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The conversion of CO2 into valuable chemicals remains a significant challenge for achieving environmental sustainability, primarily due to the stability of the CO2 molecule. This necessitates the development of efficient and ecofriendly catalysts. In recent years, frustrated Lewis pairs (FLPs) have shown promise for CO2 utilization. In this study, we introduce α‐aminodiboronic acid (DBA), a novel trifunctional aminoboronic acid, as an intramolecular FLP for converting CO2 into cyclic carbonate and formic acid. Using density functional theory (DFT) calculations, we explored the reaction mechanism and investigated DBA's electronic structure through molecular electrostatic potential surface (MESP) and natural bond orbital (NBO) analyses. Our results reveal that one −B (OH)2 group induces an unusual state of frustration in the molecule due to charge transfer from the nitrogen atom's lone pair to the π* orbitals, enhancing catalytic performance. The additional −B (OH)2 group serves as an anchoring site for reactive species. The epoxide activation energy is reduced by approximately 27 kcal/mol compared to the uncatalyzed reaction, and the reduction of CO2 occurs with a requirement of 26 kcal/mol. The additional −B (OH)2 plays a crucial role in the catalytic mechanism and minimizes the energies of various structures observed in the reaction path. The reaction energetics align with structural analysis observations, marking this study as the first report on single‐molecule trifunctional FLPs for transforming CO2 into valuable chemicals. [ABSTRACT FROM AUTHOR]

Since SrTiO 3 is attractive due to its versatile electronic properties ranging from dielectric to semiconducting behavior, the effect of systematic co-substitution of various A-site cations on the electronic structure and transport properties of oxygen-deficient SrTiO 3- δ bulk ceramics was analyzed. The materials were synthesized by reverse co-precipitation method and densified by spark plasma sintering (SPS) in a vacuum, followed by a post-thermal treatment in a reducing atmosphere (5 % H 2 /Ar). The phase purity was confirmed by X-ray diffraction (XRD), different microstructures were revealed by scanning electron microscopy (SEM), and characterization in terms of electrical conductivity (σ el) and Seebeck coefficient (S) were performed. The largest power factor was obtained with Sr 0.25 Ca 0.25 Na 0.25 La 0.25 TiO 3-δ by maintaining electrical conductivity while increasing the Seebeck coefficient. Density Functional Theory (DFT) calculations were applied to obtain information on band structures, the projected density of states (PDOS), and electron density differences (EDD). Band structures indicated that oxygen deficiency essentially changed the conductive nature of the studied materials by shifting the Fermi level to the conductive zone, while PDOS plots define the role of each element located at the A site. The electronic structure is affected to the greatest extent in the cases when Nd and Pr are present at the A-site. However, the obtained experimental and computational (DFT) results could not completely match and explain all phenomena since understanding the effect of different cations at A-site on oxygen vacancy formation seems to be a challenging task, and therefore, some hypotheses are proposed. This work attempts to understand the role of a particular cation at A-site on the electronic band structure and its relevance to the formation of oxygen vacancies, thereby providing valuable insights for future high-entropy perovskite titanates with improved transport properties. [ABSTRACT FROM AUTHOR]

Bir-MnO2 was synthesized through a hydrothermal method and modified into H-Bir by nitric acid acidification. The mechanism of its action in ozonation was explored by characterization. H-Bir possessed more oxygen vacancies and lower average oxidation state (AOS) than Bir-MnO2. The oxygen vacancies and surface hydroxyl groups are the main active sites of this catalyst. Under the reaction conditions of initial pH=7 , ozone dosage of 7 mg/L , initial pollutant concentration of 10 mg/L , and catalyst dosage of 0.5 g/L for 40 min , the degradation rates of H-Bir catalyzed ozonation of p-nitrobenzoic acid (PNBA) and 4-chlorobenzoic acid (PCBA) reached 82.68% and 85.83%, respectively. Differences in the degradation factors affecting PCBA and PNBA were found in the performance study of H-Bir catalyzed ozonation. The combination of density functional theory (DFT) and catalytic ozonation experiment results revealed the difference between the degradation of PNBA and PCBA in the H-Bir/O3 system. It was deduced that the nitro, chlorine and carboxyl groups were the main reaction sites. Possible degradation pathways for the two pollutants were also proposed. [ABSTRACT FROM AUTHOR]

An eco-friendly adsorbent was prepared by reverse suspension crosslinking method to remove multiple pollutants from aqueous solution. Both raw materials, derived from humus (HS) and chitosan (CS), are biodegradable and low-cost natural biopolymers. After combining HS with CS, the adsorption capacity was significantly improved due to compensation effects between the two components. HS/CS exhibited the features of amphoteric adsorption through pH adjustment, enabling it to adsorb not only anionic pollutants (Methyl Orange (MO) and Cr(VI)), but also cationic ones (Methylene Blue (MB) and Pb(II)). The adsorption capacities were approximately 242 mg/g, 69 mg/g, 188 mg/g and 57 mg/g for MO, Cr(VI), MB and Pb(II), respectively. HS/CS showed a slight preference for MO in MO/Cr(VI) co-adsorption system, whereas strong selectivity for MB over Pb(II) in MB/Pb(II) system under acidic condition (pH<3.0). This selective behavior would allow for potential applications in separating MB/Pb(II) effluents and selectively recycling Pb(II) in acidic environment. The isothermal and kinetic adsorption behaviors followed Langmuir model and pseudo-second-order model, respectively. The density functional theory (DFT) confirmed that the interaction between metal ions and adsorbents was primarily attributed to chelation and electrostatic adsorption, owing to nitric and oxygenic functional groups. Whereas, the adsorption mechanisms for dyes were involved in electrostatic attraction, H-bond and π–π bond, due to available hydrogen, oxygen, nitrogen atoms and aromatic groups on the surface of adsorbent and adsorbates. The adsorbent could be efficiently regenerated and retained over 90% of its adsorption capacity after five cycles, which has a potential for practical applications in water treatment. [Display omitted] [ABSTRACT FROM AUTHOR]

Developing sustainable and efficient catalysts for ammonia synthesis from atmospheric molecular N2 under ambient conditions presents a significant 21st‐century challenge. Two‐dimensional heterostructures, particularly single‐atom catalysts (SACs) supported on two‐dimensional materials, have emerged as a promising avenue due to their remarkable catalytic activity and selectivity. Electrides, characterized by an abundance of free electrons and high surface activity, have attracted substantial attention in this context. Through density functional theory (DFT) calculations, this study proposes electride‐graphene heterostructures (EGHS) as catalysts to effectively regulate charge distribution at the catalytic center, facilitating the optimization of catalytic performance. The EGHS model addresses challenges related to excessive adsorbate binding, mitigating electron transfer compared to electride monolayer adsorption. This novel approach utilizes heterogeneous heterostructures to finely tune the catalytic site, optimizing electron input for enhanced catalysis. Based on the optimized charge transfer for N2 activation, the Cr‐doped EGHS (Cr@EGHS) exhibits a promising performance in the nitrogen reduction reaction, leading to, a relatively low limiting potential of −0.85 V and high selectivity. The hypothesis charge transfer depend on N2 activation is further supported by modulating the distance between component layers of heterostructure. These findings contribute to design principles for 2D heterostructure catalysts and offer a reference for experimental synthesis. [ABSTRACT FROM AUTHOR]

