| 1. |
- Magnard, Nicolas P.L., et al.
(författare)
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Control of H-Related Defects in γ-MnO2 in a Hydrothermal Synthesis
- 2023
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Ingår i: Inorganic Chemistry. - 0020-1669. ; 62:32, s. 13021-13029
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Tidskriftsartikel (refereegranskat)abstract
- Manganese dioxide is a good candidate for effective energy storage and conversion as it possesses rich electrochemistry. The compound also shows a wide polymorphism. The γ-variety, an intergrowth of β- and R-MnO2, has been extensively studied in several types of batteries (e.g., Zn/MnO2, Li-ion) and is a common electrode material for commercial batteries. It is well known that the insertion of protons thermodynamically stabilizes γ-MnO2 with respect to β-MnO2. Protons can enter the structure either by forming groups of 4 hydroxyls around a Mn4+ vacancy, called a Ruetschi defect, or by forming a hydroxyl group near a Mn3+ ion, called a Coleman defect. These defects differently affect the electrochemistry of manganese oxide, and tailoring their amount in the structure can be used to tune the material properties. Previous studies have addressed the proton insertion process, but the role of the synthesis pathway on the amount of defects created is not well understood. We here investigate how the parameters in a hydrothermal synthesis of γ-MnO2 nanoparticles influence the amount and type of H-related defects. Structural investigations are carried out using Pair Distribution Function analysis, X-ray absorption spectroscopy, thermogravimetric analysis, and inelastic neutron scattering. We demonstrate the possibility to control the amount and type of defects introduced during the synthesis. While the amount of Ruetschi defects increases with synthesis temperature, it decreases with extended synthesis time, along with the amount of Coleman defects. Moreover, we discuss the arrangement of the defects in the γ-MnO2 nanoparticles.
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| 2. |
- Quinson, Jonathan, et al.
(författare)
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Surfactant-Free Colloidal Syntheses of Gold-Based Nanomaterials in Alkaline Water and Mono-alcohol Mixtures
- 2023
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 35:5, s. 2173-2190
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Tidskriftsartikel (refereegranskat)abstract
- Gold nanoparticles (Au NPs) and gold-based nanomaterials combine unique properties relevant for medicine, imaging, optics, sensing, catalysis, and energy conversion. While the Turkevich-Frens and Brust-Schiffrin methods remain the state-of-the-art colloidal syntheses of Au NPs, there is a need for more sustainable and tractable synthetic strategies leading to new model systems. In particular, stabilizers are almost systematically used in colloidal syntheses, but they can be detrimental for fundamental and applied studies. Here, a surfactant-free synthesis of size-controlled colloidal Au NPs stable for months is achieved by the simple reduction of HAuCl4 at room temperature in alkaline solutions of low-viscosity mono-alcohols such as ethanol or methanol and water, without the need for any other additives. Palladium (Pd) and bimetallic AuxPdy NPs, nanocomposites and multimetallic samples, are also obtained and are readily active (electro)catalysts. The multiple benefits over the state-of-the-art syntheses that this simple synthesis bears for fundamental and applied research are highlighted.
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