Surface-Enhanced Raman Spectroscopy and Artificial Neural Networks for Detection of MXene Flakes' Surface Terminations.

The properties of MXene flakes, a new class of two-dimensional materials, are strictly determined by their surface termination. The most common termination groups are oxygen-containing (=O or -OH) and fluorine (-F), and their relative ratio is closely related to flake stability and catalytic activity. The surface termination can vary significantly among MXene flakes depending on the preparation route and is commonly determined after flake preparation by using X-ray photoelectron spectroscopy (XPS). In this paper, as an alternative approach, we propose the combination of surface-enhanced Raman spectroscopy (SERS) and artificial neural networks (ANN) for the precise and reliable determination of MXene flakes' (Ti3C2Tx) surface chemistry. Ti3C2Tx flakes were independently prepared by three scientific groups and subsequently measured using three different Raman spectrometers, employing resonant excitation wavelengths. Manual analysis of the SERS spectra did not enable accurate determination of the flake surface termination. However, the combined SERS-ANN approach allowed us to determine the surface termination with a high accuracy. The reliability of the method was verified by using a series of independently prepared samples. We also paid special attention to how the results of the SERS-ANN method are affected by the flake stability and differences in the conditions of flake preparation and Raman measurements. This way, we have developed a universal technique that is independent of the above-mentioned parameters, providing the results with accuracy similar to XPS, but enhanced in terms of analysis time and simplicity.

Rapid and Universal Synthesis of 2D Transition Metal (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W) Sulfides through Oxide Sulfurization in CS2 Vapor.

Transition metal (TM) sulfides belong to the class of 2D materials with a wide application range. Various methods, including solvothermal, hydrothermal, chemical vapor deposition, and quartz ampoule-based approaches, have been employed for the synthesis of TM sulfides. Some of them face limitations due to the low stability of TM sulfides and their susceptibility to oxidation, and others require more sophisticated equipment or complex and rare precursors or are not scalable. In this work, we propose an alternative approach for the synthesis of 2D TM sulfides by sulfurization of corresponding metal oxides in the vapor of CS2 at elevated temperature. Subsequent treatment in liquid nitrogen allows exfoliation of created sulfides to a 2D structure. A proposed approach was successfully applied to nine transition metals: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W. The resulting materials were extensively characterized using various analytical techniques with a focus on their crystalline structure and 2D nature. Our approach offers several advantages including the use of simple precursors (CS2 and metal oxides), universality (in all cases, the sulfides were obtained), equipment simplicity (tube furnace and quartz reactor), short preparation time (3 h), and the ability of morphology and phase tuning (in particular cases) of the created materials by adjusting the temperature. In addition, gram-scale bulk materials can be obtained in the entry-level laboratories using the proposed approach.

Laser-Induced Reactions of 4-Aminobenzenthiol Species Adsorbed on Ag, Au, and Cu Plasmonic Structures Followed by SERS Spectroscopy. The Role of Substrate and Excitation Energy - Surface-Complex Photochemistry and Plasmonic Catalysis.

This study focuses on investigating the laser-induced reactions of various surface complexes of 4-aminobenzenethiol on Ag, Au, and Cu surfaces. By utilizing different excitation wavelengths, the distinct behavior of the molecule species on the plasmonic substrates was observed. Density functional theory (DFT) calculations were employed to establish the significant role of chemical enhancement mechanisms in determining the observed behavior. The interaction between 4-aminobenzenethiol (4-ABT) molecules and plasmonic surfaces led to the formation of surface complexes with absorption bands red-shifted into the visible and near-infrared regions. Photochemical transformations were induced by excitation wavelengths from these regions, with the nature of the transformations varying based on the excitation wavelength and the plasmonic metal. Resonance with the electronic absorption transitions of these complexes amplifies surface-enhanced Raman scattering (SERS), enabling the detailed examination of ongoing processes. A kinetic study on the Ag surface revealed processes governed by both first- and second-order kinetics, attributed to the dimerization process and transformation processes of individual molecules interacting with photons or plasmons. The behavior of the molecules was found to be primarily determined by the position and variability of the band between 1170 and 1190 cm-1, with the former corresponding to molecules in the monomer state and the latter to dimerized molecules. Notably, laser-induced dimerization occurred most rapidly on the Cu surface, followed by Ag, and least on Au. These findings highlight the influence of plasmonic surfaces on molecular behavior and provide insights into the potential applications of laser-induced reactions for surface analysis and manipulation.

