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Chirality in inorganic nanostructures has recently stimulated the attention of many researchers, both to unravel fundamental questions on the origin of chirality in inorganic and hybrid materials, as well as to introduce novel promising properties that are originated by the symmetry breaking. MoS2 is one of the most investigated among the large family of layered transition metal dichalcogenides. In particular, the metastable metallic 1T-MoS2 phase is of large interest for potential applications. However, due to thermodynamic reasons, the synthesis of 1T-MoS2 phase is quite challenging. Herein, we present the first synthesis of chiral 1T-MoS2 phase which shows remarkably high chiroptical activity with a g-factor up to 0.01. Chiral 1T-MoS2 was produced using tartaric acid as a chiral ligand to induce symmetry breaking during the material's growth under hydrothermal conditions, leading to the formation of distorted hierarchical nanosheet assemblies exhibiting chiral morphology. Thorough optimization of the synthetic conditions was carried out to maximize chiroptical activity, which is strongly related to the nanostructures' morphology. Finally, the formation mechanism of the chiral 1T-MoS2 nanosheet assemblies was investigated, focusing on the role of molecular intermediates in the growth of the nanosheets and the transfer of chirality.
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In this work, the production of novel multishell silver indium selenide quantum dots (QDs) shelled with zinc selenide and zinc sulfide through a multistep synthesis precisely designed to develop high-quality red-emitting QDs is explored. The formation of the multishell nanoheterostructure significantly improves the photoluminescence quantum yield of the nanocrystals from 3% observed for the silver indium selenide core to 27 and 46% after the deposition of the zinc selenide and zinc sulfide layers, respectively. Moreover, the incorporation of the multishelled QDs in a poly(methyl methacrylate) (PMMA) matrix via in situ radical polymerization is investigated, and the role of thiol ligand passivation is proven to be fundamental for the stabilization of the QDs during the polymerization step, preventing their decomposition and the relative luminescence quenching. In particular, the role of interface chemistry is investigated by considering both surface passivation by inorganic zinc chalcogenide layers, which allows us to improve the optical properties, and organic thiol ligand passivation, which is fundamental to ensuring the chemical stability of the nanocrystals during in situ radical polymerization. In this way, it is possible to produce silver-indium selenide QD-PMMA composites that exhibit bright red luminescence and high transparency, making them promising for potential applications in photonics. Finally, it is demonstrated that the new silver indium selenide QD-PMMA composites can serve as an efficient color conversion layer for the production of red light-emitting diodes.
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Chiral inorganic nanostructures have attracted a lot of attention over the last few years. Here we report the first observation of chirality in indium sulfide nanoparticles, which have been produced by a co-precipitation reaction in the presence of cysteine as a chiral agent. The process resulted in the production of spherical nanoparticles with an average diameter of around 3.6 nm. Circular dichroism spectroscopy of the nanoparticles showed an intense chiroptical signal corresponding to the indium sulfide excitonic transition, confirming the successful transfer of chirality to the In2S3 inorganic matrix. Nuclear magnetic resonance analysis of a colloidal solution of the nanoparticles demonstrated critical evidence of chemisorption of the chiral ligand on the surface of the nanoparticles and revealed a characteristic fast chemical exchange between the ligand chemisorbed on the surface of the nanoparticles and the free ligand in solution. Finally, the effect of the chiral ligand's structure on the transfer of chirality was investigated, with consideration of other amino acid ligands, and the critical role of the thiolate group in the optimisation of the chiral transfer was observed. This research is expected to stimulate further development and applications of new chiral semiconductor nanomaterials.
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Herein we report new chiral luminescent Cs3Cu2Br5 needle-like microcrystals and the analysis of their optical properties and the effect of the ligand structure on the transfer of chirality.
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The development of multimodal nano- and micro-structures has become an increasingly popular area of research in recent years. In particular, the combination of two or more desirable properties within a single structure opens multiple opportunities from biomedicine, sensing, and catalysis, to a variety of optical applications. Here, for the first time, we report the synthesis and characterization of multimodal chiroptically active CaCO3 nanocomposites. These composites have been prepared by a modified microemulsion method in the presence of an amino acid (cysteine). Following this, additional modalities have been introduced by loading the composites with luminescent nanoparticles or doping with Eu3+ ions. The luminescent composites have been produced by the incorporation of CuInZnS/ZnS or CdSe@ZnS/ZnS core/shell quantum dots, or via doping with trivalent europium. In this manner, we have produced chiroptically active composites with orange, green, and red luminescence. Overall, this work demonstrates the unique advantage and potential of our approach and new class of chiroptically active CaCO3 nanocomposites, which display tunable functionality to specific requirements via the incorporation of desired ions, nanoparticles, and chirality of the structure.
