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MXenes, a family of two-dimensional (2D) transition metal carbides, have been discovered as exciting candidates for various energy storage and conversion applications, including green hydrogen production by water splitting. Today, these materials mostly remain interesting objects for in-depth fundamental studies and scientific curiosity due to issues related to their preparation and environmental stability, limiting potential industrial applications. This work proposes a simple and inexpensive concept of composite electrodes composed of molybdenum- and titanium-containing MAX phases and MXene as functional materials. The concept is based on the modification of the initial MAX phase by the addition of metallic Ni, tuning Al- and carbon content and synthesis conditions, followed by fluoride-free etching under alkaline conditions. The proposed methodology allows producing a composite electrode with a well-developed 3D porous MAX phase-based structure acting as a support for electrocatalytic species, including MXene, and possessing good mechanical integrity. Electrochemical tests have shown a high electrochemical activity of such electrodes towards the hydrogen evolution reaction (HER), combined with a relatively high areal capacitance (up to 10 F cm-2).
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A two-dimensional (2D) silicene-germanene alloy, siligene (SixGey), a single-phase material, has attracted increased attention due to its two-elemental low-buckled composition and unique physics and chemistry. This 2D material has the potential to address the challenges caused by low electrical conductivity and the environmental instability of corresponding monolayers. Yet, the siligene structure was studied in theory, demonstrating the material's great electrochemical potential for energy storage applications. The synthesis of free-standing siligene remains challenging and therefore hinders the research and its application. Herein we demonstrate nonaqueous electrochemical exfoliation of a few-layer siligene from a Ca1.0Si1.0Ge1.0 Zintl phase precursor. The procedure was conducted in an oxygen-free environment applying a -3.8 V potential. The obtained siligene exhibits a high quality, high uniformity, and excellent crystallinity; the individual flake is within the micrometer lateral size. The 2D SixGey was further explored as an anode material for lithium-ion storage. Two types of anode have been fabricated and integrated into lithium-ion battery cells, namely, (1) siligene-graphene oxide sponges and (2) siligene-multiwalled carbon nanotubes. The as-fabricated batteries both with/without siligene exhibit similar behavior; however there is an increase in the electrochemical characteristics of SiGe-integrated batteries by 10%. The corresponding batteries exhibit a 1145.0 mAh·g-1 specific capacity at 0.1 A·g-1. The SiGe-integrated batteries demonstrate a very low polarization, confirmed by their good stability after 50 working cycles and a decrease in the solid electrolyte interphase level that occurs after the first discharge/charge cycle. We anticipate the growing potential of emerging two-component 2D materials and their great promise for energy storage and beyond.
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The "gold dust defect" (GDD) appears at the surface of ferritic stainless steels (FSS) and degrades their appearance. Previous research showed that this defect might be related to intergranular corrosion and that the addition of aluminium improves surface quality. However, the nature and origin of this defect are not properly understood yet. In this study, we performed detailed electron backscatter diffraction analyses and advanced monochromated electron energy-loss spectroscopy experiments combined with machine-learning analyses in order to extract a wealth of information on the GDD. Our results show that the GDD leads to strong textural, chemical, and microstructural heterogeneities. In particular, the surface of affected samples presents an α-fibre texture which is characteristic of poorly recrystallised FSS. It is associated with a specific microstructure in which elongated grains are separated from the matrix by cracks. The edges of the cracks are rich in chromium oxides and MnCr2O4 spinel. In addition, the surface of the affected samples presents a heterogeneous passive layer, in contrast with the surface of unaffected samples, which shows a thicker and continuous passive layer. The quality of the passive layer is improved with the addition of aluminium, explaining the better resistance to the GDD.
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The conversion of CO2 into desirable multicarbon products via the electrochemical reduction reaction holds promise to achieve a circular carbon economy. Here, we report a strategy in which we modify the surface of bimetallic silver-copper catalyst with aromatic heterocycles such as thiadiazole and triazole derivatives to increase the conversion of CO2 into hydrocarbon molecules. By combining operando Raman and X-ray absorption spectroscopy with electrocatalytic measurements and analysis of the reaction products, we identified that the electron withdrawing nature of functional groups orients the reaction pathway towards the production of C2+ species (ethanol and ethylene) and enhances the reaction rate on the surface of the catalyst by adjusting the electronic state of surface copper atoms. As a result, we achieve a high Faradaic efficiency for the C2+ formation of ≈80% and full-cell energy efficiency of 20.3% with a specific current density of 261.4 mA cm-2 for C2+ products.