Improvement in Abrasive Wear Resistance of Metal Matrix Composites Used for Diamond-Impregnated Tools by Heat Treatment.

This work presents the possibilities of producing a substitute for a commercial matrix material for sintered metal-diamond tools which is characterized by increased tribological properties required in machining natural stones and concrete. In this study, the improvement in wear behavior of sintered pre-alloyed matrix caused by a thermal treatment was investigated. Several mixtures made of commercially available powders were homogenized by ball milling and consolidated at 900 °C using the spark plasma sintering (SPS) method. During cooling down, the specimens were subjected to isothermal holding at 350 or 250 °C for 1 h. After consolidation, all specimens were tested for density and hardness, whereas selected specimens were characterized by scanning electron microscopy (SEM) and flexural strength tests. The specimens made of BDCM50 powder (a mixture of the base and pre-alloyed powders in 50:50 proportion) shows excellent properties including σ0.2 = 1045 MPa in the three-point bending test and HV10 ≈ 380. Resistance to abrasive wear evaluated in both three-body and two-body conditions in the MWT abrasion test was estimated at Ai3=18.1±3.9 µm/20 m and Ai2=95.9±11.8 µm/20 m, respectively. A series of diamond-impregnated specimens (segments) was also produced and tested for wear rate on abrasive concrete. The potential graphitization of the diamond grits was investigated using Raman spectroscopy and X-ray diffraction. As a reference, both the base Fe-Mn-Cu-Sn-C and commercially available Co+20%WC alloy were used to compare selected properties of the investigated materials. It has been proved that heat-treated specimens made of the base mixture modified with pre-alloyed powders are characterized by increased hardness and resistance to abrasive wear. The BDCM50 matrix has a negligible effect on diamond graphitization and shows excellent field performance, which makes it a good potential substitute for replacing Co+20%WC in sintered diamond-impregnated tools.

High-Energy Excimer Annealing of Nanodiamond Layers.

Here, we aimed to achieve exposure of a nanodiamond layer to a high-energy excimer laser. The treatment was realized in high-vacuum conditions. The carbon, in the form of nanodiamonds (NDs), underwent high-temperature changes. The induced changes in carbon form were studied with Raman spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction (XRD) and we searched for the Q-carbon phase in the prepared structure. Surface morphology changes were detected by atomic force microscopy (AFM) and scanning electron microscopy (SEM). NDs were exposed to different laser energy values, from 1600 to 3000 mJ cm-2. Using the AFM and SEM methods, we found that the NDs layer was disrupted with increasing beam energy, to create a fibrous structure resembling Q-carbon fibers. Layered micro-/nano-spheres, representing the role of diamonds, were created at the junction of the fibers. A Q-carbon structure (fibers) consisting of 80% sp3 hybridization was prepared by melting and quenching the nanodiamond film. Higher energy values of the laser beam (2000 and 3000 mJ cm-2), in addition to oxygen bonds, also induced carbide bonds characteristic of Q-carbon. Raman spectroscopy confirmed the presence of a diamond (sp3) phase and a low-intensity graphitic (G) peak occurring in the Q-carbon form samples.

Beyond the Platinum Era─Scalable Preparation and Electrochemical Activation of TaS2 Flakes.

Among 2D materials, transition-metal dichalcogenides (TMDCs) of group 5 metals recently have attracted substantial interest due to their superior electrocatalytic activity toward hydrogen evolution reaction (HER). However, a straightforward and efficient synthesis of the TMDCs which can be easily scaled up is missing. Herein, we report an innovative, simple, and scalable method for tantalum disulfide (TaS2) synthesis, involving CS2 as a sulfurizing agent and Ta2O5 as a metal precursor. The structure of the created TaS2 flakes was analyzed by Raman, XRD, XPS, SEM, and HRTEM techniques. It was demonstrated that a tuning between 1T (metallic) and 3R (semiconductor) TaS2 phases can be accomplished by varying the reaction conditions. The created materials were tested for HER, and the electrocatalytic activity of both phases was significantly enhanced by electrochemical self-activation, up to that comparable with the Pt one. The final values of the Tafel slopes of activated TaS2 were found to be 35 and 43 mV/dec for 3R-TaS2 and 1T-TaS2, respectively, with the corresponding overpotentials of 63 and 109 mV required to reach a current density of 10 mA/cm2. We also investigated the mechanism of flake activation, which can be attributed to the changes in the flake morphology and surface chemistry. Our work provides a scalable and simple synthesis method to produce transition-metal sulfides which could replace the platinum catalyst in water splitting technology.

