Catalyst Supraparticles: Tuning the Structure of Spray-Dried Pt/SiO2 Supraparticles via Salt-Based Colloidal Manipulation to Control their Catalytic Performance.

The structure of supraparticles (SPs) is a key parameter for achieving advanced functionalities arising from the combination of different nanoparticle (NP) types in one hierarchical entity. However, whenever a droplet-assisted forced assembly approach is used, e.g., spray-drying, the achievable structure is limited by the inherent drying phenomena of the method. In particular, mixed NP dispersions of differently sized colloids are heavily affected by segregation during the assembly. Herein, the influence of the colloidal arrangement of Pt and SiO2 NPs within a single supraparticulate entity is investigated. A salt-based electrostatic manipulation approach of the utilized NPs is proposed to customize the structure of spray-dried Pt/SiO2 SPs. By this, size-dependent separation phenomena of NPs during solvent evaporation, that limit the catalytic performance in the reduction of 4-nitrophenol, are overcome by achieving even Pt NP distribution. Additionally, the textural properties (pore size and distribution) of the SiO2 pore framework are altered to improve the mass transfer within the material leading to increased catalytic activity. The suggested strategy demonstrates a powerful, material-independent, and universally applicable approach to deliberately customize the structure and functionality of multi-component SP systems. This opens up new ways of colloidal material combinations and structural designs in droplet-assisted forced assembly approaches like spray-drying.

Supraparticles for naked-eye H2 indication and monitoring: Improving performance by variation of the catalyst nanoparticles.

The recent transition to H2-based energy storage demands reliable H2 sensors that allow for easy, fast, and reliable detection of leaks. Conventional H2 detectors are based on the changes of physical properties of H2 probes induced by subsurface H-atoms to a material such as electrical conductivity. Herein, we report on highly reactive gasochromic H2 detectors based on the adsorption of H2 on the material surface. We prepared supraparticles (SPs) containing different types of noble metal nanoparticles (NPs), silica NPs, and the dye resazurin by spray-drying and tested their performance for H2 detection. The material undergoes a distinct color change due to the hydrogenation of the purple resazurin to pink resorufin and, finally, colorless hydroresorufin. The stepwise transition is fast and visible to the naked eye. To further improve the performance of the sensor, we tested the reactivity of SPs with different catalytically active NPs by means of in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). We show that the choice of the NP catalyst has a pronounced effect on the response of the H2 indicator. In addition, we demonstrate that the performance depends on the size of the NPs. These effects are attributed to the availability of reactive H-atoms on the NP surface. Among the materials studied, Pt-containing SPs gave the best results for H2 detection.

Influence of cation concentration and valence on the structure and texture of spray-dried supraparticles from colloidal silica dispersions.

The structure and texture of supraparticles determine their properties and performance, thus playing a critical role in research studies as well as industrial applications. The addition of salts is a well-known strategy to manipulate the colloidal stability of nanoparticles. In this study, this approach is used to tune the structure of spray-dried supraparticles. Three different salts (NaCl, CaCl2, and AlCl3) were added to binary silica (SiO2) nanoparticle dispersions (of 40 and 400 nm in size) to change their colloidal stability by lowering the electrostatic repulsion or enhancing the cation bridging. Dependent on the cation valence of the added salt and the nanoparticle size, the critical salt concentration, which yields nanoparticle agglomeration, is reached at different salt amounts. This phenomenon is exploited to tune the final structure of supraparticles - obtained by spray-drying binary dispersions - from core-shell to Janus-like to well-mixed structures. This consequently also tunes textural properties, like surface roughness and the pore system of the obtained supraparticles. Our results provide insights for controlling the structure of spray-dried supraparticles by manipulating the stability of binary nanoparticle dispersions, and they establish a framework for composite particle design.

Supraparticles on beads for supported catalytically active liquid metal solutions - the SCALMS suprabead concept.

A novel GaPt-based supported catalytically active liquid metal solution (SCALMS) material is developed by exploiting the suprabead concept: Supraparticles, i.e. micrometer-sized particles composed of nanoparticles assembled by spray-drying, are bonded to millimeter-sized beads. The suprabeads combine macroscale size with catalytic properties of nanoscale GaPt particles entrapped in their silica framework.

Magnetizing Polymer Particles with a Solvent-Free Single Stage Process Using Superparamagnetic Iron Oxide Nanoparticles (SPION)s.

Magnetic polymer composites are used in a variety of applications in many industries. Their production methods are usually time-consuming and solvent-intensive as they are performed in liquid phase processes, such as emulsion polymerization or precipitation. In this work, a quick, easy, and solvent-free method is presented to coat polymer particles with a discrete, non-coherent coating of superparamagnetic nanoparticles. The results of the dry coating process are evaluated optically, by means of scanning electron microscopy (SEM), via powder X-ray diffraction and thermally by means of differential scanning calorimetry, before finally demonstrating the effectiveness of dry coating by means of a vibrating sample magnetometer.

Core-Satellite Supraparticles To Ballistically Stamp Nanostructures on Surfaces.

Nanostructured surfaces are of great importance in a very wide range of fields. They can be obtained by imprint or deposition techniques. However, these are usually sophisticated to perform. Generally, it is not easy to equip an object/product with a nanostructure after manufacturing. Yet, it would be very beneficial to achieve a modification of an arbitrary surface with a nanostructure of choice at a later stage by an approach that is simple to perform without the need of sophisticated equipment or excessive treatment by physicochemical methods. Herein, such a process is reported, which combines two "old-fashioned" techniques, namely, sandblasting and rubber-stamping, and translates them to the "nanoworld". By creating core-satellite supraparticles via spray-drying, a ballistic core-satellite stamp particle system is obtained, which can be used to easily transfer a wide range of nanoparticles to a great variety of surfaces to equip these with a nanostructure and subsequently advanced properties. These include water-repellant, antifouling, or antidust surfaces. Moreover, it is also demonstrated that the approach can be used to manufacture well-defined nanoimprinted surfaces. Such surfaces showed an improved spreading behavior for aliphatic alcohols, thus making such surfaces, for instance, very susceptible for disinfectants. All in all, the simple technique described herein has a great potential for creating nanostructured surfaces on nearly any surface.