Search Results (26)

The competitive retention of pollutants in water tables determines their environmental fate and guides routes for their removal. To distinguish the fine differences in competitive binding at zeolite adsorption centers, a group of neonicotinoid pesticides is compared, relying on theoretical (energy of adsorption, orientation, charge distribution) and experimental (spectroscopic and thermogravimetric) analyses for quick, inexpensive, and reliable screening. The MOPAC/QuantumEspresso platform was used for theoretical calculation, indicating close adsorption energy values for acetamiprid and imidacloprid (−2.2 eV), with thiamethoxam having a lower binding energy of −1.7 eV. FTIR analysis confirmed hydrogen bonding, among different dipole-dipole interactions, as the dominant adsorption mechanism. Due to their comparable binding energies, when the mixture of all three pesticides is examined, comparative adsorption capacities are evident at low concentrations, owing to the excellent adsorption performance of the FAU zeotype. At higher concentrations, competition for adsorption centers occurs, with the expected thiamethoxam binding being diminished due to the lower bonding energy. The catalytic impact of zeolite on the thermal degradation of pesticides is evidenced through TG analysis, confirming the adsorption capacities found by UV/VIS and HPLC/UV measurements. Detailed analysis of spectroscopic results in conjunction with theoretical calculation, thermal profiles, and UV detection offers a comprehensive understanding of neonicotinoids’ adsorption and can help with the design of future adsorbents. Full article

We studied the interaction between a Cu-doped graphene layer and a CO₂ molecule, using DFT, ab initio calculations, and the pseudopotential formalism. We used the Quantum ESPRESSO code package, with the PBE XC functional expression and the semiempirical Grimme’s DFT-D3 Van der Waals correction. We found that the Cu atom, being absorbed in a C vacancy on the graphene surface, has a catalytic effect on the absorption of CO₂ in said surface. The Van der Waals correction calculations showed that the CO₂ is physisorbed, with an adsorption energy of −0.1786 eV. Our results are congruent with previously published results. The Cu-doped graphene surface could be suitable for the development of a CO₂ sensor. Full article

In this work, a density functional theory (DFT) with Hubbard correction (U) approaches implemented through the Quantum ESPRESSO code is utilized to investigate the effects of fluorine (F) doping on the structural, electronic, and optical properties of rutile TiO₂. Rutile TiO₂ is a promising material for renewable energy production and environmental remediation, but its wide bandgap limits its application to the UV spectrum, which is narrow and expensive. To extend the absorption edge of TiO₂ into the visible light range, different concentrations of F were substituted at oxygen atom sites. The structural analysis reveals that the lattice constants and bond lengths of TiO₂ increased with F concentrations. Ab initio molecular dynamics simulations (AIMD) at 1000 K confirm that both pristine and F-doped rutile TiO₂ maintains structural integrity, indicating excellent thermal stability essential for high-temperature photocatalytic applications. Band structure calculations show that pure rutile TiO₂ has a bandgap of 3.0 eV, which increases as the F concentration rises, with the 0.25 F-doped structures exhibiting an even larger bandgap, preventing it from responding to visible light. The absorption edge of doped TiO₂ shifts towards the visible region, as shown by the imaginary part of the dielectric function. This research provides valuable insights for experimentalists, helping them understand how varying F concentrations influence the properties of rutile TiO₂ for photocatalytic applications. Full article

The electronic and phonon bands of Skaergaardite are investigated using density functional theory (DFT) as implemented in Quantum ESPRESSO. Skaergaardite is a copper palladium mineral (CuPd) found in the Skaergaard intrusion with a CsCl-type (B2) structure. Due to its porous structure, it presents a large surface area available for interactions, which makes it a promising catalyst. The PBE-GGA functional with a Hubbard-like localized term (DFT+U) is combined with ultrasoft and norm-conserving pseudopotentials, and a conventional approach with a dense Monkhorst–Pack grid of k-points 12 × 12 × 12 is applied. The electronic valence bands are mainly constituted by 3d orbitals of Cu and 4d orbitals of Pd and a pseudo-gap can be recognized. With respect to DFT, DFT+U causes a general downward shift in the valence band. The acoustic and optical phonon branches are separated by a few cm⁻¹ gap at about 150 cm⁻¹ and show a density of state curve typical of ordered materials. These results highlight the reliability of DFT+U in studying bimetallic systems with scarce experimental benchmarks, offering insights into the behavior of Skaergaardite and its potential applications in material science such as reduction reactions and hydrogen storage. Full article