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In this study, substochiometric hole-selective molybdenum oxide (MoOx) contacts in crystalline silicon (c-Si) solar cells were investigated by a combination of transmission electron microscopy (TEM) and spatially resolved electron energy-loss spectroscopy (SR-EELS). It was observed that a ≈ 4 nm SiOx interlayer grows at the MoOx/c-Si interface during the evaporation of MoOx over a c-Si substrate. SR-EELS analyses revealed the presence of a 1.5 nm diffused MoOx/indium tin oxide (ITO) interface in both as-deposited and annealed samples. Moreover, the presence of a 1 nm thin layer with a lower oxidation state of Mo was detected at the SiOx/MoOx interface in an as-deposited state, which disappears upon annealing. Overall, it was evident that no hole-blocking interlayer is formed at the MoOx/ITO interface during annealing and homogenization of the MoOx layer takes place during the annealing process. Furthermore, device simulations revealed that efficient hole collection is dependent on MoOx work function and that reduction in the work function of MoOx results in loss of band bending and negatively impacts hole selectivity.
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As nanomaterials are dominating 21st century's scene, multiple functionality in a single (nano)structure is becoming very appealing. Inspired by the Land of the Rising Sun, we designed a bifunctional (gas-sensor/photochromic) nanomaterial, made with TiO2 whose surface was simultaneously decorated with copper and silver (the Cu/Ag molar ratio being 3:1). This nanomaterial outperformed previous state-of-the-art TiO2-based sensors for the detection of acetone, as well as the Cu-TiO2-based photochromic material. It indeed possessed splendid sensitivity toward acetone (detection limit of 100 ppb, 5 times lower than previous state-of-the-art TiO2-based acetone sensors), as well as reduced response/recovery times at very low working temperature, 150 °C, for acetone sensing. Still, the same material showed itself to be able to (reversibly) change in color when stimulated by both UV-A and, most remarkably, visible light. Indeed, the visible-light photochromic performance was almost 3 times faster compared to the standard Cu-TiO2 photochromic material-that is, 4.0 min versus 10.8 min, respectively. It was eventually proposed that the photochromic behavior was triggered by different mechanisms, depending on the light source used.
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We have synthesized quaternary chalcogenide-based misfit nanotubes LnS(Se)-TaS2(Se) (Ln = La, Ce, Nd, and Ho). None of the compounds described here were reported in the literature as a bulk compound. The characterization of these nanotubes, at the atomic level, has been developed via different transmission electron microscopy techniques, including high-resolution scanning transmission electron microscopy, electron diffraction, and electron energy-loss spectroscopy. In particular, quantification at sub-nanometer scale was achieved by acquiring high-quality electron energy-loss spectra at high energy (â¼between 1000 and 2500 eV). Remarkably, the sulfur was found to reside primarily in the distorted rocksalt LnS lattice, while the Se is associated with the hexagonal TaSe2 site. Consequently, these quaternary misfit layered compounds in the form of nanostructures possess a double superstructure of La/Ta and S/Se with the same periodicity. In addition, the interlayer spacing between the layers and the interatomic distances within the layer vary systematically in the nanotubes, showing clear reduction when going from the lightest (La atom) to the heaviest (Ho) atom. Amorphous layers, of different nature, were observed at the surface of the nanotubes. For La-based NTs, the thin external amorphous layer (inferior to 10 nm) can be ascribed to a Se deficiency. Contrarily, for Ho-based NTs, the thick amorphous layer (between 10 and 20 nm) is clearly ascribed to oxidation. All of these findings helped us to understand the atomic structure of these new compounds and nanotubes thereof.
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We propose an innovative, easy-to-implement approach to synthesize aligned large-area single-crystalline graphene flakes by chemical vapor deposition on copper foil. This method doubly takes advantage of residual oxygen present in the gas phase. First, by slightly oxidizing the copper surface, we induce grain boundary pinning in copper and, in consequence, the freezing of the thermal recrystallization process. Subsequent reduction of copper under hydrogen suddenly unlocks the delayed reconstruction, favoring the growth of centimeter-sized copper (111) grains through the mechanism of abnormal grain growth. Second, the oxidation of the copper surface also drastically reduces the nucleation density of graphene. This oxidation/reduction sequence leads to the synthesis of aligned millimeter-sized monolayer graphene domains in epitaxial registry with copper (111). The as-grown graphene flakes are demonstrated to be both single-crystalline and of high quality.
