Imaging Radial Distribution Functions of Complex Particles by Relayed Dynamic Nuclear Polarization

The physical properties of many modern multi-component materials are determined by their internal microstructure. Tools capable of characterizing complex nanoscale architectures in composite materials are, therefore, essential to design materials with targeted properties. Depending on the morphology and the composition, structures may be measured by laser diffraction, scattering methods, or by electron microscopy. However, it can be difficult to obtain contrast in materials where all the components are organic, which is typically the case for formulated pharmaceuticals, or multi-domain polymers. In nuclear magnetic resonance (NMR) spectroscopy, chemical shifts allow a clear distinction between organic components and can in principle provide the required chemical contrast. Here, we introduce a method to obtain radial images of the internal structure of multi-component particles from NMR measurements of the relay of nuclear hyperpolarization obtained from dynamic nuclear polarization. The method is demonstrated on two samples of hybrid core–shell particles composed of a core of polystyrene with a shell of mesostructured silica filled with the templating agent CTAB and is shown to yield accurate images of the core–shell structures with a nanometer resolution

Synthesis and Photocatalytic Activity of Titania Monoliths Prepared with Controlled Macro- and Mesopore Structure

Herein, we report a one-pot synthesis of crack-free titania monoliths with hierarchical macro-mesoporosity and crystalline anatase walls. Bimodal macroporosity is created through the polymer-induced phase separation of poly­(furfuryl alcohol). The cationic polymerization of furfuryl alcohol is performed in situ and subsequently the polymer becomes immiscible with the aqueous phase, which includes titanic acid. Addition of template, Pluronic F127, increases the mesopore volume and diameter of the resulting titania, as the poly­(ethylene glycol) block interacts with the titania precursor, leading to assisted assembly of the metal oxide framework. The hydrophobic poly­(propylene glycol) micelle core could itself be swollen with monomeric and oligomeric furfuryl alcohol, allowing for mesopores as large as 18 nm. Variations in synthesis parameters affect porosity; for instance furfuryl alcohol content changes the size and texture of the macropores, water content changes the grain size of the titania and Pluronic F127 content changes the size and volume of the mesopore. Morphological manipulation improves the photocatalytic degradation of methylene blue. Light can penetrate several millimeters into the porous monolith, giving these materials possible application in commercial devices

One-Pot Preparation and CO₂ Adsorption Modeling of Porous Carbon, Metal Oxide, and Hybrid Beads

Hierarchically porous carbon (C), metal oxide (ZrTi), or carbon–metal oxide (CZrTi) hybrid beads are synthesized in one pot through the in situ self-assembly of Pluronic F127, titanium and zirconium propoxides, and polyacrylonitrile (PAN). Upon contact with water, a precipitation of PAN from the liquid phase occurs concurrently with polymerization and phase separation of the inorganic precursors. The C, ZrTi, and CZrTi materials have similar morphologies but different surface chemistries. The adsorption of carbon dioxide by each material has been studied and modeled using the Langmuir–Freundlich equation, generating parameters that are used to calculate the surface affinity distributions. The Langmuir, Freundlich, Tóth, and Temkin models were also applied but gave inferior fits, indicating that the adsorption occurred on an inhomogeneous surface reaching a maximum capacity as available surface sites became saturated. The carbon beads have higher surface affinity for CO₂ than the hybrid and metal oxide materials

Understanding the Formation Mechanisms of Silicon Particles from the Thermal Disproportionation of Hydrogen Silsesquioxane

Crystalline silicon particles sustaining Mie resonances are readily obtained from the thermal processing of hydrogen silsesquioxane (HSQ). Here, the mechanisms involved in silicon particle formation and growth from HSQ are investigated through real-time in situ analysis using an environmental transmission electron microscope and X-ray diffractometer. The nucleation of Si nanodomains is observed starting around 1000 °C. For the first time, a highly mobile intermediate phase is experimentally observed, thus demonstrating a previously unknown growth mechanism. At least two growth processes occur simultaneously: the coalescence of small particles into larger particles and growth mode by particle displacement through the matrix toward the HSQ grain surface. Postsynthetic characterization by scanning electron microscopy further supports the latter growth mechanism. The gaseous environment employed during synthesis impacts particle formation and growth under both in situ and ex situ conditions, impacting the particle yield and structural homogeneity. Understanding the formation mechanisms of particles provides promising pathways for reducing the energy cost of this synthetic route

Understanding the Formation Mechanisms of Silicon Particles from the Thermal Disproportionation of Hydrogen Silsesquioxane

Crystalline silicon particles sustaining Mie resonances are readily obtained from the thermal processing of hydrogen silsesquioxane (HSQ). Here, the mechanisms involved in silicon particle formation and growth from HSQ are investigated through real-time in situ analysis using an environmental transmission electron microscope and X-ray diffractometer. The nucleation of Si nanodomains is observed starting around 1000 °C. For the first time, a highly mobile intermediate phase is experimentally observed, thus demonstrating a previously unknown growth mechanism. At least two growth processes occur simultaneously: the coalescence of small particles into larger particles and growth mode by particle displacement through the matrix toward the HSQ grain surface. Postsynthetic characterization by scanning electron microscopy further supports the latter growth mechanism. The gaseous environment employed during synthesis impacts particle formation and growth under both in situ and ex situ conditions, impacting the particle yield and structural homogeneity. Understanding the formation mechanisms of particles provides promising pathways for reducing the energy cost of this synthetic route

Understanding the Formation Mechanisms of Silicon Particles from the Thermal Disproportionation of Hydrogen Silsesquioxane

Crystalline silicon particles sustaining Mie resonances are readily obtained from the thermal processing of hydrogen silsesquioxane (HSQ). Here, the mechanisms involved in silicon particle formation and growth from HSQ are investigated through real-time in situ analysis using an environmental transmission electron microscope and X-ray diffractometer. The nucleation of Si nanodomains is observed starting around 1000 °C. For the first time, a highly mobile intermediate phase is experimentally observed, thus demonstrating a previously unknown growth mechanism. At least two growth processes occur simultaneously: the coalescence of small particles into larger particles and growth mode by particle displacement through the matrix toward the HSQ grain surface. Postsynthetic characterization by scanning electron microscopy further supports the latter growth mechanism. The gaseous environment employed during synthesis impacts particle formation and growth under both in situ and ex situ conditions, impacting the particle yield and structural homogeneity. Understanding the formation mechanisms of particles provides promising pathways for reducing the energy cost of this synthetic route

Understanding the Formation Mechanisms of Silicon Particles from the Thermal Disproportionation of Hydrogen Silsesquioxane

Crystalline silicon particles sustaining Mie resonances are readily obtained from the thermal processing of hydrogen silsesquioxane (HSQ). Here, the mechanisms involved in silicon particle formation and growth from HSQ are investigated through real-time in situ analysis using an environmental transmission electron microscope and X-ray diffractometer. The nucleation of Si nanodomains is observed starting around 1000 °C. For the first time, a highly mobile intermediate phase is experimentally observed, thus demonstrating a previously unknown growth mechanism. At least two growth processes occur simultaneously: the coalescence of small particles into larger particles and growth mode by particle displacement through the matrix toward the HSQ grain surface. Postsynthetic characterization by scanning electron microscopy further supports the latter growth mechanism. The gaseous environment employed during synthesis impacts particle formation and growth under both in situ and ex situ conditions, impacting the particle yield and structural homogeneity. Understanding the formation mechanisms of particles provides promising pathways for reducing the energy cost of this synthetic route