When combined with ceramics, ternary carbides, nitrides, and borides form a class of materials known as MAX phases. These materials exhibit a multilayer hexagonal structure and are very strong, damage tolerant, and thermally stable. Further, they have a low thermal expansion and exhibit outstanding resistance to corrosion and oxidation. However, despite the numerous MAX phases that have been identified, the search for better MAX phases is ongoing, including the recently discovered Zr₃InC₂ and Hf₃InC₂. The properties of MAX phases are still being tailored in order to lower their ductility. This study investigated Ti₃AlC₂ alloyed with nitrogen, gallium, hafnium, and zirconium with the aim of achieving better mechanical and thermal performances. Density functional theory within Quantum Espresso module was used in the computations. The Perdew–Burke–Ernzerhof generalised gradient approximation functionals were utilised. (ZrHf)₄AlN₃ exhibited an enhanced bulk and Young’s moduli, entropy, specific heat, and melting temperature. The best thermal conductivity was observed in the case of (ZrHf)₃AlC₂. Further, Ti₃AlC₂ exhibited the highest shear modulus, Debye temperature, and electrical conductivity. These samples can thus form part of the group of MAX phases that are used in areas wherein the above properties are crucial. These include structural components in aerospace and automotive engineering applications, turbine blades, and heat exchanges. However, the samples need to be synthesised and their properties require verification. Full article

Perovskites are currently becoming common in the field of optoelectronics, owing to their promising properties such as electrical, optical, thermoelectric, and electronic. Although mechanical and thermal properties also play a crucial part in the functioning of the optoelectronic devices, they have scarcely been explored. The present work performed an ab initio study of the mechanical and thermal properties of the cubic EuAlO₃ and GdAlO₃ perovskites for the first time using density functional theory. Quantum Espresso and Themo_pw codes were utilized by employing the generalized gradient approximation. Although the results showed that both materials have good mechanical and thermal properties that are ideal for the above–mentioned applications, EuAlO₃ possessed better structural and thermal stability, bulk modulus, Poisson ratio, thermal expansion coefficient, and thermal stress; while GdAlO₃ possessed better Young’s modulus and shear modulus. Moreover, the mechanical properties of the two materials turned out to be much better than those of the common materials for optoelectronic applications, while their thermal properties were comparable to that of sapphire glass. Since this study was computational, an experimental verification of the computed properties of the two materials needs to be carried out before they can be commercialized. Full article

Ranging from the most demanding technical applications to soft, extremely ductile wrapping foil, aluminum is one of the most versatile and reasonably priced metallic materials. These are attributable to the unique blend of features that it provides, together with its alloys, owing to its lightweight, and some of its alloys have higher strengths than that of structural steel. However, it is expected that the demand for aluminum will quadruple within the next 10 years, and as a result, the aerospace industry is increasingly turning to recycled alloys to fulfill its high demand. This study uses the ab initio method, implemented in the quantum espresso code, to examine the influence of pressure on the structural and mechanical properties of cubic silicon carbide alloyed with aluminum (Al) and magnesium (Mg). The study is motivated by the aerospace industry’s growing need for sustainable materials. Some of the carbon atoms were swapped out for Al or Mg or both (co-doping) atoms in order to create the alloys. The results demonstrated that the application of pressure significantly influences both the structural and mechanical properties of the alloys, making them a promising option for the construction of environmentally friendly aircraft components. Full article

The co-production of CO₂ continues to remain the bane of several hydrogen production technologies, including the steam reforming of methane and the dry reforming of methane processes. Efficient utilization of abundant greenhouse gas in the form of methane provides opportunities for the design of an innovative system that will maximize the use of such a raw material in the most environmentally friendly manner. The study of the mechanism of the pyrolysis of methane reactions over molten metals provides promise for improved hydrogen yield and methane conversion with a greater turnover frequency. Catalyst electronic properties computed via Density Functional Theory using the Quantum Espresso code provided data that were built into a database. Using Bismuth as the base metal, active transition metals including Ni, Cu, Pd, Pt, Ag, and Au of different concentrations of 5, 10, 15, and 25% were placed on 96 atoms of the base metal and relaxed to obtain the optimized geometric structures for the catalytic reaction studies. The kinetics of the individual elementary steps of the pyrolysis reaction at preset temperatures over the bi-metals were calculated using the Car-Parinello (CP) method and Nudge Elastic Band (NEB) computations. The collated data of the various pyrolysis of methane reactions over the different bi-metals was used to train machine learning models for the prediction of reaction outcome, catalytic performance, and efficient operating conditions for the pyrolysis of methane over molten metals. The turnover frequency, which is determined using the transition state energies of the fundamental reaction cycles, will be used to simulate the stability of the catalyst. Full article

