Solvent controlled 2D structures of bottom-up fabricated nanoparticle superlattices.

We demonstrate that oleyl phosphate ligand-stabilized iron oxide nanocubes as building blocks can be assembled into 2D supercrystalline mono- and multilayers on flat YSZ substrates within a few minutes using a simple spin-coating process. As a bottom-up process, the growth takes place in a layer-by-layer mode and therefore by tuning the spin-coating parameters, the exact number of deposited monolayers can be controlled. Furthermore, ex situ scanning electron and atomic force microscopy as well as X-ray reflectivity measurements give evidence that the choice of solvent allows the control of the lattice type of the final supercrystalline monolayers. This observation can be assigned to the different Hansen solubilities of the solvents used for the nanoparticle dispersion because it determines the size and morphology of the ligand shell surrounding the nanoparticle core. Here, by using toluene and chloroform as solvents, it can be controlled whether the resulting monolayers are ordered in a square or hexagonal supercrystalline lattice.

Adsorption and Inactivation of SARS-CoV-2 on the Surface of Anatase TiO2(101).

We investigated the adsorption of severe acute respiratory syndrome corona virus 2 (SARS-CoV-2), the virus responsible for the current pandemic, on the surface of the model catalyst TiO2(101) using atomic force microscopy, transmission electron microscopy, fluorescence microscopy, and X-ray photoelectron spectroscopy, accompanied by density functional theory calculations. Three different methods were employed to inactivate the virus after it was loaded on the surface of TiO2(101): (i) ethanol, (ii) thermal, and (iii) UV treatments. Microscopic studies demonstrate that the denatured spike proteins and other proteins in the virus structure readsorb on the surface of TiO2 under thermal and UV treatments. The interaction of the virus with the surface of TiO2 was different for the thermally and UV treated samples compared to the sample inactivated via ethanol treatment. AFM and TEM results on the UV-treated sample suggested that the adsorbed viral particles undergo damage and photocatalytic oxidation at the surface of TiO2(101) which can affect the structural proteins of SARS-CoV-2 and denature the spike proteins in 30 min. The role of Pd nanoparticles (NPs) was investigated in the interaction between SARS-CoV-2 and TiO2(101). The presence of Pd NPs enhanced the adsorption of the virus due to the possible interaction of the spike protein with the NPs. This study is the first investigation of the interaction of SARS-CoV-2 with the surface of single crystalline TiO2(101) as a potential candidate for virus deactivation applications. Clarification of the interaction of the virus with the surface of semiconductor oxides will aid in obtaining a deeper understanding of the chemical processes involved in photoinactivation of microorganisms, which is important for the design of effective photocatalysts for air purification and self-cleaning materials.

Evolution of Hierarchically Porous Nickel Alumina Catalysts Studied by X-Ray Ptychography.

The synthesis of hierarchically porous materials usually requires complex experimental procedures, often based around extensive trial and error approaches. One common synthesis strategy is the sol-gel method, although the relation between synthesis parameters, material structure and function has not been widely explored. Here, in situ 2D hard X-ray ptychography (XRP) and 3D ptychographic X-ray computed tomography (PXCT) are applied to monitor the development of hierarchical porosity in Ni/Al2 O3 and Al2 O3 catalysts with connected meso- and macropore networks. In situ XRP allows to follow textural changes of a dried gel Ni/Al2 O3 sample as a function of temperature during calcination, activation and CO2 methanation reaction. Complementary PXCT studies on dried gel particles of Ni/Al2 O3 and Al2 O3 provide quantitative information on pore structure, size distribution, and shape with 3D spatial resolution approaching 50 nm, while identical particles are imaged ex situ before and after calcination. The X-ray imaging results are correlated with N2 -sorption, Hg porosimetry and He pycnometry pore characterization. Hard X-ray nanotomography is highlighted to derive fine structural details including tortuosity, branching nodes, and closed pores, which are relevant in understanding transport phenomena during chemical reactions. XRP and PXCT are enabling technologies to understand complex synthesis pathways of porous materials.

Resolving physical interactions between bacteria and nanotopographies with focused ion beam scanning electron microscopy.

