Search Results (130)

This study investigates the effects of samarium (Sm) promotion on the catalytic activity of 5 weight percent Ni catalysts for partial oxidation of methane (POM)-based hydrogen production supported on a Si-Al mixed oxide (10SiO₂+90Al₂O₃) system. Several 5% Ni-based catalysts supported on silica–alumina was used to test the POM at 600 °C. Sm additions ranged from 0 to 2 wt.%. Impregnation was used to create these catalysts, which were then calcined at 500 °C and examined using BET, H₂-TPR, XRD, FTIR, TEM, Raman spectroscopy, and TGA methods. Methane conversion (57.85%) and hydrogen yield (56.89%) were greatly increased with an ideal Sm loading of 1 wt.%, indicating increased catalytic activity and stability. According to catalytic tests, 1 wt.% Sm produced high CH₄ conversion and H₂ production, as well as enhanced stability and resistance to carbon deposition. Nitrogen physisorption demonstrated a progressive decrease in pore volume and surface area with the addition of Sm, while maintaining mesoporosity. At moderate Sm loadings, H₂-TPR and XRD analyses showed changes in crystallinity and increased NiO reducibility. Sm incorporation into the support and its impact on the ordering of carbon species were indicated by FTIR and Raman spectra. The optimal conditions to maximize H₂ yield were successfully identified through optimization of the best catalyst, and there was good agreement between the theoretical predictions (87.563%) and actual results (88.39%). This displays how successfully the optimization approach achieves the intended outcome. Overall, this study demonstrates that the performance and durability of Ni-based catalysts for generating syngas through POM are greatly enhanced by the addition of a moderate amount of Sm, particularly 1 wt.%. Full article

In this study, we perform density functional theory (DFT) simulations to investigate the Raman spectra of the bulk and surface phases of β-Li₃PS₄ (LPS) and Li₂S, as well as their interfaces at varying compositional ratios. This analysis is relevant given the widespread application of these materials in Li–S solid-state batteries, where Li₂S functions not only as a cathode material but also as a protective layer for the lithium anode. Understanding the interfacial structure and how compositional variations influence its chemical and mechanical stability is therefore crucial. Our results demonstrate that the LPS/Li₂S interface remains stable regardless of the compositional ratio. However, when the content of both materials is low, the Raman-active vibrational mode associated with the [PS₄]³⁻ tetrahedral cluster dominates the interface spectrum, effectively obscuring the characteristic peaks of Li₂S and other interfacial features. Only when sufficient amounts of both LPS and Li₂S are present does the coupling between their vibrational modes become sufficiently pronounced to alter the Raman profile and reveal distinct interfacial fingerprints. Full article

Vibrational analysis of peptides in solution and the theoretical determination of the effects of the microenvironment on infrared and Raman spectra are of key importance in many fields of chemical interest. In this work, we present a computational study combining static quantum mechanical calculations with ab initio molecular dynamics simulations to investigate the vibrational behavior of three peptide models in both the gas phase and in explicit water, under non-periodic boundary conditions. The vibrational spectra of the main amide bands, namely amide I-III and A, were analyzed using a time–frequency approach based on the wavelet transform, which allows the resolution of transient frequency shifts and mode couplings along the trajectories. This combined approach enabled us to perform a time-resolved vibrational analysis revealing how vibrational frequencies, especially of the C=O and N–H stretching modes, evolve over time due to dynamical microsolvation. These fluctuations modulate vibrational couplings and lead to spectral broadening and frequency shifts that correlate with the local structuring of the solvent. In conclusion, our results highlight how the proposed protocol allows for the direct connection between vibrational modes and local structural changes, providing a link from the spectroscopic observable to the structure, the peptide backbone, and its microenvironment. Full article