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We present for the first time a nonaqueous sol-gel route to produce ultrasmall (<2 nm) magnetic bimetallic CoPt3 nanoparticles (NPs). The one-pot procedure is carried out at low temperature (180 °C) using benzyl alcohol, acting as both reducing agent and solvent. The highly monodisperse CoPt3 NPs were investigated with innovative advanced X-ray methods (whole powder pattern modeling), HR-STEM, XPS, and SQUID magnetometry. XPS showed Co was mostly in metallic form, but with a very small amount of CoO on the NP surface. The spherical NPs had an ultrasmall diameter of 1.6 nm and could self-assemble in aligned linear chains, or nanobelts, of single NPs. They are superparamagnetic, with blocking temperature of â¼20 K and coercivity at 10 K of 27.9 kA m-1 (â¼350 Oe). However, there is evidence of a second magnetic phase (probably CoO) in the ZFC magnetization curve, which enhances their magnetization values, without significantly affecting their superparamagnetism.
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Misfit layered compounds (MLCs) have generated significant interest in recent years as potential thermoelectric materials. MLC nanotubes could reveal behavior that is entirely different from the bulk material. Recently, new chemical strategies were exploited for the synthesis of nanotubular forms of chalcogenide-based MLCs, which are promising candidates for thermoelectric materials. However, analogous synthesis of oxide-based MLC nanotubes has not been demonstrated until now. Here, we report a chemical strategy for synthesis of cobalt-oxide-based misfit nanotubes. A combination of high-resolution (scanning) transmission electron microscopy (including image simulations), spatially resolved electron energy-loss spectroscopy, electron diffraction, and density functional theory (DFT) calculations is used to discover the formation of a phase within these nanotubes that differs significantly from bulk calcium cobaltite MLCs. Furthermore, DFT calculations show that this phase is semiconducting with a band gap in excess of 1 eV, unlike bulk calcium cobaltite MLCs, which are known to be metallic. Through systematic experiments, we propose a formation mechanism for these nanotubes that could also apply more generally to realizing other oxide-based MLC nanotubes.
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The electron energy-loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) database has been completely rewritten, with an improved design, user interface, and a number of new tools. The database is accessible at https://eelsdb.eu/ and can now be used without registration. The submission process has been streamlined to encourage spectrum submissions and the new design gives greater emphasis on contributors' original work by highlighting their papers. With numerous new filters and a powerful search function, it is now simple to explore the database of several hundred EELS and XAS spectra. Interactive plots allow spectra to be overlaid, facilitating online comparison. An application-programming interface has been created, allowing external tools and software to easily access the information held within the database. In addition to the database itself, users can post and manage job adverts and read the latest news and events regarding the EELS and XAS communities. In accordance with the ongoing drive toward open access data increasingly demanded by funding bodies, the database will facilitate open access data sharing of EELS and XAS spectra.
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Ultrathin Ag2Mo3O10·2H2O nanowires (NWs) were synthesized by soft chemistry under atmospheric pressure from a hybrid organic-inorganic polyoxometalate (CH3NH3)2[Mo7O22] and characterized by powder X-ray diffraction, DSC/TGA analyses, FT-IR and FT-Raman spectroscopies, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Their diameters are a few tens of nanometers and hence much thinner than that found for silver molybdates commonly obtained under hydrothermal conditions. The optical properties of Ag2Mo3O10·2H2O NWs before and after UV irradiation were investigated by UV-vis-NIR diffuse reflectance spectroscopy revealing, in addition to photoreduction of Mo(6+) to Mo(5+) cations, in situ photogeneration of well-dispersed silver Ag(0) nanoparticles on the surface of the NWs. The resulting Ag@Ag2Mo3O10·2H2O heterostructure was confirmed by electron energy-loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS), and Auger spectroscopy. Concomitant reduction of Mo(6+) and Ag(+) cations under UV excitation was discussed on the basis of electronic band structure calculations. The Ag@Ag2Mo3O10·2H2O nanocomposite is an efficient visible-light-driven plasmonic photocatalyst for degradation of Rhodamine B dye in aqueous solution.
