Hollow Silica Nano and Micro Spheres with Polystyrene Templating: A Mini-Review.

Synthesis of monodisperse hollow silica nanospheres, especially using a hard template route, has been shown to be successful, but a high yield is needed for this strategy to be used on an industrial scale. On the other hand, there is a research gap in the synthesis of hollow silica microspheres due to the popularity and easiness of the synthesis of silica nanospheres despite the larger spheres being beneficial in some fields. In this review, current trends in producing hollow silica nanospheres using hard templates, especially polystyrene, are briefly presented. Soft templates have also been used to make highly polydisperse hollow silica spheres, and complex designs have improved polydispersity. The effect of the main parameters on the coating is presented here to provide a basic understanding of the interactions between the silica and template surface in the absence or presence of surfactants. Surface charge, surface modification, parameters in the sol-gel method and interaction between the silica and templates need to be further improved to have a uniform coating and better control over the size, dispersity, wall thickness and porosity. As larger organic templates will have lower surface energy, the efficiency of the micro sphere synthesis needs to be improved. Control over the physical structure of hollow silica spheres will open up many opportunities for them to be extensively used in fields ranging from waste removal to energy storage.

Engineering of Microcage Carbon Nanotube Architectures with Decoupled Multimodal Porosity and Amplified Catalytic Performance.

New approaches for the engineering of the 3D microstructure, pore modality, and chemical functionality of hierarchically porous nanocarbon assemblies are key to develop the next generation of functional aerogel and membrane materials. Here, interfacially driven assembly of carbon nanotubes (CNT) is exploited to fabricate structurally directed aerogels with highly controlled internal architectures, composed of pseudo-monolayer, CNT microcages. CNT Pickering emulsions enable engineering at fundamentally different length scales, whereby the microporosity, mesoporosity, and macroporosity are decoupled and individually controlled through CNT type, CNT number density, and process energy, respectively. In addition, metal nanocatalysts (Cu, Pd, and Ru) are embedded within the architectures through an elegant sublimation and shock-decomposition approach; introducing the first approach that enables through-volume functionalization of intricate, pre-designed aerogels without microstructural degradation. Catalytic structure-function relationships are explored in a pharma-important amidation reaction; providing insights on how the engineered frameworks enhance catalyst activity. A sophisticated array of advanced tomographic, spectroscopic, and microscopic techniques reveal an intricate 3D assembly of CNT building-blocks and their influence on the functional properties of the enhanced nanocatalysts. These advances set a basis to modulate structure and chemistry of functional aerogel materials independently in a controlled fashion for a variety of applications, including energy conversion and storage, smart electronics, and (electro)catalysis.

Volatility of the catalytic hydrogenation products of 1,4 bis(phenylethynyl)benzene.

Measurements of equilibrium vapor pressures by effusion thermogravimetry and melting points by differential scanning calorimetry reveal that the melting temperature and equilibrium vapor pressures of 1,4-bis(phenylethynyl)benzene (DEB) do not vary monotonically with the hydrogenation extent. Contrary to intuition which suggests increasing volatility with hydrogenation, results indicate decreasing volatility for the first two hydrogenation steps before a non-monotonic upward trend, in which trans-isomers are less volatile. Insights on structural packing and functional groups were obtained from x-ray diffraction and infrared studies to shed light on the observed variation in the volatility of DEB with hydrogenation. Density functional theory calculations were performed to obtain molecular level information and to establish the thermodynamics of DEB hydrogenation reactions. A major factor influencing the observed melting points and volatility of the hydrogenated intermediate species is identified as the local attractive or repulsive carbon-hydrogen (CH) dipole interactions among the getter molecules in their respective crystal structures. Such collective CH dipole interactions can be used to predict the trends in the volatilities of catalytic hydrogenation processes.