This study focused on composites of magnetite magnetic nanoparticles (MNP) and poly(lactic acid) (PLA) prepared via sonochemical synthesis. The evaluation of MNP loadings (2, 5, 10, 15, and 20 wt.%) provided insights into the structural and reactivity properties of the materials. Methods used included XRD, FT-IR and Raman spectroscopy, SEM and TEM microscopy, textural and thermal analysis (TG and DTA), and magnetic property measurements. The agreement between theoretical and experimental MNP loadings was good. XRD patterns showed predominantly MNP and semicrystalline phases, with a minor maghemite phase detected by FT-Raman and magnetic measurements. FT-IR analysis revealed interactions between MNP and PLA, confirmed by thermal analysis showing higher transition temperatures for the composites (145 °C) compared to pure PLA (139 °C). FT-Raman spectra also indicated that PLA helps prevent iron oxide oxidation, enhancing nanoparticle stability. SEM and TEM micrographs showed well-dispersed, spherical nanoparticles with minimal agglomeration, dependent on MNP loading. The nanocomposites exhibited low N₂ adsorption, resulting in low surface area (~2.1 m²/g) and porosity (~0.03 cm³/g). Magnetic analysis indicated that in the 2MNP/PLA sample, MNP were in a superparamagnetic-like regime at 300 K, suggesting good dispersion of 2 wt.% MNP in the PLA matrix. Full article

Spinel ferrites have emerged as fascinating materials, not just for their diverse functionalities, but for the dynamic structural transformations they undergo under varying conditions. These phase transitions, often subtle yet deeply influential, play a pivotal role in tuning their electronic, magnetic, and vibrational properties. At the heart of this complexity lies the versatile arrangement of divalent and trivalent cations between the tetrahedral (A) and octahedral (B) sites, giving rise to a rich spectrum of magnetic interactions, charge dynamics, and lattice responses. This intricate cation interplay makes spinel ferrites a playground for exploring structure–property relationships in advanced functional materials. In this study, we investigated the structural, vibrational, and magnetic properties of Cd ferrite using advanced hybrid functionals (B3LYP, HSE06, and PBE0). Our calculations reveal that the normal spinel phase is the most stable configuration, with minimal energy differences between spin arrangements (~0.005–0.008 eV) and slightly larger differences when including zero-point energy (~0.023 eV). All the investigated structures exhibit a semiconducting nature, with band gaps varying depending on the spin arrangements. The IR and Raman spectra highlight the influence of spin ordering on vibrational modes. The simulations of the Raman spectra demonstrate that both the frequencies and intensities of the Raman peaks strongly depend on the magnetic ordering. The present theoretical study offers a consistent framework for assigning vibrational modes, which may help resolve ambiguities and contribute to a deeper understanding of the vibrational properties of Cd ferrite. These findings provide a robust foundation for further experimental and computational exploration of this material. Full article

Chromium (Cr) is a vital metal utilized in materials physics, healthcare, and various other domains. In this study, we propose an eco-friendly method for separating Cr from potassium chromate (K₂CrO₄) based on photon–phonon resonance absorption theory. Using first-principles density functional theory calculations, we obtained the Raman and infrared spectra of K₂CrO₄ and assigned the vibrational modes to the peaks observed in the experimental spectra. We confirmed that the strongest infrared absorption peak corresponds to the Cr-O bond stretching vibration theoretically located at 931 cm⁻¹. We propose employing a high-power terahertz laser at this resonant frequency for photothermal energy transfer. This approach is expected to enhance the efficiency of separating Cr from K₂CrO₄. Experimental investigations are expected in the future. Full article

Cesium hexafluorosilicate (Cs₂SiF₆, CSF) and potassium hexafluorosilicate (K₂SiF₆, KSF) compounds are suitable hosts for luminescent impurities. In this work, the results of first-principle calculations of the basic properties of both these compounds are discussed and compared with the available experimental and theoretical data. The simulations were performed using the CRYSTAL23 computer code within the linear combination of atomic orbitals (LCAO) method of the density functional theory (DFT) and the advanced hybrid DFT-HF exchange-correlation B1WC functional. A comparative study of the structural, electronic, and elastic properties of the two materials is presented, along with a study of the dependence of properties on external pressure in the range of 0–20 GPa. In particular, the electronic properties with an emphasis on the effective atomic charges (by means of Mulliken analysis) and the chemical bonding properties (by means of crystal orbital overlap population (COOP) analysis) were addressed, with regards to the pressure effects. The structure of the valence bands at 0 and 20 GPa was compared. The vibrational properties of CSF and KSF were calculated, including the simulation of the one-phonon IR and Raman spectra. The calculated Raman spectra exhibit excellent agreement with the experimental ones. The pressure dependences of sound speeds and the Debye temperature are evaluated. Full article

