Gas-Phase Nitrogen Doping of Monolithic TiO2 Nanoparticle-Based Aerogels for Efficient Visible Light-Driven Photocatalytic H2 Production.

The development of visible light-active photocatalysts is essential for increasing the conversion efficiency of solar energy into hydrogen (H2). Here, we present a facile method for nitrogen doping of monolithic titanium dioxide (TiO2) nanoparticle-based aerogels to activate them for visible light. Plasma-enhanced chemical vapor deposition at low temperature enables efficient incorporation of nitrogen into preformed TiO2 aerogels without compromising their advantageous intrinsic characteristics such as large surface area, extensive porosity, and nanoscale properties of the semiconducting building blocks. By balancing the dopant concentration and the defects, the nitridation improves optical absorption and charge separation efficiency. The nitrogen-doped TiO2 nanoparticle-based aerogels loaded with palladium (Pd) nanoparticles show a significant enhancement in visible light-driven photocatalytic H2 production (3.1 mmol h-1 g-1) with excellent stability over 5 days. With this method, we introduce a powerful tool to tune the properties of nanoparticle-based aerogels after synthesis for a specific application, as exemplified by visible light-driven H2 production.

3D Printed Scaffolds for Monolithic Aerogel Photocatalysts with Complex Geometries.

Monolithic aerogels composed of crystalline nanoparticles enable photocatalysis in three dimensions, but they suffer from low mechanical stability and it is difficult to produce them with complex geometries. Here, an approach to control the geometry of the photocatalysts to optimize their photocatalytic performance by introducing carefully designed 3D printed polymeric scaffolds into the aerogel monoliths is reported. This allows to systematically study and improve fundamental parameters in gas phase photocatalysis, such as the gas flow through and the ultraviolet light penetration into the aerogel and to customize its geometric shape to a continuous gas flow reactor. Using photocatalytic methanol reforming as a model reaction, it is shown that the optimization of these parameters leads to an increase of the hydrogen production rate by a factor of three from 400 to 1200 µmol g-1 h-1 . The rigid scaffolds also enhance the mechanical stability of the aerogels, lowering the number of rejects during synthesis and facilitating handling during operation. The combination of nanoparticle-based aerogels with 3D printed polymeric scaffolds opens up new opportunities to tailor the geometry of the photocatalysts for the photocatalytic reaction and for the reactor to maximize overall performance without necessarily changing the material composition.

Porous Silica Microspheres with Immobilized Titania Nanoparticles for In-Flow Solar-Driven Purification of Wastewater.

In this paper, inorganic silica microspheres with interconnected macroporosity are tested as a platform for designing robust and efficient photocatalytic systems for a continuous flow reactor, enabling a low cost and straightforward purification of wastewater through solar-driven photocatalysis. The photocatalytically active microspheres are prepared by wet impregnation of porous silica scaffolds with Trizma-functionalized anatase titania (TiO2) nanoparticles (NPs). NPs loading of 22 wt% is obtained in the form of a thin and well-attached layer, covering the external surface of the microspheres as well as the internal surface of the pores. The TiO2 loading leads to an increase of the specific surface area by 26%, without impacting the typically interconnected macroporosity (≈60%) of the microspheres, which is essential for an efficient flow of the pollutant solution during the photocatalytic tests. These are carried out in a liquid medium for the decomposition of methyl orange and paracetamol. In addition to photocatalytic activity under continuous flow, the microspheres offer the advantage that they can be easily removed from the reaction medium, which is an appealing aspect for industrial applications. In this work, the typical issues of TiO2 NPs photocatalysts are circumvented, without the need for elaborate chemistries, and for low availability and expensive raw materials.

Synthesis, Spray Deposition, and Hot-Press Transfer of Copper Nanowires for Flexible Transparent Electrodes.

We report a solution-phase approach to the synthesis of crystalline copper nanowires (Cu NWs) with an aspect ratio >1000 via a new catalytic mechanism comprising copper ions. The synthesis involves the reaction between copper(II) chloride and copper(II) acetylacetonate in a mixture of oleylamine and octadecene. Reaction parameters such as the molar ratio of precursors as well as the volume ratio of solvents offer the possibility to tune the morphology of the final product. A simple low-cost spray deposition method was used to fabricate Cu NW films on a glass substrate. Post-treatment under reducing gas (5% H2 + 95% N2) atmosphere resulted in Cu NW films with a low sheet resistance of 24.5 Ω/sq, a transmittance of T = 71% at 550 nm (including the glass substrate), and a high oxidation resistance. Moreover, the conducting Cu NW networks on a glass substrate can easily be transferred onto a polycarbonate substrate using a simple hot-press transfer method without compromising on the electrical performance. The resulting flexible transparent electrodes show excellent flexibility ( R/ Ro < 1.28) upon bending to curvatures of 1 mm radius.

The Importance of Materials Design to Make Ions Flow: Toward Novel Materials Platforms for Bioelectronics Applications.

Chemical design criteria for materials for bioelectronics applications using a series of copolymer derivatives based on poly(3-hexylthiophene) are established. Directed chemical design via side-chain functionalization with polar groups allows manipulation of ion transport and ion-to-electron transduction. Insights gained will permit increased use of the plethora of materials employed in the organic electronics area for application in the bioelectronics field.