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    Design of a scalable AuNP catalyst system for plasmon-driven photocatalysis
    (Cambridge : Royal Society of Chemistry, 2018) Stolle, H.L.K.S.; Garwe, F.; MĂĽller, R.; Krech, T.; Oberleiter, B.; Rainer, T.; Fritzsche, W.; Stolle, A.
    In this work we present a simple, fast and cost-efficient synthesis of a metal nanoparticle catalyst on a glass support for plasmon driven heterogeneous photocatalysis. It is based on efficient mixing of metal salts as particle precursors with porous glass as the supporting material in a mixer ball mill, and the subsequent realization of a complete catalyst system by laser sintering the obtained powder on a glass plate as the support. By this, we could obtain catalyst systems with a high particle proportion and an even spatial particle distribution in a rapid process, which could be applied to various kinds of metal salt resulting in plasmon active metal nanoparticles. Furthermore, the catalyst production process presented here is easily scalable to any size of area that is to be coated. Finally, we demonstrate the catalytic performance of our catalysts by a model reaction of ethanol degradation in a self-designed lab-scale reactor.
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    2D/3D Metallic Nano-objects Self-Organized in an Organic Molecular Thin Film
    (Washington, DC : ACS Publications, 2020) Molodtsova, Olga V.; Aristova, Irina M.; Potorochin, Dmitrii V.; Babenkov, Sergey V.; Khodos, Igor I.; Molodtsov, Serguei L.; Makarova, Anna A.; Smirnov, Dmitry A.; Aristov, Victor Yu.
    We present the fabrication and investigation of the properties of nanocomposite structures consisting of two-dimensional (2D) and three-dimensional (3D) metallic nano-objects self-organized on the surface and inside of organic molecular thin-film copper tetrafluorophthalocyanine (CuPcF4). Metallic atoms, deposited under ultrahigh vacuum (UHV) conditions onto the organic ultrathin film, diffuse along the surface and self-assemble into a system of 2D metallic overlayers. At the same time, the majority of the metal atoms diffuse into the organic matrix and self-organize into 3D nanoparticles (NPs) in a well-defined manner. The evolution of the morphology and electronic properties of such structures as a function of nominal metal content is studied under UHV conditions using transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), and photoelectron spectroscopy (PES) techniques. Using HR-TEM, we have observed the periodicity of atomic planes of individual silver NPs. The steady formation of agglomerates from individual single nanocrystallites with intercrystallite boundaries is observed as well. PES reveals generally weak chemical interactions between silver and the organic matrix and n-doping of CuPcF4 at the initial stages of silver deposition, which is associated with charge transfer from the 2D wetting layer on the basis of core-level spectra shift analysis. Copyright © 2020 American Chemical Society.
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    Shape-Dependent Catalytic Activity of Gold and Bimetallic Nanoparticles in the Reduction of Methylene Blue by Sodium Borohydride
    (Basel : MDPI, 2021) Stolle, Heike Lisa Kerstin Stephanie; Kluitmann, Jonas Jakobus; Csáki, Andrea; Köhler, Johann Michael; Fritzsche, Wolfgang
    In this study the catalytic activity of different gold and bimetallic nanoparticle solutions towards the reduction of methylene blue by sodium borohydride as a model reaction is investigated. By utilizing differently shaped gold nanoparticles, i.e., spheres, cubes, prisms and rods as well as bimetallic gold–palladium and gold–platinum core-shell nanorods, we evaluate the effect of the catalyst surface area as available gold surface area, the shape of the nanoparticles and the impact of added secondary metals in case of bimetallic nanorods. We track the reaction by UV/Vis measurements in the range of 190–850 nm every 60 s. It is assumed that the gold nanoparticles do not only act as a unit transferring electrons from sodium borohydride towards methylene blue but can promote the electron transfer upon plasmonic excitation. By testing different particle shapes, we could indeed demonstrate an effect of the particle shape by excluding the impact of surface area and/or surface ligands. All nanoparticle solutions showed a higher methylene blue turnover than their reference, whereby gold nanoprisms exhibited 100% turnover as no further methylene blue absorption peak was detected. The reaction rate constant k was also determined and revealed overall quicker reactions when gold or bimetallic nanoparticles were added as a catalyst, and again these were highest for nanoprisms. Furthermore, when comparing gold and bimetallic nanorods, it could be shown that through the addition of the catalytically active second metal platinum or palladium, the dye turnover was accelerated and degradation rate constants were higher compared to those of pure gold nanorods. The results explore the catalytic activity of nanoparticles, and assist in exploring further catalytic applications.