Browsing by Subject "gold"

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  • Heliövaara, Eeva; Liljeqvist, Henri; Muuronen, Mikko; Eronen, Aleksi; Moslova, Karina; Repo, Timo (2021)
    Development of new, environmentally benign dissolution methods for metallic gold is driven by needs in the circular economy. Gold is widely used in consumer electronics, but sustainable and selective dissolution methods for Au are scarce. Herein, we describe a quantitative dissolution of gold in organic solution under mild conditions by using hydrogen peroxide as an oxidant. In the dissolution reaction, two thiol ligands, pyridine-4-thiol and 2-mercaptobenzimidazole, work in a cooperative manner. The mechanistic investigations suggest that two pyridine-4-thiol molecules form a complex with Au-0 that can be oxidized, whereas the role of inexpensive 2-mercaptobenzimidazole is to stabilize the formed Au-I species through a ligand exchange process. Under optimized conditions, the reaction proceeds vigorously and gold dissolves quantitatively in two hours. The demonstrated ligand-exchange mechanism with two thiols allows to drastically reduce the thiol consumption and may lead to even more effective gold dissolution methods in the future.
  • de Souza Rodrigues, Maria Paula; Dourado, Andre H. B.; Cutolo, Leonardo de O.; Parreira, Luanna S.; Alves, Tiago Vinicius; Slater, Thomas J. A.; Haigh, Sarah J.; Camargo, Pedro H. C.; Cordoba de Torresi, Susana Ines (2021)
    State of the art electrocatalysts for the hydrogen evolution reaction (HER) are based on metal nanoparticles (NPs). It has been shown that the localized surface plasmon resonance (LSPR) excitation in plasmonic NPs can be harvested to accelerate a variety of molecular transformations. This enables the utilization of visible light as an energy input to enhance HER performances. However, most metals that are active toward the HER do not support LSPR excitation in the visible or near-IR ranges. We describe herein the synthesis of gold-rhodium core-shell nanoflowers (Au@Rh NFs) that are composed of a core made up of spherical Au NPs and shells containing Rh branches. The Au@Rh NFs were employed as a model system to probe how the LSPR excitation from Au NPs can lead to an enhancement in the HER performance for Rh. Our data demonstrate that the LSPR excitation at 533 nm (and 405 nm) leads to an improvement in the HER performance of Rh, which depends on the morphological features of the Au Rh NFs, offering opportunities for optimization of the catalytic performance. Control experiments indicate that this improvement originates from the stronger interaction of Au@Rh NFs with H2O molecules at the surface, leading to an icelike configuration, which facilitated the HER under LSPR excitation.
  • Zippel, Christoph; Israil, Roumany; Schüssler, Lars; Hassan, Zahid; Schneider, Erik K.; Weis, Patrick; Nieger, Martin; Bizzarri, Claudia; Kappes, Manfred M.; Riehn, Christoph; Diller, Rolf; Braese, Stefan (2021)
    The modular synthesis of Au(I)/Ru(II) decorated mono- and heterobimetallic complexes with pi-conjugated [2.2]paracyclophane is described. [2.2]Paracyclophane serves as a rigid spacer which holds the metal centers in precise spatial orientations and allows metal-to-metal distance modulation. A broad set of architectural arrangements of pseudo -geminal, -ortho, -meta, and -para substitution patterns were employed. Metal-to-metal distance modulation of Au(I)/Ru(II) heterobimetallic complexes and the innate transannular pi-communication of the cyclophanyl scaffold provides a promising platform for the investigations of structure-activity relationship and cooperative effects. The Au(I)/Ru(II) heterobimetallic cyclophanyl complexes are stable, easily accessible, and exhibit promising catalytic activity in the visible-light promoted arylative Meyer-Schuster rearrangement.
  • Räisänen, Minna; Heliövaara, Eeva; Al-Qaisi, Feda'a; Muuronen, Mikko; Eronen, Aleksi; Liljeqvist, Henri; Nieger, Martin; Kemell, Marianna; Moslova, Karina; Hämäläinen, Jani; Lagerblom, Kalle; Repo, Timo (2018)
    Dissolution of elemental gold in organic solutions is a contemporary approach to lower the environmental burden associated with gold recycling. Herein, we describe fundamental studies on a highly efficient method for the dissolution of elemental Au that is based on DMF solutions containing pyridine-4-thiol (4-PSH) as a reactive ligand and hydrogen peroxide as an oxidant. Dissolution of Au proceeds through several elementary steps: isomerization of 4-PSH to pyridine-4-thione (4-PS), coordination with Au-0, and then oxidation of the Au-0 thione species to Au-I simultaneously with oxidation of free pyridine thione to elemental sulfur and further to sulfuric acid. The final dissolution product is a Au-I complex bearing two 4-PS ligands and SO42- as a counterion. The ligand is crucial as it assists the oxidation process and stabilizes and solubilizes the formed Au cations.