Sulfamic acid (SA) is extensively utilised in industry as a component in the production of flameproof materials, a catalyst for swift and highly efficient synthesis, in dye and pigment manufacturing processes, or as herbicide. Under ambient conditions, this compound exists as a solid in zwitterionc form, undergoing pressure-induced isosymmetric polymorphic phase transition (IPT), starting at approximately 10.0 GPa. In this work, multiple computational approaches were used to predict and describe this transition. While geometry optimisation at an increased pressure using periodic DFT-level calculations have not resulted in the anticipated IPT, the comparison of the experimental and theoretical Raman spectra confirmed this transformation. Thermodynamic calculations enabled the comparison of the stability of the modelled phases and explained the experimental observations. Ab initio molecular dynamics simulations revealed the mechanisms behind the observed transition. This work presents a complex methodology that can be successfully used to predict the IPT of molecular crystals. Full article

The interaction between terahertz (THz) photons and phonons of materials is crucial for the development of THz photonics. In this work, typical two-dimensional (2D) van der Waals (vdW) transition metal chalcogenide (TMD) layers and heterostructures are used in THz time-domain spectroscopy (TDS) measurements, low-wavenumber Raman spectroscopy measurements, calculation of 2D materials’ phonon spectra, and theoretical analysis of thermal responses. The TDS results reveal strong absorption of THz photons in the frequency range of 2.5–10 THz. The low-wavenumber Raman spectra show the phonon vibration characteristics and are used to establish phonon energy bands. We also set up a computational simulation model for thermal responses. The temperature increases and distributions in the individual layers and their heterostructures are calculated, showing that THz photon absorption results in significant increases in temperature and differences in the heterostructures. These give rise to interesting photothermal effects, including the Seebeck effect, resulting in voltages across the heterostructures. These findings provide valuable guidance for the potential optoelectronic application of the 2D vdW heterostructures. Full article

Two new 2-N-phenylamino-(4 or 6)-methyl-3-nitropyridine derivatives were synthesized. Their structures were characterized on the basis of X-ray diffraction, IR, and Raman spectra as well as electron UV-Vis and emission spectra measurements. The experimental results were analyzed in terms of theoretical data in which the quantum chemical DFT and NBO calculations were applied. To elucidate the relaxation pathways of electronically excited states, multiple excitation wavelengths were employed to probe energy dissipation mechanisms in the studied compounds. A systematic analysis was conducted to evaluate how variations in methyl substituent positioning modulate both the structural architecture and photophysical behavior of the isomeric systems. The spectroscopic, structural and theoretical considerations allow us to propose the potential technological applications derived from the unique properties of these isomers. Full article

Background: Surface-enhanced Raman spectroscopy (SERS) analysis of urine is a promising liquid biopsy technique for cancer detection. However, its clinical translation is hindered by two major challenges that impact classification efficacy. First, the SERS signal of urine is confounded by fluctuations induced by physiological differences in urine composition such as pH and dilution. Second, the molecular origin of the SERS signal of urine is incompletely understood, limiting the interpretability of machine learning classifiers in terms of specific biochemical markers. Methods: In this pilot study, we analyzed urine samples from breast cancer patients (n = 18) and control subjects (n = 10) at three pH levels (5, 7, and 9). Additionally, we analyzed simulated urine mixtures consisting of uric acid, hypoxanthine, xanthine, and creatinine in physiological concentrations to explain the variation in the SERS spectra at different pH values. Results: Urine at pH 9 yielded the most detailed spectral features. The SERS spectral pattern under alkaline pH reflected greater contributions from hypoxanthine, uric acid, and creatinine, while xanthine contributions diminished due to competitive interactions at the SERS substrate surface. Normalizing SERS signals to the creatinine band at 1420 cm⁻¹ effectively mitigated the confounding effects of urine dilution. Conclusions: Optimizing the pH to 9 and normalizing to creatinine significantly enhances the interpretability and accuracy of SERS-based urine analysis for cancer detection. These findings offer important theoretical and practical advancements for the development of SERS-based liquid biopsy tools for cancer detection. Full article