Metal‐organic frameworks (MOFs) are porous materials with numerous chemical and structural possibilities. Due to their ease of modification, well‐organized structure, and diverse guest molecule chemistry, MOFs are ideal platforms for uncovering improved functional material design characteristics. Quantitative analysis of glucose is crucial, especially in some food products, for quality control as well as evaluation of the glucose levels helps diagnose and treat diabetes. Recent glucose sensing devices have relied heavily on MOFs and other nanomaterials to enable user‐friendly and safe non‐invasive sensing methods. Nevertheless, the conventional synthesis methods involve multi‐day reactions, cooling, and depressurization processes. This study demonstrates the unprecedented high‐power laser‐induced rapid synthesis (LIRS) of Ni‐based MOF nanospheres with interconnected nano‐rods and noncentrosymmetric primitive triclinic crystalline structure, highlighting their multifunctional usage in sensing and gas sorption applications. Ab initio simulations show excellent agreement with the experimental physical and gas sorption properties. Furthermore, the Ni‐MOF‐based biosensor accurately measures glucose real‐life beverage samples, yielding promising glucose detection biosensor results with a low limit of the detection (LOD) of 13.96 µM and high sensitivity of 120.606 µA mM−1 cm−2. [ABSTRACT FROM AUTHOR]

FeNiOOH is regarded as the most stable active species in the oxygen evolution reaction (OER), but the high oxidation energy of NiOOH poses a challenge to directly synthesize FeNiOOH as a real OER catalyst. Herein, an anion‐mediated kinetically controlled strategy is proposed, coupled with cation‐induced geometric topology modulation, to directly synthesis FeNiOOH with ultra‐thin, densely packed nanosheet architectures. Specifically, the Cl−‐mediated in situ generation of hypochlorous acid promotes the direct formation of NiFeOOH. Concurrently, high‐valence competitive Ru3+ mitigate electrostatic repulsion, fostering a compact and densely packed assembly of Ru/FeNiOOH nanosheet branches. Furthermore, the intrinsic electron‐capturing ability of FeOOH, in synergy with the stabilizing effect of doped Ru atoms, further promote the formation and stabilization high‐valence NiOOH. Consequently, the hierarchical Ru/FeNiOOH@NiPOx nanoarray catalyst displays exceptional OER performance, with an overpotential of 172 mV at 10 mA cm−2 and outstanding stability. This study provides a novel strategy to directly construct a real catalyst. [ABSTRACT FROM AUTHOR]

Given the diminishing reserves of fossil fuels, the development of renewable alternative energy sources is of global importance. Photocatalytic hydrogen (H 2) evolution stands out as a promising and cost-effective method to harness sunlight for producing carbon-free H 2 fuel. Recently, two-dimensional (2D) covalent organic frameworks (COFs) have garnered considerable research interest in photocatalysis on account of their exceptional surface area and predictable assembly of diverse molecules with adjustable electronic properties. Herein, six 2D COFs are constructed by topologically assembling phosphorus-alkynyl functional moieties and benzene-based building units, including benzene (COF-1), triazine (COF-2), heptazine (COF-3), triphenyl-benzene (COF-4), triphenyl-triazine (COF-5), and triphenyl-heptazine (COF-6), employing first-principles calculations. Our computational results illustrate that the variation of benzene-based building units significantly regulates the electronic structures of COFs, all of which possess semiconductor properties with tunable bandgaps spanning from 1.56 to 2.56 eV. Of particular importance, COF-1, COF-2, COF-4, COF-5, and COF-6 can spontaneously stimulate the hydrogen evolution reaction (HER) under their own light-induced bias without the need for sacrificial agents and co-catalysts. Among them, COF-4 and COF-5 show the best HER activity without light-induced bias, with ΔG values of 0.02 and −0.01 eV, respectively, whose excellent photocatalytic performance can be ascribed to their appropriate electronic band structures, pronounced optical absorption, and low work functions. This finding offers profound insights for exploring other highly efficient HER photocatalysts. Synopsis: Phosphorus-alkynyl COFs (COF-1, 2, 4, 5, 6), featuring varied benzene-based units, can spontaneously initiate HER under light-induced bias, eliminating the reliance on sacrificial agents or co-catalysts. [Display omitted] • The 2D COFs are constructed by phosphorus-alkynyl moieties and benzene-based units. • Varying the benzene-based units notably modulates the electronic structures of COFs. • COF-1, 2, 4, 5, 6 can spontaneously initiate HER under their own light-induced bias. • COF-4, 5 show superior HER activity in the absence of light-induced bias. [ABSTRACT FROM AUTHOR]

Hydrogen production using the photocatalysis approach is considered a feasible option for achieving a sustainable future. In this work, we conducted a comprehensive investigation into the hydrogen evolution reaction (HER) performance of the XSeI monolayers (where X represents either Sb or Bi) using density functional theory (DFT) calculations. We simulate and optimize the structural properties of the 2D XSeI Janus monolayers in its H-phase, ensuring stability through cohesive energy and phonon analysis. For SbSeI, the computed cohesive energy is − 2.06 eV, and for BiSeI, it is − 2.14 eV. Subsequently, we explored the electronic characteristics, including density of states (DOS) and electronic band structure. The various machine learning (ML) models were integrated into our approach for predicting the band gap of Janus monolayers. Employing DFT calculations, we systematically examined the HER activity of the XSeI monolayers, assessing its responsiveness to doping, with a particular focus on Pt and Pd atoms. The calculated Gibbs free energy for Pd–SbSeI and Pd–BiSeI is 0.33 eV while for Pt–SbSeI and Pt–BiSeI, it is − 0.23 eV and − 0.21 eV, respectively. The study not only contributes insights into the fundamental electronic and catalytic properties of the XSeI monolayers but also investigate the potential for enhancing its hydrogen evolution performance through strategic doping strategies. The study demonstrates the stability and electronic properties of XSeI Janus monolayers using DFT calculations. Employing the random forest model, we predict the band gap at the HSE level for both Janus monolayers. We explored HER activity, finding promising results with Pt and Pd atom doping, especially for Pt-doped XSeI. [Display omitted] • We focused on pristine and doped XSeI (X = Sb, Bi) Janus monolayers in their H-phase. • ML models have the capability to predict the band gap of any Janus monolayer. • The examination of hydrogen evolution reaction (HER) activity within both pristine and doped Janus monolayers XSeI. • To explores the possibilities of improving their hydrogen evolution performance via strategic doping. [ABSTRACT FROM AUTHOR]

Bisphenol A is an oil‐derived, large market volume chemical with a wide spectrum of applications in plastics, adhesives, and thermal papers. However, bisphenol A and its derivative are not considered safe due to its endocrine disrupting properties and reproductive toxicity. A nontoxic alternative of bisphenol analogus has been proposed in this study using plant biomass. A study of different DFT‐based QSAR approaches has been done to show the significance of the conceptual DFT‐based selected descriptors with different QSAR models in the prediction of toxicity and to establish meaningful correlations between the molecular structure of the proposed compounds and their toxicological properties. Multiple regression analysis and ANN model are also suggested to use to relate the biological activity with the global and local reactivity descriptors. [ABSTRACT FROM AUTHOR]

