High throughput computations of the effective removal of liquified gases by novel perchlorate hybrid material

Abstract The utilization of hybrid materials in separation technology, sorbents, direct air capture (DAC) technology, sensors, adsorbents, and chiral material recognition has increased in the past decade due to the recognized impact of atmospheric pollutants and hazardous industrial gases on climate change. A novel hybrid material, perchlorate hybrid (PClH), has been proposed in this study for the effective sensory detection and trapping of atmospheric pollutants and industrial hazardous gases. The study evaluated the structural properties, adsorption mechanism, electronic sensitivity, and topological analysis of PClH using highly accurate computational methods (M062X-D3BJ/def2-ccpVTZ and DSDPBEP86/def2-ccpVTZ). The computational analysis demonstrated that PClH has considerable adsorption energies and favorable interaction with CO2, NO2, SO2, COCl2, and H2S. PClH is more suitable for detecting liquefiable gases such as COCl2, CO2, and SO2, and can be easily recovered under ambient conditions. Developing such materials can contribute to reducing hazardous gases and pollutants in the atmosphere, leading to a cleaner and safer environment

Surface engineering of non-platinum-based electrocatalysts for sustainable hydrogen production: Encapsulation, doping, and decoration approach

The hydrogen evolution reaction's electrocatalytic reduction of water to molecular hydrogen may one day provide a long-term sustainable source of energy. However, the use of precious platinum catalysts makes it difficult to commercialize. So far, all alternatives to platinum are based on non-precious metals and transition metals. Hence, tuning the catalytic activity of nanomaterials through surface engineering might offer significant advantages. Herein, we step-wisely modulate the surface of all carbon fullerene nanomaterial by encapsulation, doping and decoration with alkali and transition metals to produce a hybrid catalyst which demonstrated excellent hydrogen evolution activity with comparable Gibbs free energy with both experimentally developed and theoretically modelled electrocatalyst. The adsorption of H* intermediate on the doped and decorated metal sites has been investigated in comparison with the pristine C24 fullerene structure. The electronic properties, the density of state (PDOS), reaction-free energy (ΔG) and transition states have all been carefully considered at appropriate theoretical levels. The ΔG of hydrogen adsorption on H@IndecNidopMgencC24 was found to be closer to zero (0.0328 eV) because of the concomitant effect of the encapsulation, doping and decoration with transition metals thus, demonstrating the effectiveness of this approach to tuning catalytic activity. The encapsulated metal enhanced the catalyst surface's conductivity and electronic attributes, leading to improved HER activity. The catalytic HER was also found to follow the Volmer-Tafel pathways, resulting in a lower free energy barrier. Overall, this work demonstrates a simple structure-activity relationship between metallic effects and substrate engineering and could open new dimensions for the development of novel non-platinum-based electrocatalysts.Ministry of Education and Science of the Russian Federation24 month embargo; first published 29 October 2023This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Adsorption mechanism of AsH3 pollutant on metal-functionalized coronene C24H12-X (X = Mg, Al, K) quantum dots

Inorganic arsenic compounds are frequently found to occur naturally or as a result of mining in soils, sediments, and groundwater. Organic arsenic exists mainly in fish, shellfish, and other aquatic life and as a result of this, it may be contaminated in edible consumables such as rice and poorly purified drinking water. Exposure to this toxic gas can cause severe lung and skin cancer as well as other related cancer cases. Therefore, the need to develop more efficient sensing/monitoring devices to signal or detect the presence of excessive accumulation of this gas in our atmosphere is highly demanding. This study has effectively employed quantum mechanical approach, utilizing density functional theory (DFT) to investigate the nanosensing efficacy of metal-decorated coronene quantum dot (QD); (CadecQD, AldecQD, KdecQD, and MgdecQD) surface towards the efficient trapping of AsH3 gas molecule in an attempt to effectively detect the presence of the gas molecule which would help in reducing the health risk imposed by the AsH3. The result obtained from the electronic studies reveals that the engineered molecules interacted more favorably at the gas and water phase than other solvents, owing to their varying calculated adsorption energies (Eads). It was observed that the decoration of potassium and aluminum into the QD surface enhanced the adsorption process of AsH3 gas onto KdecQD and AldecQD surfaces with a comparably moderate level of stability exhibited by the said systems, which is evidently shown by the excellent energy gap (Eg) of 6.9599 eV and 7.3313 eV respectively for the aforementioned surfaces

Investigating the intermolecular interactions in the explicitly solvated complexes of lomustine with water and ethanol

