrid microcapsules from cage‐like methacryloxypropyl silsesquioxanes (CMSQs) and styrene (St). The presence of CMSQ can moderately reduce the interfacial tension between St and water and help to emulsify the monomer prior to polymerization. Dynamic light scattering (DLS) and TEM analysis demonstrated that uniform core–shell latex particles were achieved. The polymer latex particles were subsequently transformed into well‐defined hollow nanospheres by removing the polystyrene (PS) core with 1:1 ethanol/cyclohexane. High‐resolution TEM and nitrogen adsorption–desorption analysis showed that the final nanospheres possessed hollow cavities and had porous shells; the pore size was approximately 2–3 nm. The nanospheres exhibited large surface areas (up to 486 m² g^?1) and preferential adsorption, and they demonstrated the highest reported methylene blue adsorption capacity (95.1 mg g^?1). Moreover, the uniform distribution of the methacryloyl moiety on the hollow nanospheres endowed them with more potential properties. These results could provide a new benchmark for preparing hollow microspheres by a facile one‐step template‐free method for various applications.     

Syntheses and molecular structures of four inorganic–organic hybrid compounds from N-containing aromatic bases and perchlorometallates of Zn,Cu, Sn,and Fe

Four organic–inorganic crystals, [(HL1)₂(ZnCl₄)]·H₂O (1) (L1?=?2-methylquinoline), [(HL1)₂(CuCl₄)] (2), [(HL2)₂SnCl₆] (3) (L2?=?6-bromobenzo[d]thiazol-2-amine), and [(HL3)FeCl₄] (4) (L3?=?5,7-dimethyl-1,8-naphthyridine-2-amine), derived from N-containing aromatic Brønsted bases and metal(II) chlorides (zinc(II) chloride, copper(II) chloride dihydrate, tin(II) chloride dihydrate, and iron(III) chloride hexahydrate) were prepared at room temperature and characterized by IR, X-ray structure analysis, elemental analysis, and TG analysis. The crystals are built up by perchlorometallates (Zn, Cu, Sn, and Fe) associated with organic cations through multiple non-covalent associations. X-ray diffraction analysis reveals that 1 and 2 have 3-D network structures built from hydrogen bonds between the cations and chlorometallates. Water molecules play an important role in structure extension in 1. Anhydrous 3 and 4 produced from 2-aminoheterocyclic derivatives display 2-D sheet structures. Arrangements of anions and cations are dominated by shape and size of cations, and also by the different structures of the chlorometallates as well as non-bonding interactions in the crystal structures. Except for 1, the other compounds are thermally stable below 240°C.