Optimization of nine bis-Schiff bases derived from 5-substituted-8-aminoquinoline (I) and furan-2, 3-di-carbaldehyde (II) molecules was performed using density functional theory (DFT) in B3LYP/6-311G++ (d, p) level of theory and based on the optimized structures, structural parameters, dipole moments, as well as frontier molecular orbitals of the desired bis-Schiff bases (III) were calculated. The statistical thermodynamic functions, i.e., enthalpy changes (ΔHºr = 10.21 kcalmol−1) and Gibbs energy changes (ΔGºr = 12.62 kcalmol−1) were obtained from the theoretical harmonic frequencies (freq keyword). Each of these imines has four geometrical isomers (ZZ, EZ, ZE, and EE), and their relative stability for III-H was studied. It was found that ZZ (III-H) is the most unstable (9.20 kcalmol−1) in four isomers. To check the nonlinear optical (NLO) properties of these organic compounds the first hyperpolarizability (βtotal) and average polarizability (αave) parameters were calculated. All of these bis-Schiff bases (III) have βtotal values larger than the magnitude of the βtotal value for urea (a standard molecule) and III-NO2 is the best NLO material in studied compounds. So for III-NO2, Mulliken atomic charges analysis, frontier orbitals, and molecular electrostatic potential (MEP) surfaces have been studied. [ABSTRACT FROM AUTHOR]

• Atrazine migrates from ice to water during the freezing process. • The migration of herbicide atrazine is related to binding energy. • The migration ability of herbicide atrazine is related to free energy. • Temperature is the key to determine the magnitude of the free energy. Atrazine causes concern due to its resistant to biodegradation and could be accumulated in aquatic organisms, causing pollution in lakes. This study measured the concentration of atrazine in ice and the water under ice through a simulated icing experiment and calculated the distribution coefficient K to characterize its migration ability in the freezing process. Furthermore, density functional theory (DFT) calculations were employed to expatiate the migration law of atrazine during icing process. According to the results, it could release more energy into the environment when atrazine staying in water phase (-15.077 kcal/mol) than staying in ice phase (-14.388 kcal/mol), therefore it was beneficial for the migration of atrazine from ice to water. This explains that during the freezing process, the concentration of atrazine in the ice was lower than that in the water. Thermodynamic calculations indicated that when the temperature decreases from 268 to 248 K, the internal energy contribution of the compound of atrazine and ice molecule (water cluster) decreases at the same vibrational frequency, resulting in an increase in the free energy difference of the compound from -167.946 to -165.390 kcal/mol. This demonstrated the diminished migratory capacity of atrazine. This study revealed the environmental behavior of atrazine during lake freezing, which was beneficial for the management of atrazine and other pollutants during freezing and environmental protection. [ABSTRACT FROM AUTHOR]

Cumulenes are valuable precursors to an entire series of more complex organic derivatives. Cyclic cumulenes present a special case, since they possess an increased potential to possess a high order of symmetry. The stability of the cumulene molecule can be brought forth through the construction of crossed clusters. In this case, molecular modeling tools were employed in order to provide insights into the construction and stability of 3 C26 triple crossed C26 cyclic cumulene cluster. The study revealed that is a very little change in the total energy per atom (or per electron) of triple crossed 3 C26 when compared with C26 (0.00002 Hartree/e, which is less than 0.01 ‰). Other important parameters, such as the HOMO-LUMO gap and the angles between the planes of the molecular rings, suggest its kinship with fullerenes and the regular tetrahedron. Furthermore, in order to proof the suitability of the approach and of its results a symmetry constrained optimization study was conducted using Z-matrix internal coordinates with Gaussian software. At DFT BLYP 6-311 G* theory level a symmetry constrained optimization of the 3 C26 cluster converged, which suggests the possibility of obtaining this cluster by synthetic means. [ABSTRACT FROM AUTHOR]

In this study we illustrate the structural, electronic and optical integrity of Ca 1- x Sm (2/3) x WO 4 (x = 0.00, 0.02, 0.04, 0.06 and 0.08) crystals for optoelectronic applications via experimental and first principles approach. According to our experimental outcomes, CaWO 4 crystallizes in scheelite type tetragonal structure devoid of impurity which depends on the A-site cationic radius and dopant-host compatibility. As a result, the dopant induced lattice distortion occur due to symmetric and asymmetric stretching of (Ca, Sm)—O and W–O bonds within [CaO 8 ] and [WO 4 ] cluster. According to our FT-IR and Raman spectral analysis, the non-centrosymmetric vibration within the [WO 4 ]2- complex gives rise to internal modes while the Ca2+/Sm3+ cationic displacement and rigid molecular ionic group constitutes the external modes which equally impacts the electronic and optical characteristics of the host material. While the forbidden gap extends due to Sm3+ substitution, the delocalization of W-5d orbitals on the other hand occur due to rising distortions within the WO 4 cluster. As a result, the polarization between [WO 4 ] and [CaO 8 ] cluster and difference in the electronic transitions controls the optical characteristics of the host material. According to our experimental and theoretical predictions, a noticeable decrease in the optical band gap (5.96–5.83 eV) occurs due to heterovalent cationic substitution (Sm3+), difference in structural order-disorder and charge carrier density. As a result, a broad photoluminescence (PL) spectrum among acceptor doped samples verifies the impact of multi-phonon or multi-level processes on the luminosity of the host material. [ABSTRACT FROM AUTHOR]

Energies of the atomic and molecular orbitals belonging to one and two atom systems from the fourth and fifth periods of the periodic table have been calculated using ab initio quantum mechanical calculations. The energies of selected occupied and unoccupied orbitals surrounding the highest occupied and lowest unoccupied orbitals (HOMOs and LUMOs) of each system were selected and used as input for our artificial intelligence (AI) software. Using the AI software, correlations between orbital parameters and selected chemical and physical properties of bulk materials composed of these elements were established. Using these correlations, the materials' bulk properties were predicted. The Q2 correlation for the single-atom predictions of first ionization potential, melting point, and boiling point were 0.3589, 0.4599, and 0.1798 respectively. The corresponding Q2 correlations using orbital parameters describing two-atom systems increased the capability to predict the experimental properties to the respective values of 0.8551, 0.8207, and 0.7877. The accuracy in predicting materials' bulk properties was increased up to four-fold by using two atoms instead of one. We also present results of the prediction of molecules for materials relevant to energy systems. [ABSTRACT FROM AUTHOR]

The energy sector has demonstrated significant enthusiasm for investigating post‐combustion CO2 capture, storage, and separation. However, the practical application of current porous adsorbents is impeded by challenges related to cost competitiveness, stability, and scalability. Intregation of heteroatoms in the porous organic polymers (POPs) dispense it more susceptible for CO2 adsorption to attenuate green house gases. In this regard, two hydroxy rich hypercrosslinked POPs, namely Ph/Tt‐POP have been developed by one‐pot condensation polymerization using a facile synthetic strategy. The high surface areas of both the Ph/Tt‐POP (1057 and 893 m2g−1, respectively), and the heteroatom functionality in the POP framework instigated us to explore our material for CO2 adsorption study. The CO2 uptake capacities in Ph/Tt‐POP are found to be 2.45 and 2.2 mmol g−1, at 273 K respectively. Further, in‐situ static 13C NMR experiment shows that CO2 molecules in Tt‐POP appear to be less mobile than those in Ph‐POP which probably due to the presence of triazine functional groups along with high abundant −OH groups in the Tt‐POP framework. An in‐depth study of the CO2 adsorption mechanism by density functional theory (DFT) calculations also shows that CO2 adsorption at the cages formed by two benzyl rings represents the most stable interaction and CO2 molecule is more favorably adsorbed on the Ph‐POP with the more negative interaction energies values compared to that of Tt‐POP. Further, Non‐covalent interaction (NCI) plot reveals that CO2 molecules adsorb more on the Ph‐POP than Tt‐POP, which can be explain by hydrogen bond formation in case of Tt‐POP repeating units turning aside CO2 molecule to interact with the Ph component. Overall, our present study reflects the comprising effects of surface area of the solid adsorbents as well as their functionality can be beneficial for developing efficient hypercrosslinked porous polymers as solid CO2 adsorbent. [ABSTRACT FROM AUTHOR]