(TiO₂) is both a natural and artificial compound that is transparent under visible and near-infrared light. However, it could be prepared with other metals, substituting for Ti, thus changing its properties. In this article, we present density functional theory calculations for Ti_(1−x)A_xO₂, where A stands for any of the eight following neutral substitutional impurities, Fe, Ni, Co, Pd, Pt, Cu, Ag and Au, based on the rutile structure of pristine TiO₂. We use a fully unconstrained version of the density functional method with generalized gradient approximation plus the U exchange and correlation, as implemented in the Quantum Espresso free distribution. Within the limitations of a finite-size cell approximation, we report the band structure, energy gaps and absorption spectrum for all these cases. Rather than stressing precise values, we report on two general features: the location of the impurity levels and the general trends of the optical properties in the eight different systems. Our results show that all these substitutional atoms lead to the presence of electronic levels within the pristine gap, and that all of them produce absorptions in the visible and near-infrared ranges of electromagnetic radiation. Such results make these systems interesting for the fabrication of solar cells. Considering the variety of results, Ni and Ag are apparently the most promising substitutional impurities with which to achieve better performance in capturing the solar radiation on the planet’s surface. Full article

The search for biocompatible, non-toxic, and wear-resistant materials for orthopedic implant applications is on the rise. Different materials have been investigated for this purpose, some of which have proved successful. However, one challenge that has proven difficult to overcome is the balance between ductility and hardness of these materials. This study employed ab initio calculations to investigate the structural and mechanical properties of niobium nitride (NbN) alloyed with hafnium, indium, and zirconium, with the aim of improving its hardness. The calculations made use of density function theory within the quantum espresso package’s generalized gradient approximation, with Perdew–Burke–Ernzerhof ultrasoft pseudopotentials in all the calculations. It was found that addition of the three metals led to an improvement in both the shear and Young’s moduli of the alloys compared to those of the NbN. However, both the bulk moduli and the Poisson’s ratios reduced with the introduction of the metals. The Young’s moduli of all the samples were found to be higher than that of bone. The Vickers hardness of the alloys were found to be significantly higher than that of NbN, with that of indium being the highest. The alloys are therefore good for wear-resistant artificial bone implants in ceramic acetabulum, and also in prosthetic heads. Full article

Optical coatings are thin layers of materials applied to optical components in order to modify the transmission, reflection, or polarization properties of light. The common materials used for optical coatings include magnesium fluoride (${\mathrm{M}\mathrm{g}\mathrm{F}}_2$), scandium trifluoride (${\mathrm{S}\mathrm{c}\mathrm{F}}_3$), and aluminum trifluoride (${\mathrm{A}\mathrm{l}\mathrm{F}}_3$), owing to their desirable optical properties, spectral range, and compatibility with substrates. However, each of these materials has its own drawbacks. For instance, ${\mathrm{A}\mathrm{l}\mathrm{F}}_3$ has been found to exhibit limited resistance to attack by chemicals, as well as poor thermal stability, while ${\mathrm{M}\mathrm{g}\mathrm{F}}_2$ has low durability, as well as being hygroscopic. In this study, we undertook ab initio calculations in order to compare the thermal properties of ${\mathrm{A}\mathrm{l}\mathrm{F}}_3$, ${\mathrm{S}\mathrm{c}\mathrm{F}}_3$, ${\mathrm{A}\mathrm{l}}_{0.5}{\mathrm{S}\mathrm{c}}_{0.5}{\mathrm{F}}_3$, and ${\mathrm{I}\mathrm{n}}_{0.5}{\mathrm{S}\mathrm{c}}_{0.5}{\mathrm{F}}_3$ in order to obtain the best material for optical coatings. ${\mathrm{M}\mathrm{g}\mathrm{F}}_2$ was also included in the study as a reference. The calculations used PBE pseudopotentials and the extended generalized gradient approximation within the quantum espresso algorithm. The study demonstrated that the computed results agree with the information found in the literature. ${\mathrm{S}\mathrm{c}\mathrm{F}}_3$ exhibited a negative coefficient of thermal expansion, unlike the other four. Moreover, ${\mathrm{A}\mathrm{l}\mathrm{F}}_3$ was found to be the best candidate for optical coatings that are used in high-power laser systems with high thermal dissipation, due to its superior thermal expansion coefficient as well as its better response to thermal stress. The large variation between the ${\mathrm{c}}_{\mathrm{p}}$ and ${\mathrm{c}}_{\mathrm{v}}$ of ${\mathrm{S}\mathrm{c}\mathrm{F}}_3$ is not desirable. Moreover, due to its negative thermal expansion coefficient, ${\mathrm{S}\mathrm{c}\mathrm{F}}_3$ is not thermally stable. The highest thermal stability was exhibited by ${\mathrm{I}\mathrm{n}}_{0.5}{\mathrm{S}\mathrm{c}}_{0.5}{\mathrm{F}}_3$. Since ${\mathrm{A}\mathrm{l}}_{0.5}{\mathrm{S}\mathrm{c}}_{0.5}{\mathrm{F}}_3$ and ${\mathrm{I}\mathrm{n}}_{0.5}{\mathrm{S}\mathrm{c}}_{0.5}{\mathrm{F}}_3$ have been modeled in this study for the first time, experimental determination of their crystal structures needs to be investigated. Full article

