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Hypothesis Our previous studies have shown that the metal nanoparticle/polymer composite structures fabricated at the liquid/liquid interface have good reusability but lower catalytic activity for heterogeneous reactions in aqueous solutions. This should be attributed to the poor water wettability and more compact structure of the polymer matrices. Therefore, it should be possible to improve the catalytic activity through designing and fabricating a porous composite structure with good water wettability. Experiments A modified liquid/liquid interface adsorption and fabrication method was used. An aqueous solution of copper acetate and a chloroform/DMF mixed solution of PS- b -PAA acted as the two phases. Through spontaneous emulsification, self-assembly of the polymer molecules with Cu 2+ ions in the droplets, and adsorption of the formed spherical micelles and nanofibers to the planar liquid/liquid interface, a porous composite microstructure was formed. Findings This structure consisted of nanofiber-connected nanospheres which have a PS core and a PAA corona. Tiny and well-dispersed Cu nanoparticles were embedded in the hydrophilic corona and were adsorbed on the nanofibers surface as well. After physical cross-linking with 1,6-diaminohexane, the composite material exhibited high catalytic activity and good reusability for the reactions in aqueous solutions. For example, the rate constant for the reduction of p -nitroaniline reached 1965 s −1  g −1 . [ABSTRACT FROM AUTHOR]

An emulsion-directed assembly and adsorption approach has been used to fabricate composite films of polystyrene-b-poly(acryl acid)-b-polystyrene (PS-b-PAA-b-PS) and Eu 3+ and La 3+ ions at the planar liquid/liquid interface of the polymer DMF/chloroform (1:1, v/v) mixed solution (lower phase) and aqueous solutions of the corresponding salts (upper phase). The lower phase gradually transformed to a water-in-oil (W/O) emulsion via spontaneous emulsification due to the “ouzo effect”. Polymer molecules and the metal ions assembled around emulsion droplets that adsorbed at the planar liquid/liquid interface at last, resulting in formation of composite films. The film morphologies and structures depend on Ln 3+ ions: polymer/Eu 3+ composite films were foam films composed of microcapsules ranging in size from several hundreds of nanometers to micrometers, while polymer/La 3+ composite films were composed of hollow spheres several tens of nanometers in size. Fourier transform infrared (FTIR) spectra revealed that the coordination modes of carboxyl groups to Eu 3+ and La 3+ were bridging bidentate and ionic, respectively, in the two types of composites. These results indicate that stable microcapsules can be fabricated around droplets for polymer/Eu 3+ systems, while microcapsules of polymer/La 3+ are unstable. This leads to different film morphologies and structures. Compositions of these films were characterized using energy-dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). In addition, foam films of polymer/Eu 3+ /2,2′-bipyridine (bpy) were fabricated using this approach, and their photoluminescence properties were investigated. [ABSTRACT FROM AUTHOR]

Highlights: [•] Composite films with different structures were formed at the liquid/liquid interface. [•] These films are composed of diblock or triblock copolymers and inorganic species. [•] PS-b-P4VP/Au and PS-b-P4VP/Ag have honeycomb and foam structure, respectively. [•] P4VP-b-PS-b-P4VP/Au forms a free-standing film with a nanosphere array structure. [•] Co-adsorption and self-assembly of polymer and the ions lead to the film formation. [ABSTRACT FROM AUTHOR]

Highlights: [•] Composite films with honeycomb structure were formed at the liquid/liquid interface. [•] These films are composed of block copolymer PS-b-P2VP and Ag+ or ions. [•] Co-adsorption and self-assembly of polymer and the ions lead to the film formation. [•] Transformed metal nanoparticles exhibit high and durable catalytic activity. [ABSTRACT FROM AUTHOR]

Abstract: Free-standing films of poly(2-vinylpyridine) doped with Ag+ ions were fabricated at the planar liquid/liquid interface of an aqueous solution of AgNO3 and a chloroform solution of the polymer through adsorption of the polymer molecules, combination with Ag+ ions, and self-assembly of the composite species. Transmission electron microscopic (TEM) investigations indicated that the films were composed of planar thin layers decorated with separated microcapsules and foam structures of conglutinated microcapsules, and no Ag nanoparticles formed in the pristine films. After UV-light irradiation and KBH4 aqueous solution treatment, Ag nanoparticles with the average size of 3.2nm appeared and incorporated in the polymer matrices. X-ray photoelectron spectra (XPS) and UV–vis spectra are consistent with the TEM observations. Thermogravimetric analysis (TGA) showed good thermal stability of the composite films. The silver content was estimated to be 24.0% from the TG curve, closing to the calculated value. The catalytic performance of the composite films was evaluated by using the reduction of nitro-compounds, including nitrobenzene, 4-nitrophenol, and 4-nitrobenzoic acid by KBH4 in aqueous solutions. The results indicated that the composite films have high and durable catalytic activity. The apparent reaction constants are related to the size of the nitro-compounds, suggesting that the Ag nanoparticles were incorporated in the matrices, and the diffusion of the reactant molecules has a great influence on the catalytic reaction. [Copyright &y& Elsevier]

Abstract: Gold nanoparticle-doped poly(2-vinylpyridine) (P2VP) microcapsules and foam films were synthesized and assembled at the P2VP chloroform solution/HAuCl4 aqueous solution interface at 25°C. It was found that Au nanoparticles with the average diameter of 2.1nm were homogeneously embedded in and adsorbed on the walls of the capsules and foams, the nanoparticles were composed of Au(0) and Au(III) with the molar ratio of about 75/25, and the mass percent of Au elements was measured to be 19.65%. The formation of the nanostructures was attributed to the self-assembly of P2VP at the liquid/liquid interface, the simultaneous reduction of ions by a small amount of ethanol in the chloroform and adsorption of ions. After irradiated by UV-light for 1h, the average diameter of the nanoparticles was found to be 2.2nm, and the ions were transformed to Au(0) completely. The catalytic performance of these composite nanostructures were evaluated by using the reduction of 4-nitrophenol (4-NP) by potassium borohydride in aqueous solutions. The catalytic activity was very high in the first cycle, decreased rapidly and slightly in the second and third cycles, respectively, due to the aggregation of some nanoparticles, and stabilized after the third cycle. [Copyright &y& Elsevier]