The electrochemical nitrogen reduction reaction (NRR) is a key process for the energy transition. Transition metal atoms atomically dispersed on a solid support represent a promising approach to the design of new catalytic materials. The interest for single‐ (SACs) and dual‐atom catalysts (DACs) is steadily growing. In general, DACs are considered more active than SACs for NRR. In this work, the complex chemistry behind NRR is investigated on a set of SACs and DACs by means of density functional theory (DFT) calculations. The results indicate that self‐interaction corrected exchange‐correlation functionals must be adopted, at variance with several studies in the literature. Furthermore, it is not possible to extrapolate results obtained on conventional extended catalytic surfaces to SACs and DACs, due to a richer scenario of possible reaction paths. In general, the results show a positive effect on the catalytic activity moving from 3d to 5d metals, and from SACs and DACs. However, if the two effects work together, that is, 5d metals in DACs, the reaction intermediates may be too strongly bound, thus resulting in reduced catalytic activity. In this respect, the fact that DACs are expected to be superior to SACs in NRR is not always verified. [ABSTRACT FROM AUTHOR]

With the aim of producing new heterocycle molecules, the previously reported 2-(aminomethyl)-2-(4-chlorophenyl)-2,3-dihydroquinazolin-4(1H)-one was converted efficiently by reacting with N,N′-dithiocarbonyldiimidazole (DTCI) to produce the substituted imidazolidine-2-thione moiety inserted in a three-fused-ring scaffold of the title compound. The molecular composition was confirmed by a high-resolution MS experiment, and its structure was elucidated by 1H, 13CNMR, and IR analyses. The thioacetamide form of the product was supported by density functional theory (DFT)–NMR analysis where 13C chemical shifts of the thioacetamide form and of its iminothiol tautomer were calculated in chloroform at the BP86/Jgauss-TZP2 level of theory. The very strong linear correlation between 13C chemical shifts from experimental findings and by calculation for the NHC=S form confirmed the structure. [ABSTRACT FROM AUTHOR]

The development of density functional theory (DFT) has significantly enhanced the use of computational chemistry as a tool in the design and development of ligands for the separation of actinides (An) and lanthanides (Ln) in the nuclear waste management. In the past, identifying new ligands involved either making incremental structural changes to existing ligands or conducting extensive laboratory testing of numerous compounds. However, these experimental methods are often costly and time-consuming. With the advancements in hardware and software, theoretical and computational chemistry has become a powerful and cost-effective approach in nuclear waste management research. The density functional theory (DFT), in particular, has played a pivotal role by enabling scientists to accurately predict the effectiveness of ligands based on electronic and molecular properties, as well as reactivity indices. This computational approach provides valuable insights into the separation efficiencies of ligands without the need for extensive experimental efforts. This review highlights the role of computational chemistry in the design of ligands for the separation of lanthanides and actinides in spent nuclear fuel processing. It discusses various design strategies and computational analyses used in ligand optimization, highlighting the potential applications of computational tools in guiding ligand design and improving separation processes. The work emphasizes the synergy between computational insights and experimental observations in lanthanide/actinide chemistry, which enhances understanding of complex phenomena and aids in the interpretation of experimental results. It also explores different design approaches that allow for fine-tuning of ligand properties and selectivity toward specific metal ions, ultimately improving separation efficiency. In this review, we will discuss some widely used computational tools in chemistry without delving into complex mathematical formulas. This will be particularly helpful for researchers who come from an experimental background and may not be as familiar with advanced mathematical concepts. The tools covered are bond order analysis, population analysis, quantum theory of atoms in molecules (QTAIM) analysis, Energy Decomposition Analysis (EDA), and thermodynamic analysis. These methods are explored in a more accessible manner for non-theoretical researchers. They provide valuable insights into bonding, binding, stability, non-bonding interactions, coordinating abilities and selectivity of organic ligands in extraction of actinides and lanthanides, thus providing useful information in the designing of ligands to enhance separation strategies. This review serves as an excellent resource for future ligand design, offering valuable insights into computational techniques used to understand the coordination and complexation behaviors of ligands. Also an attempt has been made to understand the role of DFT functionals in the calculations. It provides a foundation for researchers to comprehend and apply computational tools effectively in their investigations. [ABSTRACT FROM AUTHOR]

A newly developed spherical boehmite and melamine composite with a mesoporous structure was successfully fabricated through a spray drying system utilizing a mixture of boehmite sol and melamine. EDX–SEM, FTIR, and TGA analyses confirmed the integration of melamine into the boehmite network within the resulting composite. With an increase in melamine content, the composites exhibited a gradual reduction in porosity compared to their pristine boehmite counterpart. However, the CO2 uptake of the composites continued to demonstrate improvement. The boehmite sample modified with 5 mol% of melamine (IMB#5) demonstrated the highest CO2 adsorption capacity at 19.2 cm3 g−1. This value surpassed the original boehmite sample by 46.1% under conditions of 25 °C and 1 bar. The enhanced adsorption can be attributed to the development of adsorptive affinity facilitated by N-derived functional groups (–NH2 and –CN) within the melamine structure and their interaction with CO2. As a result, the CO2/N2 separation factor and CO2/N2 adsorptive selectivity using the ideal adsorbed solution theory (IAST) over the IMB#5 sample were 113.3 and 3182, respectively, approximately 3 times and 9.2 times higher than those for the boehmite sample. Density functional theory (DFT) calculations were conducted to investigate the interaction of melamine on the boehmite surface, as well as the selective adsorption of CO2 and N2 gaseous molecules on the boehmite/melamine composite. It is shown that the melamine mainly interacts with the boehmite via a strong binding of the N atom of the triazine ring with the Al atom of the boehmite. The adsorption of CO2 has lower binding enthalpies and free energies than that of N2. These findings indicate that utilizing continuous spray drying holds promise as an effective pathway for scaling up the production of mesoporous boehmite/melamine composite spheres as CO2 selective adsorbents. [ABSTRACT FROM AUTHOR]

In the pursuit of sustainable energy, magnesium hydride (MgH2) stands out as a promising candidate for hydrogen storage due to its high capacity. Nevertheless, its high thermodynamic stability necessitates elevated operating temperatures, thereby hindering practical applications. To mitigate this limitation, our study employs a defect engineering approach by introducing a mono-vacancy to decrease its thermodynamic stability. Utilizing first-principles density functional theory calculations, we investigate the influence of a mono-vacancy on the structural and electronic properties of MgH2 crystal. Introducing the defect results in a 0.57 % contraction of the a / b lattice parameters and a 1.03 % expansion along the c-axis, causing lattice distortion. Electronically, the band gap narrows by 0.67 eV, indicating an increase in metallic character. We observe a distinct vacancy-affected zone, characterized by substantial alterations in electron density within a 26.505 Å3 volume and modifications to the potential energy distribution encompassing a 19.514 Å3 volume. The mono-vacancy enhances the polarity of the Mg-H bonds and maximally decreases the bond energy by 0.065 eV. A localized high-energy region of 0.354 eV emerges, functioning as an energy barrier to atomic diffusion. This energy barrier is encompassed by low-energy pathways, potentially facilitating H atom migration within the MgH2 crystal. [ABSTRACT FROM AUTHOR]