To robustly assess the antibacterial mechanisms of nanotopographies, it is critical to analyze the bacteria-nanotopography adhesion interface. Here, we utilize focused ion beam milling combined with scanning electron microscopy to generate three-dimensional reconstructions of Staphylococcus aureus or Escherichia coli interacting with nanotopographies. For the first time, 3D morphometric analysis has been exploited to quantify the intrinsic contact area between each nanostructure and the bacterial envelope, providing an objective framework from which to derive the possible antibacterial mechanisms of synthetic nanotopographies. Surfaces with nanostructure densities between 36 and 58 per µm2 and tip diameters between 27 and 50 nm mediated envelope deformation and penetration, while surfaces with higher nanostructure densities (137 per µm2) induced envelope penetration and mechanical rupture, leading to marked reductions in cell volume due to cytosolic leakage. On nanotopographies with densities of 8 per µm2 and tip diameters greater than 100 nm, bacteria predominantly adhered between nanostructures, resulting in cell impedance.

Solution blow spinning of polymer/nanocomposite micro-/nanofibers with tunable diameters and morphologies using a gas dynamic virtual nozzle.

Uniform endless fibers are ubiquitous and their applications range from functional textiles over biomedical engineering to high-performance filtering and drug delivery systems. Here, we report a new method for the direct, reproducible fabrication of uniform polymer and composite micro-/nanofibers using a microfluidic gas flow focusing nozzle (Gas Dynamic Virtual Nozzle (GDVN)) relinquishing the need for external fiber pulling mechanisms. Compared to other methods, this technique is inexpensive, user-friendly and permits precise fiber diameter control (~250 nm to ~15 µm), high production rate (m/s-range) and direct fiber deposition without clogging due to stable, gas-focused jetting. Control over shape (flat or round) and surface patterning are achieved by simply tuning the air pressure and polymer concentration. The main thinning process happens after the polymer exits the device and is, therefore, mostly independent of the nozzle's internal geometry. Nevertheless, the lithography-based device design is versatile, allowing for precise flow-field control for operation stability as well as particle alignment control. As an example, we demonstrate the successful production of endless hematite nanocomposite fibers which highlights this technology's exciting possibilities that can lead to the fabrication of multifunctional/stimuli-responsive fibers with thermal and electrical conductivity, magnetic properties and enhanced mechanical stability.

A versatile nanoreactor for complementary in situ X-ray and electron microscopy studies in catalysis and materials science.

Two in situ `nanoreactors' for high-resolution imaging of catalysts have been designed and applied at the hard X-ray nanoprobe endstation at beamline P06 of the PETRA III synchrotron radiation source. The reactors house samples supported on commercial MEMS chips, and were applied for complementary hard X-ray ptychography (23 nm spatial resolution) and transmission electron microscopy, with additional X-ray fluorescence measurements. The reactors allow pressures of 100 kPa and temperatures of up to 1573 K, offering a wide range of conditions relevant for catalysis. Ptychographic tomography was demonstrated at limited tilting angles of at least ±35° within the reactors and ±65° on the naked sample holders. Two case studies were selected to demonstrate the functionality of the reactors: (i) annealing of hierarchical nanoporous gold up to 923 K under inert He environment and (ii) acquisition of a ptychographic projection series at ±35° of a hierarchically structured macroporous zeolite sample under ambient conditions. The reactors are shown to be a flexible and modular platform for in situ studies in catalysis and materials science which may be adapted for a range of sample and experiment types, opening new characterization pathways in correlative multimodal in situ analysis of functional materials at work. The cells will presently be made available for all interested users of beamline P06 at PETRA III.

Electrodeposition of nanowires of a high copper content thiourea precursor of copper sulfide.

Copper thiourea complexes are an important material class for application as a precursor of copper sulfide nanocrystals with potential use in solar cells, optoelectronics, medicine, etc. They represent a type of single source precursor, comprising both copper and sulfur in one chemical compound, whose tunable stoichiometry and morphology enable control of the quality and properties of the synthesized copper sulfide nanocrystals. Here, we present a template free electrochemical route to prepare nanowires of copper thiourea (tu) chloride hemihydrate ([Cu(tu)]Cl·½H2O) by pulse deposition. We proposed the model of the growth of nanowires. We also demonstrate complete transformation from the precursor to copper sulfide nanowire by heating it to 180 °C that involves 20% volume loss due to the decomposition of organic constituents; the obtained nanowires have around 38% covellite (CuS) and 62% digenite (Cu1.8S) phases. Electrochemistry offers the advantage of spatially selected deposition e.g. in the active regions of a device.