Lomustine is an alkylating chemotherapy drug that is used to treat diverse types of cancer, including brain tumors, Hodgkin's lymphoma, and non-Hodgkin's lymphoma, which works by interfering with the DNA in cancer cells, preventing them from dividing and growing. As such the lipid bilayer of the cell and body fluids provides the environments in which lomustine (lmt) performs its biological function. Chemical reactions involving biological systems occur in the liquid phase, where accurate modeling of the reaction pathways considers the influence of the solvent used. Implicit solvation adequately accounts for these effects but falls short when evaluating solvent-solute interactions. This study aims to explore the structures, thermodynamics, reactivity, UV–vis spectroscopy, energy decomposition analysis, and the interaction energies of lmt with molecules of water and ethanol (n = 1, 2, and 3), using density functional theory (DFT) at the ωB97XD/6–311++G (d, p) level of theory. The thermodynamics results reveal that the polarity of water molecules significantly influences the interaction strength of the studied systems as the interaction observed between lmt with W1, Et1, and Et2 is feasible and spontaneous, compared to others. The stability of the different clusters depends on the intermolecular hydrogen bonds formed between the drug and the polar solvent as explicated by the H-bond interaction distance. Also, the interaction of lmt with each of the solvents causes a slight deformation in the geometry of the lmt, moreover, the reactivity descriptors predicted the interaction of lmt to increase with a corresponding increase in the addition of water molecules

Superconductivity, quantum capacitance, and electronic structure investigation of transition metals (X = Y, Zr, Nb, Mo) encapsulated silicon nanoclusters (Si59X): Intuition from quantum and molecular mechanics

Silicon nanoclusters (SiNCs) have unique structural and electronic properties that make them promising candidates for energy storage devices such as batteries, supercapacitors, and solar cells. This study theoretically investigated the superconducting and capacitance properties of transition metal (TM) doped silicon nanoclusters using density functional theory (DFT) calculations. The electronic and ionic conductivity, as well as the non-linear optic property, of TM-doped silicon nanoclusters herein, were analyzed to determine their potential as capacitor electrodes. The effects of temperature on electronic and ionic conductivity were also studied. The results suggest that TM doping enhances the superconducting and capacitance properties of silicon nanoclusters. The electronic conductivity was found to increase with increasing temperature, while the ionic conductivity showed a nonlinear relationship with temperature. Furthermore, it was observed that the doping of studied certain TM elements, such as Nb and Mo, leads to the formation of metallic states within the HOMO-LUMO energy range, indicating their potential for superconducting behaviour. The HOMO-LUMO analysis also reveals the electronic band structure and the bandgap of TM-doped silicon nanoclusters, showing that the dopants can tune the bandgap, resulting in improved superconductivity capacitance. The NBO analysis reveals the nature of bonding between the dopant atoms and the silicon atoms, indicating that charge transfer between the dopants and the silicon atoms plays a crucial role in enhancing the electronic properties Additionally, the stability of TM-doped silicon nanoclusters was analyzed, and it's found that the doping with TM elements resulted in stable structures. The result strongly suggested that doping with Y, Zr, Nb, and Mo enhances the capacitance at different voltages and conductivity at elevated temperatures especially as the electronic configuration of the d-orbital of the dopant evolves. Overall, this study provides valuable insights into the potential of TM-doped silicon nanoclusters as efficient materials for superconducting and capacitive applications.Ministry of Education and Science of the Russian Federation24 month embargo; first published 04 November 2023This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Molecular Modeling of Cu‑, Ag‑, and Au-Decorated Aluminum Nitride Nanotubes for Hydrogen Storage Application

The stabilities, electronic properties, and reactivities of hydrogen interactions with Cu-, Ag-, and Au-decorated aluminum nanotubes (AlNNT), H2-AlNNT, H2-Ag@AlNNT, H2-Au@AlNN T, and H2-Cu@AlNNT, for efficient hydrogen storage were investigated using density functional theory (DFT) computations at the ωB97XD/def2svp level of theory. The electron shared by H2-Ag@AlNNT, H2-Au@AlNNT, and H2-Cu@AlNNT, as well as the chemical bond created with the adsorbed hydrogen molecule, indicate chemisorption from the electron localization function (ELF) analysis, which is compatible with the adsorption energies obtained. H2-Cu@AlNNT exhibited molecular physisorption with an average hydrogen adsorption energy (Eads) of −0.027 eV, whereas H2-AlNNT, H2-Ag@AlNNT, and H2-Au@AlNNT exhibited chemisorption behavior. The molecular adsorption energies for H2-Ag@AlNNT and H2-Au@AlNNT were, respectively, −0.136 and −0.081 eV. Thus, in comparison to the other H2-adsorbed systems under investigation, the highest obtained adsorption energies were observed for these two decorated nanotube systems, respectively. H2-Ag@AlNNT and H2-Au@AlNNT are, therefore, better when compared to the other studied materials in terms of storage and adsorption of hydrogen molecules. Additionally, the negative value of Eads shows that the stated hydrogen molecule’s adsorption is thermodynamically efficient. Also, in comparison with the Department of Energy (DOE) standard, the calculated wt % values for the studied systems were found to be 6.0 and 5.8 wt % for the AlNNT and metal-decorated systems, respectively. This is quite lower than the recommended standard; however, adsorption of more hydrogen molecules and surface engineering could improve the obtained wt %. The desorption temperature was also found to be within the required range for storage materials, according to DOE. Ab initio molecular dynamics simulation also confirms surface stability. Correspondingly, the NCI analysis reveals that the nature of the connection is linked to van der Waals forces and that the hydrogen molecule interacts well with the adsorbent surfaces. These phenomenal results enshrined probably the noble metal-decorated AlN nanotube materials as efficient reservoir materials for hydrogen storage