It is highly desirable to design efficient and stable hydrogen evolution reaction (HER) and oxygen evolution/reduction reaction (OER/ORR) electrocatalysts for the development of renewable energy technologies. Herein, density functional theory (DFT) calculations were conducted to systematically investigate a series of TMNxO4−x-HTT (TM = Fe, Co, Ni, Ru, Rh, Pd, Ir and Pt; HTT = hexahydroxy tetraazanaphthotetraphene) analogs of two-dimensional (2D) conductive metal-organic frameworks (MOFs) as potential electrocatalysts for the HER, OER and ORR. The thermodynamic and electrochemical stability simulations suggest that these designed catalysts are stable. Remarkably, CoO4-HTT, RhN3O1-HTT and IrN3O1-HTT are predicted to be the most promising catalysts for the HER, OER and ORR, respectively, surpassing the catalytic activity of corresponding benchmark catalysts. The volcano plots were established based on the scaling relationship of adsorption Gibbs free energy of intermediates. The results reveal that regulating combinations of metal active centers and local coordination environments could effectively balance the interaction strength between intermediates and catalysts, thus achieving optimal catalytic activity. Our findings not only opt for the promising HER/OER/ORR electrocatalysts but also guide the design of efficient electrocatalysts based on 2D MOFs materials. [ABSTRACT FROM AUTHOR]

Oxide-supported metal single-atom catalysts (SACs) have exhibited excellent catalytic performance for water–gas shift (WGS) reaction. Here, we report the single-atom catalyst Pt1/FeOx exhibits excellent medium temperature catalytic performance for WGS reactions by the density functional theory (DFT) calculations and experimental results. The calculations indicate that H2O molecules are easily dissociated at oxygen vacancies, and the formed ⋆OH and ⋆O are adsorbed on Pt1 single atoms and the adjacent O atoms, respectively. After studying four possible reaction mechanisms, it is found that the optimal WGS reaction pathway is proceeded along the carboxyl mechanism (pathway III), in which the formation of ⋆COOH intermediates can promote the stability of Pt1/FeOx SAC and the easier occurrence of WGS reaction. The energy barrier of the rate-determining step during the entire reaction cycle is only 1.16 eV, showing the high activity for the medium temperature WGS reaction on Pt1/FeOx SAC, which was verified by experimental results. Moreover, the calculated turnover frequencies (TOFs) of CO2 and H2 formation on Pt1/FeOx at 610 K (337 °C) can reach up to 1.14 × 10−3 s−1·site−1 through carboxyl mechanism. In this work, we further expand the application potential of Pt1/FeOx SAC in WGS reaction. [ABSTRACT FROM AUTHOR]

Silver and its alloys undergo tarnishing with time, which is a black stain on the surface due to the formation of Ag2S. Developing a tarnish resistant Ag alloy was attempted by alloying Ag with elements that form a passive oxide layer on the surface. Germanium is proven to provide better tarnish resistance to sterling Silver alloy (92.5 wt% pure) which is available under the trade name of Argentium©. The present work investigates the tarnish resistance behavior of sterling silver alloy (92.5 wt% pure) containing various additions of Copper, Zinc, and Germanium. The alloys were prepared by melting and casting route, followed by Passivation Heat Treatment (PHT) to create a stable and continuous oxide layer. The temperature for PHT was optimized using thermogravimetry analysis (TGA) of the alloys prepared. Accelerated tarnish test was carried out to investigate the tarnishing behavior of alloy samples obtained before and after PHT. The samples were characterized using XRD, SEM-EDX, and micro-Raman Spectroscopy. The change in reflectance of the samples after tarnish test is determined using UV–Visible reflectance spectroscopy. The mechanism behind the tarnish resistance was derived using Density Functional Theory (DFT) by comparing sulphur (S2) and Oxygen (O2) adsorption energies (BE) of the alloying elements. The lower value of S2 (BE)/O2 (BE) indicates better oxidation and tarnish resistance. The ratio ranges between 222 % (Pure Ag) and 132 % (for Ag-4.2Cu-2.8Zn-1.4Ge) and the p-p between Ge and O has contributed to the reduction in the ratio.

Solar cells are currently the focus of a great deal of research. The aim is to reduce their cost price. To achieve this, we need to reduce the mass of the materials and increase the conversion efficiency of these solar cells. This has motivated research into the use of thin films such as a-Si, CdTe, CIGS. This increase in efficiency requires optimizing the performance of the photovoltaic parameters. In this modeling and simulation work, we use the SCAPS-1D software to study the effect of the recombination speed of the electrons and holes in the CIGS layer, the effect of the thickness of the layers and the effect of the gap energy of each layer of the material used for this solar cell on the short-circuit current Jsc, the open-circuit voltage Voc, the form factor FF and the electrical efficiency η of the CIGS cell for a Mo/p-CIGS/p-Si/In2S3/i-ZnO/Al-ZnO single-junction structure. In this study, we found that recombination speed affects the efficiency of the photovoltaic cell. The gap energy of the absorber layers influences the cell's efficiency, while the other layers (In2S3, ZnO, Al-ZnO) do not have a great influence on solar cell performance and increasing the thickness of the absorber layer has a major influence on efficiency, increasing it up to a certain limit. The thicknesses of the CIGS, p-Si, In2S3, i-ZnO and Al‑ZnO layers need to be in the order of 0.3µm, 0.8µm, 0.05µm, 0.07µm and 0.1µm respectively to achieve better efficiency (31.42%).

The structure of Dacarbazine was optimized by density functional theory ( DFT ) at the B3LYP / 6-31 + g ( d, p ) level. The Raman spectrum of Dacarbazine were obtained by frequency calculation and compared with the experimental Raman spectrum. The Raman characteristic peaks in the frequency range of 400 ~ 2000cm-1 were assigned. In addition,the frontier orbital and surface electrostatic potential of Dacarbazine was analyzed,and the possible sites of chemical reaction were predicted. The time dependent density functional theory (TDDFT) was used to calculate the ultraviolet absorption spectrum and the excited states of the molecule. At the same time,the charge transfer spectrum was obtained,and the charge transfer reletionship of Dacarbazine was analyzed. [ABSTRACT FROM AUTHOR]

Although the concept of geopolymers was proposed over 40 years ago, there still remains a lack of clarity regarding their atomic-level structure and formation. In this study, the Dmol3 quantum chemistry calculation program, based on density functional theory (DFT), was used to determine a range of electronic structural properties associated with the initial, intermediate (IM), transition (TS), and final states of Al2O3/[Al(OH)4]− conversion reactions in the alkali-activator. The properties analyzed included total energy, Gibbs free energy, electrostatic potential (ESP), Fukui functions, and frontier orbitals, comprising the highest-occupied molecular orbital (HOMO) and the lowest-unoccupied molecular orbital (LUMO). The simulation results indicated that electrons were transferred from the HOMO of O in H2O and OH− to the LUMO of Al in (AlO2)− or (AlO)+ , leading to an increase in the LUMO energy level of Al and a reduction in the chemical reactivity of the newly formed Al monomers. The transformation processes from Al2O3 to [Al(OH)4]− involved varying numbers of steps, energy release, and energy barriers. Notably, during the transition state conversion process, the breaking and reformation of O─ H bonds often occurred as necessary conditions for the formation of transition states. These findings have significant implications for the advancement of new technologies based on geopolymer conversion processes. [ABSTRACT FROM AUTHOR]

