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The creation of complex hollow nanostructures with precise control over size and shape represents a great challenge in supramolecular soft materials. Here, we have further developed a bioinspired methodology for the formation of aqueous nanotubes of well‐defined dimensions and pore coating through the self‐assembly of amphiphiles that are chemically programmed with complementary nucleobases. These nanotubes are endowed with a hydrophobic lumen, whose diameter can be expanded as a function of the monomer length, in which apolar dyes can be efficiently encapsulated. [ABSTRACT FROM AUTHOR]

The development of sodium ion batteries will require high‐performance electrodes with very large areal capacity and reasonable rate performance. Although red phosphorus is a very promising electrode material, it has not yet fulfilled these requirements. Here, liquid phase exfoliation is used to convert solid red phosphorus into amorphous, quasi‐2D nanoplatelets. These nanoplatelets have lateral sizes of hundreds of nanometers, thickness of 10s of nanometers and are quite stable in ambient conditions, displaying only low levels of oxidation on the nanosheet surface. By solution mixing with carbon nanotubes, these nanoplatelets can be fabricated into nanocomposite battery anodes. After employing an extended activation process, good cycling stability over 1000 cycles and low‐rate capacitances >2000 mAh gP−1 is achieved. Because of the high conductivity and mechanical robustness provided by the nanotube network, it is possible to fabricate very thick electrodes. These electrodes display extremely high areal capacities approaching 10 mAh cm−2 at currents of ≈1 mA cm−2. Detailed analysis shows these electrodes to be limited by solid‐state diffusion such that the thickest electrodes have state‐of‐the‐art rate performance and a near‐optimized combination of capacity and rate performance. [ABSTRACT FROM AUTHOR]

Gold nanoclusters (AuNCs) are nanomaterials with interesting photoluminescent properties that can be endowed with biomolecular recognition and biocompatibility when stabilized with proteins. The interplay between the optical features of AuNCs and the function added by the protein makes them perfect candidates for generating hybrid protein‐inorganic nanomaterials. Focusing on protein stabilized‐AuNCs, hitherto most of the work has covered the use of natural proteins for in situ growth of AuNCs. However, the exploitation of design proteins for such endeavors enables fine‐tuning of the photoluminescent assets of AuNCs. In this work, rational protein engineering of modular protein scaffolds is applied for capping of non‐emissive, non‐passivated naked AuNCs, resulting in a fast and easy method for the synthesis of customizable and emissive protein‐AuNC nanomaterials. Tuning of the photoluminescent properties of the final hybrid module is obtained by appropriate choice of the coordination residues grafted on the same protein scaffold. The effects of ligands and coordination bonds are studied using time‐resolved photoluminescence and X‐ray absorbance spectroscopies, shedding light on the mechanisms behind the emerging properties of these hybrid materials. Moreover, the described versatile strategy opens new avenues for the synthesis of on‐demand photoluminescent hybrids for a wide spectrum of optical applications. [ABSTRACT FROM AUTHOR]

Abstract: Identifying cheap, yet effective, oxygen evolution catalysts is critical to the advancement of water splitting. Using liquid exfoliated Co(OH)2 nanosheets as a model system, a simple procedure is developed to maximize the activity of any oxygen evolution reaction nanocatalyst. First the nanosheet edges are confirmed as the active areas by analyzing the catalytic activity as a function of nanosheet size. This allows the authors to select the smallest nanosheets (length ≈50 nm) as the best performing catalysts. While the number of active sites per unit electrode area can be increased via the electrode thickness, this is found to be impossible beyond ≈10 µm due to mechanical instabilities. However, adding carbon nanotubes increases both toughness and conductivity significantly. These enhancements mean that composite electrodes consisting of small Co(OH)2 nanosheets and 10 wt% nanotubes can be made into freestanding films with thickness of up to 120 µm with no apparent electrical limitations. The presence of diffusion limitations results in an optimum electrode thickness of 70 µm, yielding a current density of 50 mA cm−2 at an overpotential of 235 mV, close to the state of the art in the field. Applying this procedure to a high‐performance catalyst such as NiFeOx should significantly surpass the state of the art. [ABSTRACT FROM AUTHOR]

Many promising supercapacitor electrode materials have high resistivity and require conductive additives to function effectively. However, the detailed role of the additive is not understood. Here, this question is resolved by applying a quantitative model for resistance-limited supercapacitor electrodes to Co(OH)2-nanosheet/carbon nanotube composites. Without nanotubes, theory predicts and experiments show that while the low-rate capacitance increases linearly with electrode thickness, the high rate capacitance decreases with thickness due to slow charging. Experiments supported by theory show that nanotube addition has two effects. First, the nanotube network effectively distributes charge, increasing the intrinsic electrode performance to the limit associated with its accessible surface area. Second, at high-rate, the increased electrode conductivity shifts the rate-limiting resistance from electrode to electrolyte, thus removing the thickness-dependent capacitance falloff. Furthermore, the analysis quantifies the out-of-plane conductivity of the nanotube network, identifies the cross-over from resistance-limited to diffusion-limited behavior, and allows full electrode modeling, facilitating rational design. [ABSTRACT FROM AUTHOR]