Chemistry and Production Technology of Hallstatt Period Glass Beads from Bohemia.

The presented study evaluated a set of beads primarily originating from the Hallstatt period (800-400 BC) and uncovered in the region of Bohemia. Utilizing an SEM/EDS method, the chemical composition of the glass samples was determined and their homogeneity measured. Owing to the presence of opaque glass, Raman spectroscopy was applied, enabling the definition of the phases causing the opacity of the glass, as well as its coloring. This article discusses opacifying agents, including the possible ways in which they entered the artefacts. In addition, the techniques used to produce the glass beads are described, for both the single-colored beads, as well as the so-called eye beads that are present in a significant amount in the set. The majority of the beads examined were found to be made of the LMG glass type (low-magnesium soda-lime glass). An unexpected result was the identification of glass with a high content of K2O not corresponding to the mixed alkali type (LMHK), which is frequently discussed in the literature. The glass type in question most likely does not come from the traditional area of glass production: the eastern Mediterranean territory.

Carbon Transformation Induced by High Energy Excimer Treatment.

The main aim of this study was to describe the treatment of carbon sheet with a high-energy excimer laser. The excimer modification changed the surface chemistry and morphology of carbon. The appearance of specific carbon forms and modifications have been detected due to exposure to laser beam fluencies up to 8 J cm-2. High fluence optics was used for dramatic changes in the carbon layer with the possibility of Q-carbon formation; a specific amorphous carbon phase was detected with Raman spectroscopy. The changes in morphology were determined with atomic force microscopy and confirmed with scanning electron microscopy, where the partial formation of the Q-carbon phase was detected. Energy dispersive spectroscopy (EDS) was applied for a detailed study of surface chemistry. The particular shift of functional groups induced on laser-treated areas was determined by X-ray photoelectron spectroscopy. For the first time, high-dose laser exposure successfully induced a specific amorphous carbon phase.

Raman mapping of coal halos induced by uranium mineral radiation.

Raman mapping microspectroscopy was used as an advantageous high spatial resolution method for detailed assessment of the structure of radiation-induced halos in bituminous coal (Upper Paleozoic) with numerous inclusions of uraninite and coffinite. The uranium content in inclusions in the samples studied ranged from 40 to 50 wt%. Raman structural parameters such as full width at half maximum, the positions of the D-band and G-band peaks and their area ratios were calculated, and these correlated well with vitrinite reflectance. Using linear profiles across the entire halos, changes in the degree of radiolytic alteration of coal matter caused by ionising radiation resulting from the decay of uranium and its daughter products, were described. Using micro-ATR-FTIR, oxidative radiolytic alteration of coal was identified in halos, with oxidisation to alcohols, ketones and carboxyl groups, which were then converted to COO- ions bound to the cations present, including UO22+. From our data, we conclude that the conversion of the original coal to a type of anthracite occurred during the process of CH and CC cleavage, dehydroaromatisation of naphthenic rings and oxidation resulting in the transformation of aliphatic structures into aromatic clusters. Generally, radiolytic alteration increased the structural organisation of coal. Monte Carlo simulations of the observed radiation alteration by the ionising energy loss and non-ionising energy loss were performed.

Plasmon-assisted grafting of anisotropic nanoparticles - spatially selective surface modification and the creation of amphiphilic SERS nanoprobes.

Amphiphilic nanoparticles (NPs) with a spatially selective distribution of grafted functional groups have great potential in the field of sensing, advanced imaging, and therapy due to their unique surface properties. The main techniques for the spatially selective functionalization of NPs utilize the surface-assisted approaches, which significantly restrict their production throughput. In this work, we propose an alternative plasmon-based route for the spatially selective grafting of anisotropic gold nanorods (AuNRs) using iodonium and diazonium salts. Utilization of longer laser wavelengths leads to the excitation of longitudinal plasmon resonances on AuNR tips, plasmon-assisted homolysis of the C-I bond in iodonium salts and the formation of aryl radicals, which are further grafted to the tips of AuNRs. The sides of AuNRs were subsequently decorated through spontaneous diazonium surface grafting. As a result, the AuNRs with spatially separated functional groups were prepared in a versatile way, primarily in solution and without the need for a sophisticated technique of NP immobilization or surface screening. The versatility of the proposed approach was proved on three kinds of AuNRs with different architectures and wavelength positions of plasmon absorption bands. Moreover, the applicability of the prepared amphiphilic AuNRs was shown by efficient trapping and SERS sensing of amphiphilic biomolecules.