We investigate theoretically the design and application of nine triazine (Tr)-core star-shaped molecules built with thiophene (Th), phenyl (Ph), and carbazole (Cz) moieties in dye-sensitized solar cells (DSSCs) and bulk heterojunction (BHJ) organic solar cells. Density functional theory and time-dependent density functional theory are employed to rationalize the electronic structure, charge transfer properties, and photovoltaic performance of these systems. Tr-Th-Cz and Tr-Ph-p-Th-Cz display power conversion efficiency (PCE ) values close to 30% due to a favorable alignment of the energy levels. Computed open-circuit voltage values show that lack of π-bridges, as in the Tr-Th and Tr-Cz, favor higher voltage generation. Systems containing thiophene (Th) and carbazole (Cz) present the most favorable values for efficient electron injection and dye regeneration. Furthermore, the incorporation of these Th and Cz donor substituents into the triazine core combined with π-bridges significantly impacts other optoelectronic properties of the organic solar cells. The computed high singlet–triplet gap values indicate limited potential of these molecules as thermally activated delayed fluorescence (TADF) emitters for applications in organic light-emitting diodes (OLEDs). [ABSTRACT FROM AUTHOR]

The harmful effect of lead Pb2+ base materials like PbTiO3 on the environment and human health has raised ecological concerns, which has led to the investigation of lead Pb2+ free ferroelectric materials that are safe for the environment and human health and can be used in technological applications. In this research, the structural, electronic, and elastic properties of the cubic phase of SnTiO3 were investigated using first principle calculation. The electronic structure calculation was done by using the generalized gradient approximation and PerdewBurke Ernzerhof (GGA-PBE) functional as implemented in the pseudopotential plane wave approach within the framework of density functional theory (DFT) by using Quantum Espresso open sources computer code. The convergence test of total energy concerning energy cut-off wave function and k-point sampling was performed to ensure the accuracy of the calculations. Thermo_pw code was employed to compute the elastic constant using the Quantum Espresso software package and the result obtained was used to calculate mechanical parameters such as the elastic properties, anisotropy factor A, shear modulus G, bulk modulus B, Young’s modulus E, and Poison’s ratio n of the SnTiO3. Furthermore, Debye temperature and longitudinal and transversal sound velocities were determined using the elastic constant. Therefore, the cubic phase of SnTiO3 with a space group of (Pm3m) is a good ferroelectric material due to its Debye temperature and the covalent bonding nature of the atom within the solid crystal of the material.

An entropy-stabilized multicomponent ultrahigh-temperature ceramic (UHTC) coating, (Ti0.25V0.25Zr0.25Hf0.25)B2, on a graphite substrate was in-situ sintered by spark plasma sintering (SPS) from constituent transition metal diboride powders. The (Ti0.25V0.25Zr0.25Hf0.25)B2 coating had a hardness of 31.2±2.1 GPa and resisted 36.9 GPa of stress before delamination, as observed at the interface. The temperature-dependent thermal properties of the multicomponent diboride (Ti0.25V0.25Zr0.25Hf0.25)B2 were obtained by molecular dynamics (MD) simulations driven by a machine learning force field (MLFF) trained on density functional theory (DFT) calculations. The thermal conductivity, density, heat capacity, and coefficient of thermal expansion obtained by the MD simulations were used in time-dependent thermal stress finite element model (FEM) simulations. The low thermal conductivity (< 6.52 W∙m−1∙K−1) of the multicomponent diboride coupled with its similar coefficient of thermal expansion to that of graphite indicated that stresses of less than 10 GPa were generated at the interface at high temperatures, and therefore, the coating was mechanically resistant to the thermal stress induced during ablation. Ablation experiments at 2200 °C showed that the multicomponent diboride coating was resistant to thermal stresses with no visible cracking or delamination. The ablation mechanisms were mechanical denudation and evaporation of B2O3 and light V–Ti oxides, which caused a decrease in the mass and thickness of the coating and resulted in mass and linear ablation rates of −0.51 mg·s−1 and −1.38 µm·s−1, respectively, after 60 s. These findings demonstrated the thermal and mechanical stability of multicomponent entropy-stabilized diborides as coatings for carbon materials in engineering components under extreme environments.

The reaction mechanism for the chlorination and bromination of 2-naphthol with PIDA or PIFA and AlX3 (X = Cl, Br), previously reported by our group, was elucidated via quantum chemical calculations using density functional theory. The chlorination mechanism using PIFA and AlCl3 demonstrated a better experimental and theoretical yield compared to using PIDA. Additionally, the lowest-energy chlorinating species was characterized by an equilibrium of Cl–I(Ph)–OTFA–AlCl3 and [Cl–I(Ph)][OTFA–AlCl3], rather than PhICl2 being the active species. On the other hand, bromination using PIDA and AlBr3 was more efficient, wherein the intermediate Br–I(Ph)–OAc–AlBr3 was formed as active brominating species. Similarly, PhIBr2 was higher in energy than our proposed species. The reaction mechanisms are described in detail in this work and were found to be in excellent agreement with the experimental yield. These initial results confirmed that our proposed mechanism was energetically favored and therefore more plausible compared to halogenation via PhIX2.

In this study, choline chloride/lactic acid/guaiacol ternary deep eutectic solvent (DES) was used to extract Ganoderma lucidum polysaccharides (GLPs). The operational parameters of GLPs extraction by DES were optimized, and the obtained GLPs structure was characterized by Fourier transform infrared spectrophotometer (FT-IR) and gel chromatography (GPC). Furthermore, the in vitro antioxidant activities of GLPs were investigated. In the end, density functional theory (DFT) was leveraged to gain preliminary insights into the molecular mechanism underpinning polysaccharide extraction facilitated by DES. Results unveiled that when the moisture content within DES was maintained at 50%, extraction was carried out at a temperature of 80 ℃ for 1 h, and the liquid-to-solid mass-volume ratio stood at 1:30 g/mL, the extraction yield of GLPs reached 9.20%±0.27%. FT-IR and GPC results showed that GLPs had typical polysaccharide structures in the 4000~500 cm−1 regions, and the number average mass weight (Mn) of GLPs was 8057 Da with the polydispersity index (PDI) of 1.6. In the context of in vitro antioxidant activity experiments, when GLPs content was 5 mg/mL, the total reducing power was measured at 0.67±0.04. Notably, the IC50 values for GLPs' scavenging capabilities against DPPH, OH, and ABTS+ free radicals were determined to be 2.366, 6.179, and 2.440 mg/mL, respectively. DES simulation analyses revealed a binding energy of 65.29 kcal/mol between DES and glucose, a substantially higher value compared to the binding energy observed between water and glucose (20.38 kcal/mol). The GLPs extraction by DES was facilitated through the pivotal role of triple hydrogen bond interactions. The findings in this study elucidated the intrinsic mechanism at molecular level that underscores the superior effectiveness of DES in comparison to traditional hot water extraction methods.