Abstract: Many promising supercapacitor electrode materials have high resistivity and require conductive additives to function effectively. However, the detailed role of the additive is not understood. Here, this question is resolved by applying a quantitative model for resistance‐limited supercapacitor electrodes to Co(OH)2‐nanosheet/carbon nanotube composites. Without nanotubes, theory predicts and experiments show that while the low‐rate capacitance increases linearly with electrode thickness, the high rate capacitance decreases with thickness due to slow charging. Experiments supported by theory show that nanotube addition has two effects. First, the nanotube network effectively distributes charge, increasing the intrinsic electrode performance to the limit associated with its accessible surface area. Second, at high‐rate, the increased electrode conductivity shifts the rate‐limiting resistance from electrode to electrolyte, thus removing the thickness‐dependent capacitance falloff. Furthermore, the analysis quantifies the out‐of‐plane conductivity of the nanotube network, identifies the cross‐over from resistance‐limited to diffusion‐limited behavior, and allows full electrode modeling, facilitating rational design. [ABSTRACT FROM AUTHOR]

While liquid phase exfoliation can be used to produce nanosheets stabilized in polymer solutions, very little is known about the resultant nanosheet size, thickness, or monolayer content. The present study uses semiquantitative spectroscopic metrics based on extinction, Raman, and photoluminescence (PL) spectroscopy to investigate these parameters for WS2 nanosheets exfoliated in aqueous poly(vinyl alcohol) (PVA) solutions. By measuring Raman and PL simultaneously, the monolayer content can be tracked via the PL/Raman intensity ratio while varying processing conditions. The PL is found to be maximized for a stabilizing polymer concentration of 2 g L−1. In addition, the monolayer content can be controlled via the centrifugation conditions, exceeding 5% by mass in some cases. These techniques have allowed tracking the ratio of PL/Raman in a droplet of polymer-stabilized WS2 nanosheets as the water evaporates during composite formation. No evidence of nanosheet aggregation is found under these conditions although the PL becomes dominated by trion emission as drying proceeds and the balance of doping from PVA/water changes. Finally, bulk PVA/WS2 composites are produced by freeze drying where >50% of the monolayers remain unaggregated, even at WS2 volume fractions as high as 10%. [ABSTRACT FROM AUTHOR]

The creation of complex hollow nanostructures with precise control over size and shape represents a great challenge in supramolecular soft materials. Here, we have further developed a bioinspired methodology for the formation of aqueous nanotubes of well-defined dimensions and pore coating through the self-assembly of amphiphiles that are chemically programmed with complementary nucleobases. These nanotubes are endowed with a hydrophobic lumen, whose diameter can be expanded as a function of the monomer length, in which apolar dyes can be efficiently encapsulated., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

The bottom-up synthesis of an unprecedentedly large cove-edged nanographene, hexa-peri-hexabenzo-bis-peri-octacene (HBPO), is reported in this work. Chiral high-performance liquid chromatography and density functional theory (DFT) calculations revealed multiple conformations in solution. Two different molecular conformations, "waggling" and "butterfly", were found in crystals by X-ray crystallography, and the selectivity of conformations could be tuned by solvents. The optoelectronic properties of HBPO were investigated by UV/Vis absorption and fluorescence spectroscopies, cyclic voltammetry, and DFT calculations. The contorted geometry and branched alkyl groups suppress the aggregation of HBPO in solution, leading to a high fluorescence quantum yield of 79 %. The optical-gain properties were explored through transient absorption and amplified spontaneous emission spectroscopies, which enrich the choices of edge structures for potential applications in laser cavities., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Titanium disulfide is a promising material for a range of applications, including lithium-ion battery (LIB) anodes. However, its application potential has been severely hindered by the tendency of exfoliated TiS2 to rapidly oxidize under ambient conditions. Herein, we confirm that, although layered TiS2 powder can be exfoliated by sonication in aqueous surfactant solutions, the resultant nanosheets oxidise almost completely within hours. However, we find that upon performing the exfoliation in the solvent cyclohexyl-pyrrolidone (CHP), the oxidation is almost completely suppressed. TiS2 nanosheets dispersed in CHP and stored at 4 °C in an open atmosphere for 90 days remained up to 95% intact. In addition, CHP-exfoliated nanosheets did not show any evidence of oxidation for at least 30 days after being transformed into dry films even when stored under ambient conditions. This stability, probably a result of a residual CHP coating, allows TiS2 nanosheets to be deployed in applications. To demonstrate this, we prepared lithium ion battery anodes from nano : nano composites of TiS2 nanosheets mixed with carbon nanotubes. These anodes displayed reversible capacities (920 mA h g-1) close to the theoretical value and showed good rate performance and cycling capability.