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Pickering emulsions (PEs), i.e. particle stabilized emulsions, are used as reaction environments in biphasic catalysis for the hydroformylation of 1-dodecene into tridecanal using the catalyst rhodium (Rh)–sulfoxantphos (SX). The present study connects the knowledge about particle–catalyst interactions and PE structure with the reaction results. It quantifies the efficiency of the catalytic performance of the catalyst localized in the voids between the particles (liquid–liquid interface) and the catalyst adsorbed on the particle surface (liquid–solid interface) using a new numerical approach. First, it is ensured that the overall packing density and geometry at the droplet interface and the size of the water droplets of the resulting w/o PEs are predictable. Second, it is shown that approximately all particles assemble at the droplet surface after emulsion preparation and neither the packing parameter nor the droplet size change with the particle surface charge or size when the total particle cross section is kept constant. Third, studies on the influence of the catalyst on the emulsion structure reveal that irrespective of the particle charge the surface active and negatively charged catalyst Rh–SX reduces the PE droplet size significantly and decreases the particle packing parameter from s = 0.91 (hexagonal packing in 2D) to s = 0.69 (shattered structure). In this latter case, large voids of the free w/o interface form and become covered with the catalyst. With a deep knowledge about the PE structure the reaction efficiencies of the liquid–liquid vs. the solid–liquid interface are quantified. By excluding any other influence factors, it is shown that the activity of the catalyst is the same at the fluid and solid interface and the performance of the reaction is explained by the geometry of the system. After the reaction, the catalyst retention via membrane filtration is shown to be successfully achieved without damaging the emulsions. This enables the continuous recovery of the catalyst, i.e. the most expensive compound in PE-based catalytic reactions, being a crucial criterion for industrial applications.

In this work, the effect of porphyrin loading and template size is varied systematically to study its impact on the oxygen reduction reaction (ORR) activity and selectivity as followed by rotating ring disc electrode experiments in both acidic and alkaline electrolytes. The structural composition and morphology are investigated by 57 Fe Mössbauer spectroscopy, transmission electron microscopy, Raman spectroscopy and Brunauer–Emmett–Teller analysis. It is shown that with decreasing template size, specifically the ORR performance towards fuel cell application gets improved, while at constant area loading of the iron precursor (here expressed in number of porphyrin layers), the iron signature does not change much. Moreover, it is well illustrated that too large area loadings result in the formation of undesired side phases that also cause a decrease in the performance, specifically in acidic electrolyte. Thus, if the impact of morphology is the focus of research it is important to consider the area loading rather than its weight loading. At constant weight loading, beside morphology the structural composition can also change and impact the catalytic performance. This article is part of the theme issue ‘Bio-derived and bioinspired sustainable advanced materials for emerging technologies (part 2)’.

The formation of colloidal crystals and their use as photonic materials are of high interest for various technologies in the field of sensing applications, as templates, absorber materials, catalysts, and membranes. In this study, core-shell particles consisting of a cross-linked poly(methyl methacrylate) core featuring a (polyacrylonitrile-co-styrene) shell are synthesized by starved-feed emulsion polymerization. The resulting particles are investigated with respect to size and monodispersity, as well as the core-to-shell ratio, by means of dynamic light scattering and transmission electron microscopy. Optimized particle sizes are 218 nm for the cores and 276 nm for the core-shell particles. For the formation of highly ordered and free-standing opal films, the particles are processed by the melt-shear organization technique. The resulting films show angle-dependent reflection colors, while reflected colors can be tailored by the design of the core-shell particles. As a focus of this work, polyacrylonitrile as part of the copolymer particle shell is advantageously used both for particle opal film stabilization and for tailoring the reflection colors of the opal films. It is shown that the cyclization reactions at the interface of the particles and within the matrix material significantly influence the optical properties of the opal films upon thermal treatment at 240 °C and for different heat holding times. For instance, the change of color can be simply set from red to blue upon defined thermal treatment conditions. Via this convenient protocol, brilliant reflection colors can thus be obtained based on the insights into the structure-property relationships of the underlying particle architectures and interface reactions. The scalable opal films will pave the way to functional colored materials as interesting candidates for a manifold of sensing applications and temperature-responsive polymeric materials.

Pickering emulsions (PEs), i.e. particle stabilized emulsions, are used as reaction environments in biphasic catalysis for the hydroformylation of 1-dodecene into tridecanal using the catalyst rhodium (Rh)-sulfoxantphos (SX). The present study connects the knowledge about particle-catalyst interactions and PE structure with the reaction results. It quantifies the efficiency of the catalytic performance of the catalyst localized in the voids between the particles (liquid-liquid interface) and the catalyst adsorbed on the particle surface (liquid-solid interface) using a new numerical approach. First, it is ensured that the overall packing density and geometry at the droplet interface and the size of the water droplets of the resulting w/o PEs are predictable. Second, it is shown that approximately all particles assemble at the droplet surface after emulsion preparation and neither the packing parameter nor the droplet size change with the particle surface charge or size when the total particle cross section is kept constant. Third, studies on the influence of the catalyst on the emulsion structure reveal that irrespective of the particle charge the surface active and negatively charged catalyst Rh-SX reduces the PE droplet size significantly and decreases the particle packing parameter from s = 0.91 (hexagonal packing in 2D) to s = 0.69 (shattered structure). In this latter case, large voids of the free w/o interface form and become covered with the catalyst. With a deep knowledge about the PE structure the reaction efficiencies of the liquid-liquid vs. the solid-liquid interface are quantified. By excluding any other influence factors, it is shown that the activity of the catalyst is the same at the fluid and solid interface and the performance of the reaction is explained by the geometry of the system. After the reaction, the catalyst retention via membrane filtration is shown to be successfully achieved without damaging the emulsions. This enables the continuous recovery of the catalyst, i.e. the most expensive compound in PE-based catalytic reactions, being a crucial criterion for industrial applications.