An efficient method for the conversion of biphenyl acrylamides to dibenzoazepinones with −SCF3 incorporation is described. This operationally simple radical cascade reaction employs CAN as an oxidant and exhibits good functional group tolerance. Substrates featuring −OCH3, −CH3, −Br or −Cl at the para‐position of the aromatic ring exhibits a preference for an ipso‐cyclization due to the intervention of DMSO in the reaction. Density functional theory (DFT) calculations provide valuable insights into the reaction's energetics and product selectivity. [ABSTRACT FROM AUTHOR]

Our rigorous investigation, employing first principles-based dispersion-corrected density functional theory (DFT-D) and second-order Møller-Plesset perturbation theory (MP2) methods, has illuminated the remarkable promise of lithium-decorated organic linkers of Covalent Organic Frameworks (COFs). We have computationally designed 36 complexes with nine pure linkers of COFs and Li-decorated linkers, and these designed linkers show the physisorption of H 2 molecules. The synergy of Li atoms with these linkers shows a Li binding energy about −0.5 to −1.3 eV, which enables each Li atom to capture two H 2 molecules with an average ΔH per H 2 molecule about -0.02 to -0.20 eV. We computationally obtained a significant weight percentage (wt.%) of H 2 uptake, with a maximum of wt.% for the molecular structure of Linker-3 using DFT-D methods. The true highlight of our work is the average binding enthalpy of -0.20 eV per H 2 molecule when coupled with Li-decorated Linker-5. Our study unveils the intricate interplay between dispersion and electrostatic forces that play a dominant role in binding enthalpy. We performed GCMC simulations in our designed pure COFs to study the H 2 uptake at 77 K and 298 K at varying low and high-pressure ranges. COF-IITI appears more effective in absolute H 2 loading than the Pristine COF because of its larger surface area. This groundbreaking research is essential for realizing efficient, secure, compact, and cost-effective hydrogen storage materials. It aligns perfectly with the ambitious goals set by the U.S. Department of Energy, propelling us closer to a sustainable energy future. [Display omitted] • A Li-decoration technique is proposed to enhance H 2 uptake in COF's linkers. • The Li binding energy for COF's linkers lies in the range of -0.5 to -1.3 eV. • The H 2 binding enthalpy in Li-decorated linkers satisfies the physisorption. • Dispersion and electrostatic interactions play a major role in binding enthalpy. [ABSTRACT FROM AUTHOR]

By using density functional theory (DFT), the adsorption behavior of gas molecules on defective graphene doped with manganese and nitrogen were investigated. The geometric structure, electronic structure, and magnetic properties of two substrates were calculated and the sensing mechanism was also analyzed. The results indicate that the MnSV-GP and MnN3-GP have stronger structural stability, in which Mn atoms and their coordination atoms will become the adsorption point for five gas molecules (CH2O, CO, N2O, SO2, and NH3), respectively. Moreover, at room temperature (298 K), the recovery time of the MnSV-GP sensor for N2O gas molecules is approximately 1.1 s. Therefore, it can be concluded that the MnSV-GP matrix as a magnetic gas sensor has a promising potential for detecting N2O. These results also provide a new pathway for the potential application of Mn-doped graphene in the field of gas sensors. [ABSTRACT FROM AUTHOR]

First-principles periodic density functional theory (DFT) calculations have been performed to understand the structural, elastic, mechanical, and electronic properties of CdWO4 under pressure up to 15 GPa. The calculated structural parameters and elastic constants at zero pressure are found in excellent agreement with the experimental and other theoretical values. Furthermore, with the increase in the external pressure, the lattice constant as well as unit cell volume decreases in accordance with the experimental results. The pressure has a more significant influence on the b axis than the a- and c-axis. Mechanical properties such as elastic constants, Young modulus, shear modulus, B/G ratio and Poisson ratio have been obtained under pressure. According to the B/G ratio and Poisson ratio, monoclinic CdWO4 shows a brittle manner. Additionally, the main features of the valence and conduction bands have been analyzed from the total and partial density of states. [ABSTRACT FROM AUTHOR]

A theoretical thermodynamic study was conducted to investigate the antioxidant activity and mechanism of 1,3,4-oxadiazol-2-ylthieno[2,3-d]pyrimidin-4-amine derivatives (OTP) using a Density Functional Theory (DFT) approach. The study assessed how solvent environments influence the antioxidant properties of these derivatives. With the increasing prevalence of diseases linked to oxidative stress, such as cancer and cardiovascular diseases, antioxidants are crucial in mitigating the damage caused by free radicals. Previous research has demonstrated the remarkable scavenging abilities of 1,3,4-oxadiazole derivatives, prompting this investigation into their potential using computational methods. DFT calculations were employed to analyze key parameters, including bond dissociation enthalpy (BDE), ionization potential (IP), proton dissociation enthalpy (PDE), and electron transfer enthalpy (ETE), to delineate the antioxidant mechanisms of these compounds. Our findings indicate that specific electron-donating groups such as amine on the phenyl rings significantly enhance the antioxidant activities of these derivatives. The study also integrates global and local reactivity descriptors, such as Fukui functions and HOMO-LUMO energies, to predict the stability and reactivity of these molecules, providing insights into their potential as effective synthetic antioxidants in pharmaceutical applications. [ABSTRACT FROM AUTHOR]

This research paper explores the structural, electronic, magnetic, elastic, dynamic, and thermoelectric properties of sp-based half-Heusler (HH) RbBaX (X = Si and Ge) compounds using density functional theory (DFT) and the full-potential linearized augmented plane wave (FP-LAPW) method within the WIEN2k software package. We evaluate the exchange correlation potential using two different approaches: The generalized gradient approximation (GGA) and the modified Becke–Johnson approach. We observe that RbBaX (X = Si and Ge) adopts a ferromagnetic configuration based on the analysis of total energy against volume. We establish that these alloys possess a genuine half-metallic character because of the full spin polarization observed at the Fermi level in their electronic spectrum. Both compounds under investigation have a total magnetic moment of 1.00 μ B, in agreement with the Slater–Pauling principle. The Born stability criteria for cubic structures and phonon dispersion patterns confirm the mechanical and dynamic stability of RbBaX (X = Si and Ge) alloys. The thermoelectric properties reveal a p-type semiconductor nature, characterized by significant positive Seebeck values. The thermoelectric figure of merit (ZT) calculated for both alloys at 300 K approaches unity, highlighting their remarkable thermoelectric efficiency. [ABSTRACT FROM AUTHOR]

Semiconductor nanocrystals (NCs), particularly cadmium selenide (CdSe) quantum dots (QDs), are nanoscale particles that exhibit unique size-dependent optical and electronic properties, which make them valuable for applications in optoelectronics, bioimaging, and catalysis. The stabilization and synthesis of QDs are critically influenced by surfactants, which control the size, shape, and surface properties of the QDs. In this study, we investigated the effects of benzoic acid (BA), benzoate (BZ), and eight para-substituted derivatives on the properties of CdSe nanoclusters using density functional theory (DFT). The binding energies and electronic properties of the surfactant-nanocluster complexes were analyzed, demonstrating significant variations based on the nature of the substituent. Electron-donating groups (EDGs) generally enhance binding strength and electronic properties more effectively than electron-withdrawing groups (EWGs). Notably, benzoate derivatives exhibited stronger binding and more substantial modifications to the electronic properties of CdSe nanoclusters than benzoic acid derivatives. These computational insights provide a detailed understanding of the binding interactions, potentially guiding the rational design of surfactants for specific nanocrystal applications. [ABSTRACT FROM AUTHOR]