Chemical characterization of mountain forest soils: impact of long-term atmospheric deposition loadings (Czech-Polish-German border region).

The composition of lipids in soil offers clues to soil degradation processes due their persistency and selectivity in soil, and close relation to long-term processes in the ecosystem, thanks to their role in cell membranes of organisms. Organic solvent-extractable compounds were recovered from soils collected at two sites differing in the degree of forest damage. Gas chromatography/mass spectroscopy and Fourier transform infrared spectroscopy were applied in order to characterize solvent-extractable lipids. Raman spectroscopy was also applied as it provides distinct advantages for determining the structural order of carbonaceous materials. The organic matter measurement techniques were combined with an established simultaneous multi-element measurement technique. Variations in individual soil horizons from the sites were reflected in the crystallinity of epicuticular waxes, presence of long-chain aliphatic hydrocarbons, concentrations of n-alkanes, saturated and unsaturated fatty acids, dicarboxylic acids, and in the content of aromatic structures, hydroxyl, ester, and carboxylic acid groups. The results are explained by differently transformed organic matter. The concentrations of elements in the soils were also affected by atmospheric depositions, including higher accumulations of arsenic and antimony, and lower contents of natural nutrients. These data have potential to be used as sensitive biogenic indicators of ecosystem damage by long-term atmospheric depositions.

Characterization of Eocene fossil resin from Moravia, Czech Republic: Insights into macromolecular structure.

Two pieces of studlovite - Eocene amber from Studlov (Southeast Moravia, Czech Republic) were investigated. To arrive at a more detailed description, attenuated total reflection Fourier transform infrared spectroscopy, Raman spectroscopy, pyrolysis-gas chromatography/mass spectrometry, and gas chromatography-mass spectrometry were used. Both studlovite samples revealed signs of the same plant source, with higher polymerisation and a higher degree of maturation of the fossilized matter. Despite their close spectral resemblance, they differed in their detailed chemical composition, and in structure. Layering of one of the pieces studied showed how the resin was built and what impact the process had on the chemical composition of the amber. Characterization of the organic matter was completed with an analysis of trace elements in amber samples using scanning electron microscope combined with elemental distribution analysis (SEM/EDAX). The results demonstrated the paleoenvironmental conditions that occurred in the plant during resin exudation following wounding.

Ultrasensitive and reproducible SERS platform of coupled Ag grating with multibranched Au nanoparticles.

Surface-enhanced Raman scattering (SERS) spectroscopy is an extremely sensitive analytical technique that is capable of identifying the vibration signatures of target molecules up to single-molecule sensitivity. In this work, the ultrahigh sensitivity of SERS has been achieved through the immobilization of sharp-edges specific nanoparticles - so-called gold multibranched NPs (AuMs) on the silver grating surface through the biphenyl dithiol. This approach allows combining the extremely high SERS enhancement factor (better than that in the case of AuMs immobilized on the flat Ag film) with perfect reproducibility of Raman signals. The grating was created on the polymer substrate using the excimer laser modification and further metal deposition and has an "active" area 5 × 10 mm2, enabling the macroscale SERS substrate preparation. The wet-chemistry synthesized AuMs were then immobilized on the grating surface and the produced structure allows SERS measurements with a portable Raman spectrophotometer. The prepared structures were checked using the AFM, UV-Vis, and Raman spectroscopy techniques.

Structural changes in amber due to uranium mineralization.

The presence of uranium, with a bulk mass fraction of about 1.5 wt% and radiolytic alterations are a feature of Cenomanian amber from Krizany, at the northeastern edge of the North Bohemian Cretaceous uranium ore district. Pores and microcracks in the amber were filled with a mineral admixture, mainly in the form of Zr-Y-REE enriched uraninite. As a result of radiolytic alterations due to the presence of uranium, structural changes were observed in the Krizany amber in comparison with a reference amber from Nové Strasecí in central Bohemia; this was of similar age and botanical origin but did not contain elevated levels of uranium. Structural changes involved an increase in aromaticity due to dehydroaromatization of aliphatic cyclic hydrocarbons, loss of oxygen functional groups, an increase in the degree of polymerization, crosslinking of CC bonds, formation of a three-dimensional hydrocarbon network in the bulk organic matrix, and carbonization of the organic matrix around the uraninite infill.