Transition-metal dichalcogenide (TMD) nanosheets have become an intensively investigated topic in the field of 2D nanomaterials, especially due to the direct semiconductor nature, and the broken inversion symmetry in the odd-layer number, of some of their family members. These properties make TMDs attractive for different technological applications such as photovoltaics, optoelectronics, valleytronics, and hydrogen evolution reactions. Among them, MoX 2 (X = S and Se) are turned to direct gap when their thickness is thinned down to monolayer, and thus, efforts toward obtaining large-scale monolayer TMDs are crucial for technological applications. Colloidal synthesis of TMDs has been developed in recent years, as it provides a cost-efficient and scalable way to produce few-layer TMDs having homogeneous size and thickness, yet obtaining a monolayer has proven challenging. Here, we present a method for the colloidal synthesis of mono-and few-layer MoX 2 (X = S and Se) using elemental chalcogenide and metal chloride as precursors. Using a synthesis with slow injection of the MoCl 5 precursor under a nitrogen atmosphere, and optimizing the synthesis parameters with a design of experiments approach, we obtained a MoX 2 sample with the semiconducting (1H) phase and optical band gaps of 1.96 eV for 1H−MoS 2 and 1.67 eV for 1H−MoSe 2 , respectively, consistent with a large monolayer yield in the ensemble. Both display photoluminescence at cryogenic and room temperature, paving the way for optical spectroscopy studies and photonic applications of colloidal TMD nanosheets.
In this paper we report on the use of an Ullmann-like aryl halide homocoupling reaction to obtain long Graphyne Molecular Wires (GY MWs) organized in dense, ordered arrays.
The growth of controlled 1D carbon-based nanostructures on metal surfaces is a multistep process whose path, activation energies, and intermediate metastable states strongly depend on the employed substrate. Whereas this process has been extensively studied on gold, less work has been dedicated to silver surfaces, which have a rather different catalytic activity. In this work, we present an experimental and theoretical investigation of the growth of poly-p-phenylene (PPP) chains and subsequent narrow graphene ribbons starting from 4,4″-dibromo-p-terphenyl molecular precursors deposited at the silver surface. By combing scanning tunneling microscopy (STM) imaging and density functional theory (DFT) simulations, we describe the molecular morphology and organization at different steps of the growth process and we discuss the stability and conversion of the encountered species on the basis of calculated thermodynamic quantities. Unlike the case of gold, at the debromination step we observe the appearance of organometallic molecules and chains, which can be explained by their negative formation energy in the presence of a silver adatom reservoir. At the dehydrogenation temperature, the persistence of intercalated Br atoms hinders the formation of well-structured graphene ribbons, which are instead observed on gold, leading only to a partial lateral coupling of the PPP chains. We numerically derive very different activation energies for Br desorption from the Ag and Au surfaces, thereby confirming the importance of this process in defining the kinetics of the formation of molecular chains and graphene ribbons on different metal surfaces.
This
work is focused on the structural control of graphene nanoribbons
(GNRs) and intermediate polymeric wires [poly(p-phenylene),
PPP] during their thermoactivated bottom-up synthesis from room temperature
to 480 °C. The first step of the synthesis relies on the Ullmann
coupling between 4,4″-dibromo-p-terphenyl
(DBTP) molecular precursor units that lead to PPP wires in the temperature
range between 170 and 200 °C. Thermal annealing at higher temperatures
(360–480 °C) triggers the PPP lateral fusion to yield
GNRs. We systematically studied the deposition of DBTP on the three
main low-Miller-index gold surfaces, i.e., Au(100), Au(110), and Au(111),
to elucidate the templating effects of such surfaces due to the pronounced
anisotropy of their reconstructions via a multitechnique approach
(scanning tunneling microscopy, X-ray photoelectron spectroscopy,
and low-energy electron diffraction). The best results are obtained
on Au(100) in terms of (i) GNR length (up to 80 nm), (ii) narrow width
distribution (only 6- and 9-GNRs), (iii) long-range order, and (iv)
excellent alignment along the reconstruction. Au(111) produces longer
GNRs than Au(100) but poorer molecular ordering. Concerning PPP wires,
they are stable within a wide temperature range and exhibit an interesting
improvement of the long-range order with increasing temperature on
Au(100), but the best overall organization and unidirectionality have
been achieved on Au(110).
Prostate malignancy represents the second leading cause
of cancer-specific
death among the male population worldwide. Herein, enhanced intracellular
magnetic fluid hyperthermia is applied in vitro to
treat prostate cancer (PCa) cells with minimum invasiveness and toxicity
and highly specific targeting. We designed and optimized novel shape-anisotropic
magnetic core–shell–shell nanoparticles (i.e., trimagnetic
nanoparticles - TMNPs) with significant magnetothermal conversion
following an exchange coupling effect to an external alternating magnetic
field (AMF). The functional properties of the best candidate in terms
of heating efficiency (i.e., Fe3O4@Mn0.5Zn0.5Fe2O4@CoFe2O4) were exploited following surface decoration with PCa cell
membranes (CM) and/or LN1 cell-penetrating peptide (CPP). We demonstrated
that the combination of biomimetic dual CM-CPP targeting and AMF responsiveness
significantly induces caspase 9-mediated apoptosis of PCa cells. Furthermore,
a downregulation of the cell cycle progression markers and a decrease
of the migration rate in surviving cells were observed in response
to the TMNP-assisted magnetic hyperthermia, suggesting a reduction
in cancer cell aggressiveness.
All‐inorganic perovskites are a promising solution for the fabrication of thermally stable perovskite solar cells (PSCs) with remarkable performances. However, a high annealing temperature is required for the stabilization of the photoactive phase of CsPbI3, which represents a limiting factor for their potential scaling‐up and manufacturing at industrial scale. This work demonstrates a new process for the stabilization of CsPbI3‐xBrx perovskite at lower annealing temperature of 180°, based on a rational halogen substitution enabled by the introduction of dimethylammonium (DMA) additives. Bromide inclusion favors indeed the conversion from the intermediate phases to CsPbI3‐xBrx. Standard mesoscopic solar cells prepared with this approach achieve a power conversion efficiency (PCE) of 14.86%, with reduced voltage losses and increased fill factor (FF) compared to the reference device. Moreover, this work proves that a rational substitution of the halide in the DMA salt is also beneficial for the devices annealed at higher temperature, achieving an encouraging PCE of 16.23%. By reducing the processing temperature, this new method widens the range of applications of all‐inorganic PSCs toward temperature‐sensitive materials and industrial applications.This article is protected by copyright. All rights reserved.
Hydrophobic coatings have the ability to promote dropwise condensation on metal surfaces. In this work, reduced graphene oxide coatings are fabricated by dip coating copper substrates into a graphene oxide colloidal suspension, followed by thermal reduction. The formation of reduced graphene oxide is demonstrated by Raman and X‐ray photoelectron spectroscopy characterizations, while scanning electron microscopy, atomic force microscopy and dynamic water contact angle analyses are employed to verify the morphology and the wettability of the coatings. The prepared coatings demonstrate applicability in the promotion of dropwise condensation of pure steam, with an 8‐fold enhancement of the heat transfer coefficient compared to film‐wise condensation. In addition, durability of the reduced graphene oxide coatings of more than 100 hours in the tested condition is reported.
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