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Chiral semiconductor quantum dots have recently received broad attention due to their promising application in several fields such as sensing and photonics. The extensive work in the last few years was focused on the observation of the chiroptical properties in binary Cd based systems. Herein, we report on the first evidence of ligand-induced chirality in silver indium sulfide semiconductor quantum dots. Ternary disulfide quantum dots are of great interest due to their remarkable optical properties and low toxicity. Non-stoichiometric silver indium sulfide quantum dots were produced via a room temperature coprecipitation in water, in the presence of cysteine as a capping agent. The obtained nanocrystals show a notable photoluminescence quantum yield of 0.24 in water dispersions. Several critical aspects of the nanocrystal growth and chemico-physical characterization, and the optimisation of the surface passivation by the chiral ligand in order to optimize the nanoparticle chirality are thoroughly investigated. Optical spectroscopy methods such as circular dichroism and luminescence as well as nuclear magnetic resonance techniques are exploited to analyze the coordination processes leading to the formation of the ligand-nanocrystal chiral interface. This study highlights the dynamic nature of the interaction between the nanocrystal surface and the chiral ligand and clarifies some fundamental aspects for the transfer and optimization of the chiroptical properties.
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We report on a Cu(ii) catalyzed process for the production of cysteine based chiral carbon dots; the process does not require any thermal treatment and the carbon dot formation is driven by the production of reactive radical species that are generated in the reaction media by the catalytic role played by the multivalent transition metal. The nanomaterial presents a well-defined chirality and the enantioselectivity of the synthesis is proved by the isolation of both the carbon dot enantiomers. We focused our attention on the processes that take place during the carbon dot formation and the relationship with the structure of the organic starting material. Thanks to the comparison of reactions conducted with different organic substrates whose thiyl radical chemistry is known, we recognized a non-trivial role of the radical hydrogen abstraction reactions in the carbon dot formation process. The reported process allows access to a large variety of analyses to monitor the reaction mixtures during the reaction course. Finally, we report a detailed analysis on the evolution of optical chirality during the synthesis and related this feature with the formation mechanism of the nanomaterial revealing significant evidence on the chirality origin and structure of chiral carbon dots.
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We report a microwave assisted synthesis of NaNbO3 perovskite mesocrystals with a hierarchical morphology formed by the self-assembly of nanoparticles in particle clusters. The synthesis method combines non-aqueous sol-gel synthesis and microwave heating in a single step process that allows us to isolate crystalline single phase NaNbO3 in few minutes. A detailed investigation of the effect of the reaction temperature on the crystallinity and morphology of the product was conducted. The synthesis stabilizes the unusual orthorhombic phase Pmma, a property that can be ascribed to the crystal size (24 nm). TEM and SAED analyses show that the hierarchical polycrystalline particles behave as single crystals, a feature related to a non-classical crystallization mechanism. Moreover, the optical bandgap of this NaNbO3 phase was estimated for the first time. The results suggest the potential of this synthetic procedure for the fast production of high quality tertiary oxide nanocrystals.
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This work systematically compares both structural features and photocatalytic performance of a series of graphitic and amorphous carbon dots (CDs) prepared in a bottom-up manner from fructose, glucose, and citric acid. We demonstrate that the carbon source and synthetic procedures diversely affect the structural and optical properties of the CDs, which in turn unpredictably influence their photo electron transfer ability. The latter was evaluated by studying the photo-reduction of methyl viologen. Overall, citric acid-CDs were found to provide the best photocatalytic performance followed by fructose- and glucose-CDs. However, while the graphitization of glucose- and citric acid-CDs favored the photo-reaction, a reverse structure-activity dependence was observed for fructose-CDs due to the formation of a large graphitic-like supramolecular assembly. This study highlights the complexity to design in advance photo-active bio-based carbon nanomaterials.