Studying the interaction of inorganic systems with organic ones is a highly important avenue for finding new drugs and treatment methods. Tumor cells show an increased demand for amino acids due to their rapid proliferation; thus, targeting their metabolism is becoming a potential oncological therapeutic strategy. One of the inorganic materials that show antitumor properties is titanium dioxide, while its doping was found to enhance interactions with biological systems. Thus, in this study, we investigated the energy landscape of glutamine (L), an amino acid, on pristine and doped TiO₂ surfaces. We first locally optimized 2D-slab structures of pristine and Au/Ag/Cu-doped anatase (001 and 101 surfaces) and similarly optimized a single molecule of glutamine in vacuum. Next, we placed the pre-optimized glutamine molecule in various orientations and on a variety of locations onto the relaxed substrate surfaces (in vacuum) and performed ab initio relaxations of the molecule on the substrate slabs. We employed the DFT method with a GGA-PBE functional implemented in the Quantum Espresso code. Comparisons of the optimized conformations and electronic structures of the amino acid in vacuum and on the surfaces yield useful insights into various biological processes. Full article

Al–Mg–Si alloys are used in aircraft, train, and car manufacturing industries due to their advantages, which include non-corrosivity, low density, relatively low cost, high thermal and electrical conductivity, formability, and weldability. This study investigates the bulk mechanical properties of Al–Mg–Si alloys and the influence of the Si/Mg ratio on these properties. The Al cell was used as the starting structure, and then nine structures were modeled with varying percentages of aluminium, magnesium, and silicon. Elastic constant calculations were conducted using the stress–strain method as implemented in the quantum espresso code. This study found that the optimum properties obtained were a density of 2.762 g/cm³, a bulk modulus of 83.3 GPa, a shear modulus of 34.4 GPa, a Vickers hardness of 2.79 GPa, a Poisson’s ratio of 0.413, a Pugh’s ratio of 5.42, and a yield strength of 8.38 GPa. The optimum Si/Mg ratio was found to be 4.5 for most of the mechanical properties. The study successfully established that the Si/Mg ratio is a critical factor when dealing with the mechanical properties of the Al–Mg–Si alloys. The alloys with the optimum Si/Mg ratio can be used for industrial applications such as plane skins and mining equipment where these properties are required. Full article

Using first-principle calculations, we investigate the impact of strain on the electronic structures and effective masses of Janus WSTe and MoSTe monolayers. The calculations were performed using the QUANTUM-ESPRESSO package, employing the PBE and HSE06 functionals. Our results demonstrate that strain fundamentally changes the electronic structures of the Janus WSTe and MoSTe monolayers. We observe that deformation causes a shift in the maxima and minima of the valence and conduction bands, respectively. We find that the effective electrons and hole masses of MoSTe and WSTe can be changed by deformation. In addition, the strain’s effect on carrier mobility is also investigated in this work via the deformation potential theory. Full article