The narrow bandgap InN material, with exceptional physical properties, has recently gained considerable attention, encouraging many scientists/engineers to design infrared photodetectors, light-emitting diodes, laser diodes, solar cells, and high-power electronic devices. The InN/Sapphire samples of different film thicknesses that we have used in our methodical experimental and theoretical studies are grown by plasma-assisted molecular-beam epitaxy. Hall effect measurements on these samples have revealed high-electron-charge carrier concentration, η. The preparation of InN epifilms is quite sensitive to the growth temperature T, plasma power, N/In ratio, and pressure, P. Due to the reduced distance between N atoms at a higher P, one expects the N-flow kinetics, diffusion, surface components, and scattering rates to change in the growth chamber which might impact the quality of InN films. We believe that the ionized N, rather than molecular, or neutral species are responsible for controlling the growth of InN/Sapphire epifilms. Temperature- and power-dependent photoluminescence measurements are performed, validating the bandgap variation (~0.60–0.80 eV) of all the samples. High-resolution X-ray diffraction studies have indicated that the increase in growth temperature caused the perceived narrow peaks in the X-ray-rocking curves, leading to better-quality films with well-ordered crystalline structures. Careful simulations of the infrared reflectivity spectra provided values of η and mobility μ, in good accordance with the Hall measurements. Our first-order Raman scattering spectroscopy study has not only identified the accurate phonon values of InN samples but also revealed the low-frequency longitudinal optical phonon plasmon-coupled mode in excellent agreement with theoretical calculations. Full article

A surface-enhanced Raman scattering (SERS) study of diquat (DQ) on silver and copper electrodes is presented in this work in order to complete previous studies on the SERS of DQ on metal nanoparticles. We supported the experimental results with theoretical calculations of different species of DQ, analyzing the most important molecular differences and their corresponding Raman spectra. DQ SERS spectra on Ag and Cu electrodes were obtained at different excitation wavelengths. An analysis of the SERS spectra revealed that at more positive electrode potentials, the interaction of DQ with the metal formed a charge-transfer complex via the chloride anion previously adsorbed on the surface; additionally, at more negative potentials, other species of diquat, such as DQ²⁺, could be directly adsorbed on the metal’s surface. Finally, we detected new SERS bands corresponding to DQ at negative electrode potentials that were sensitive to the excitation wavelength, suggesting that lateral interactions between radical cation species on the electrode surface lead to intramolecular dimerization and a possible multilayer of the adsorbate. Full article

Four differently shaped monolithic catalyst supports were made using 3D printing technology. Two catalytically active mixed oxides, MnFeO_x and MnCuO_x, were applied to the monolithic supports using the impregnation technique. Catalysts were characterized using an adhesion test, field emission scanning electron microscopy, X-ray diffraction, and Raman spectroscopy in a manner similar to the density functional theory model. Excellent mechanical stability of the catalyst layer was obtained, with catalyst mass loss under 2% after 30 min of ultrasound exposure. SEM analysis revealed that the catalyst layer was rough but homogeneous in appearance and ~6 μm thick. The presence of double oxides—FeMnO₃ and CuMn₂O₄—as well as single oxides of Mn, Fe, and Cu was established via XRD and Raman spectroscopy. Additional theoretical calculations of Raman spectra for FeMnO₃ and CuMn₂O₄ were performed in order to aid in the interpretation of Raman spectra. The catalytic activity of the prepared catalysts for the catalytic oxidation of a gaseous mixture of benzene, toluene, ethylbenzene, and o-xylene (BTEX) was investigated. The monolithic support with the most complex shape and, consequently, the greatest surface area proved to enable the highest efficiency, while both catalysts performed well having similar conversions. Full article

Three novel multicomponent crystals of trimethylglycine with 2-cyanoguanidine, guanidinium and aminoguanidinium chlorides are synthesized and structurally characterized. All three crystal packings are based on the supramolecular synthon formed by two N–H groups of the guanidine species and carboxylate group of trimethylglycine (graph set notation R²₂(8)). Its enthalpy is about 50 kJ/mol. The three-dimensional structure of crystals is stabilized by intermolecular interactions of various types. The energy of C–H∙∙∙X⁻ interactions, where X = O, Cl, reaches 16 kJ/mol due to the acidic nature of methyl hydrogens. The possible structure of the trimethylglycine–urea–2H₂O complex is discussed. Its theoretical metric and spectroscopic parameters are in reasonable agreement with the available literature data on the deep eutectic solvent trimethylglycine–urea. Full article