Preparation of High Internal Water-Phase Double Emulsions Stabilized by a Single Anionic Surfactant for Fabricating Interconnecting Porous Polymer Microspheres

Herein we report a one-step method to prepare high internal water-phase double emulsions (W/O/W) via catastrophic phase inversion of water-in-oil high internal phase emulsions (W/O HIPEs) stabilized solely by 12-acryloxy-9-octadecenoic acid (AOA) through increasing the content of water phase. This is the first time for double emulsions to be stabilized solely by a single small molecular surfactant, which are usually costabilized by both hydrophilic and hydrophobic surfactants. After neutralized with ammonia, AOA is confirmed to be capable of stabilizing both W/O emulsions and O/W emulsions, which may account for its unique ability to stabilize double emulsions. The effects of different conditions (including changing the concentrations of AOA and salt (NaCl), pH value, the polarity of oils, the addition interval of water and stirring rate, etc.) on the formation and the stability of double emulsions as well as the inversion point have been investigated by using optical microscopy and conductivity monitoring. Finally, porous polymer microspheres with high interconnection (polyHIPE microspheres) were fabricated by γ-ray initiated polymerization of the as-prepared double emulsions composed of different monomers (styrene, or <i>n</i>-butyl acrylate, or methyl methacrylate), which have been confirmed by scanning electron microscopy. Our method is facile and effective for preparing high interconnecting porous polymer microspheres without tedious post-treatment of the products in common emulsion polymerization due to the use of polymerizable surfactant

Mechanical Activation of Platinum–Acetylide Complex for Olefin Hydrosilylation

Harnessing mechanical forces to activate latent catalysts has emerged as a novel approach to control the catalytic reactions in organic syntheses and polymerization processes. However, using polymer mechanochemistry to activate platinum-based catalysts, a class of important organometallic catalysts in industry, has not been demonstrated so far. Here we show that the platinum–acetylide complex is mechanoresponsive and can be incorporated into a polymer backbone to form a new mechanophore. The mechanically induced chain scission was demonstrated to be able to release catalytically active platinum species which could catalyze the olefin hydrosilylation process. Various control experiments were conducted to confirm that the chain scission and catalytic reaction were originated from the ultrasound-induced dissociation of platinum–acetylide complex. This work further exemplifies the utilization of organometallic complexes in design and synthesis of latent catalysts for mechanocatalysis and development of self-healing materials based on silicone polymers

Fabrication and Morphology of Spongelike Polymer Material Based on Cross-Linked Sulfonated Polystyrene Particles

A novel spongelike polymer material has been fabricated by γ-ray induced polymerization of methylmethacrylate (MMA) in an emulsion containing cross-linked sulfonated polystyrene (CSP) particles. Scanning electron microscopy (SEM) images reveal that the spongelike structure is made up of interlinked nanosized PMMA particles with micrometer-sized CSP-PMMA particles embedded inside. The nitrogen adsorption isotherm discloses that the spongelike material has a high specific surface area of 29 m²/g and a narrow pore size distribution of 60–120 nm. The formation mechanism is discussed in this paper, which indicates that the key steps to form the spongelike material include a Pickering emulsion stabilized by the CSP particles, followed by the swelling process of MMA into these particles. This approach offers a more convenient alternative to prepare polymeric spongelike material without any etching procedure

Nitrogen-Doped Hollow Carbon Nanospheres for High-Performance Li-Ion Batteries

N-doped carbon materials is of particular attraction for anodes of lithium-ion batteries (LIBs) because of their high surface areas, superior electrical conductivity, and excellent mechanical strength, which can store energy by adsorption/desorption of Li⁺ at the interfaces between the electrolyte and electrode. By directly carbonization of zeolitic imidazolate framework-8 nanospheres synthesized by an emulsion-based interfacial reaction, we obtained N-doped hollow carbon nanospheres with tunable shell thickness (20 nm to solid sphere) and different N dopant concentrations (3.9 to 21.7 at %). The optimized anode material possessed a shell thickness of 20 nm and contained 16.6 at % N dopants that were predominately pyridinic and pyrrolic. The anode delivered a specific capacity of 2053 mA h g^–1 at 100 mA g^–1 and 879 mA h g^–1 at 5 A g^–1 for 1000 cycles, implying a superior cycling stability. The improved electrochemical performance can be ascribed to (1) the Li⁺ adsorption dominated energy storage mechanism prevents the volume change of the electrode materials, (2) the hollow nanostructure assembled by the nanometer-sized primary particles prevents the agglomeration of the nanoparticles and favors for Li⁺ diffusion, (3) the optimized N dopant concentration and configuration facilitate the adsorption of Li⁺; and (4) the graphitic carbon nanostructure ensures a good electrical conductivity

Hollow Metal–Organic Framework Nanospheres via Emulsion-Based Interfacial Synthesis and Their Application in Size-Selective Catalysis

Metal–organic frameworks (MOFs) represent an emerging class of crystalline materials with well-defined pore structures and hold great potentials in a wide range of important applications. The functionality of MOFs can be further extended by integration with other functional materials, e.g., encapsulating metal nanoparticles, to form hybrid materials with novel properties. In spite of various synthetic approaches that have been developed recently, a facile method to prepare hierarchical hollow MOF nanostructures still remains a challenge. Here we describe a facile emulsion-based interfacial reaction method for the large-scale synthesis of hollow zeolitic imidazolate framework 8 (ZIF-8) nanospheres with controllable shell thickness. We further demonstrate that functional metal nanoparticles such as Pd nanocubes can be encapsulated during the emulsification process and used for heterogeneous catalysis. The inherently porous structure of ZIF-8 shells enables encapsulated catalysts to show size-selective hydrogenation reactions