Organosilicate glass (OSG) films are a critical component in modern electronic devices, with their electrical properties playing a crucial role in device performance. This comprehensive review systematically examines the influence of chemical composition, vacuum ultraviolet (VUV) irradiation, and plasma treatment on the electrical properties of these films. Through an extensive survey of literature and experimental findings, we elucidate the intricate interplay between these factors and the resulting alterations in electrical conductivity, dielectric constant, and breakdown strength of OSG films. Key focus areas include the impact of diverse organic moieties incorporated into the silica matrix, the effects of VUV irradiation on film properties, and the modifications induced by various plasma treatment techniques. Furthermore, the underlying mechanisms governing these phenomena are discussed, shedding light on the complex molecular interactions and structural rearrangements occurring within OSG films under different environmental conditions. It is shown that phonon-assisted electron tunneling between adjacent neutral traps provides a more accurate description of charge transport in OSG low-k materials compared to the previously reported Fowler–Nordheim mechanism. Additionally, the quality of low-k materials significantly influences the behavior of leakage currents. Materials retaining residual porogens or adsorbed water on pore walls show electrical conductivity directly correlated with pore surface area and porosity. Conversely, porogen-free materials, developed by Urbanowicz, exhibit leakage currents that are independent of porosity. This underscores the critical importance of considering internal defects such as oxygen-deficient centers (ODC) or similar entities in understanding the electrical properties of these materials. [ABSTRACT FROM AUTHOR]

As new pesticides continue to emerge in agricultural systems, understanding their environmental behavior is crucial for effective risk assessment. Tiafenacil (TFA), a promising novel pyrimidinedione herbicide, was the focus of this study. We developed an efficient QuEChERS-UHPLC-QTOF-MS/MS method to measure TFA and its transformation products (TP1, TP2, TP3, TP4, and TP5) in soil. Our calibration curves exhibited strong linearity (R2 ≥ 0.9949) ranging from 0.015 to 2.0 mg/kg within a low limit of quantification (LOQ) of 2.0 µg/kg. Inter-day and intra-day recoveries (0.10 to 2.0 mg/kg, 80.59% to 110.05%, RSD from 0.28% to 12.93%) demonstrated high sensitivity and accuracy. Additionally, TFA dissipation under aerobic conditions followed first-order kinetics, mainly yielding TP1 and TP4. In contrast, TP1 and TP2 were mainly found under sterilized and anaerobic conditions, and TFA dissipation followed second-order kinetics. Moreover, we predicted the transformation pathways of TFA using density functional theory (DFT) and assessed the toxicity levels of TFA and its TPs to aquatic organisms using ECOSAR. Collectively, these findings hold significant implications for a better understanding of TFA fate in diversified soil, benefiting its risk assessment and rational utilization. [ABSTRACT FROM AUTHOR]

Glucose plays a key role in the regulation of the levels of blood sugar, and the body closely monitors it to maintain proper metabolic function. Although glucose is essential for human health, its excessive consumption can lead to negative effects such as obesity and diabetes. As a result, high-sensitive and accurate glucose detection is considered an essential measure in clinical analysis. Surface-enhanced Raman scattering (SERS) is an accurate method for identifying trace substances. In the present study, SERS-active substrates were used for detecting different concentrations of glucose. First, gold nanoparticles (AuNPs) were prepared by employing a chemical reduction method. Afterward, the fluorine-doped tin oxide (FTO) glass substrates were decorated with AuNPs using the electrodeposition method. Then, glucose was deposited as an analyte on SERS substrates. Interestingly, the limit of detection (LOD) of SERS-active FTO-covered glass substrates (SERS-FGS) for the detection of glucose was 10−9 M. Density functional theory (DFT) method was used to simulate and validate the Raman spectra and peak signals obtained experimentally. Moreover, the average relative standard deviation (RSD) was calculated as 3.06% for ten repeated measurements. Furthermore, the enhancement factor for these SERS-based biosensors, for the identification of molecular vibrations of 10−5 M glucose, was obtained to be 1.4310 × 104 experimentally and 1.5397 × 104 numerically. Therefore, the SERS-FGS developed in this study showed promising results for detecting glucose and controlling diseases, such as diabetes and other problems resulting from an abnormality in glucose levels. [ABSTRACT FROM AUTHOR]

The present study employs rigorous DFT analysis using WIEN2k for the best suitability of the Cr2O3 as an electron transport layer, synergetic with nontoxic and thermally stable CsSnCl3 perovskite solar energy storage device, configured as FTO/Cr2O3/CsSnCl3/CBTS/Au. The main objective of our investigation is to improve the device performance by optimizing thickness, carrier concentration, bulk defect density of each layer, interface defects, operating temperature, as well as the impact of parasitic elements on device performance. SCAPS‐1D tool was used to optimize the novel device architecture. The simulation results reveal that a CsSnCl3 layer with an optimized thickness of 800 nm and a doping concentration of 1 × 1015 cm−3 yields noteworthy outcomes, specifically, champion efficiency (휂) of 22.01% along with an open‐circuit voltage (Voc) of 1.12 V, a short‐circuit current (Jsc) of 23.86 mA/cm2, and a fill factor of 81.65%. These improved findings were compared with existing theoretical and experimental reported data and found to exhibit the best performance. The present research substantially enhances the understanding of eco‐friendly CsSnCl3 perovskite solar cell optimization, thereby extending its applicability to future photovoltaic and optoelectronic devices. [ABSTRACT FROM AUTHOR]

Employing the constructs of density functional theory (DFT) and the Nonequilibrium Green's Function (NEGF), the investigation extensively explores the electronic and transport properties of zigzag graphene nanoribbons (ZGNRs) doped with vanadium (V). Notably, this inquiry unveils that strategic doping can transform V‐doped ZGNRs into spintronic nanodevices with distinctive transport attributes. Initially, the simulations showcase remarkably high spin‐filtering efficiencies (SFEs) at certain bias voltages. Furthermore, a giant magnetoresistance (GMR) peaking at 6.87 ×$\times$ 103$^3$ is detected. In conclusion, the examination discerns a spin rectifier that exhibits a significant rectification ratio (RR) of 9.62 ×$\times$ 102$^2$. This research delineates a viable trajectory for the refinement of high‐performance spintronics in ZGNRs via vanadium doping. The implications of this study indicate that the model harbors considerable promise for application in miniature spintronic devices. [ABSTRACT FROM AUTHOR]

2D transition metal dichalcogenide alloys are considered as the promising duo for energy storage and catalyst for light‐driven energy conversion applications due to their novel physicochemical properties. However, heterostructuring with other 2D materials is an effective strategy to enhance the charge storage kinetics as well as comprehensive spectral light response and efficient charge separation. Herein, Molybdenum sulfo selenide (MoSSe)/black phosphorous (BP) heterostructure is synthesized by a one‐pot solvothermal technique, and energy storage and conversion efficiency are characterized. Interestingly, the fabricated symmetric supercapacitor based on the MoSSe/BP hybrid shows an exceptional capacitance of 230 mF cm−2 with an excellent energy density of 31.9 µWh cm−2 and a power density of 805.7 µW cm−2. To validate the experimental findings, Density Functional Theory (DFT) computational simulations are carried out concurrently. The lower diffusion energy barrier for electrolytic ions, in the case of hybrid MoSSe/BP compared to pristine MoSSe, supports the higher charge storage performance. Finally, MoSSe/BP nanocomposites' photocatalytic hydrogen evolution reaction (HER) performance is evaluated under 400 W of UV–vis light, with eosin Y dye acting as a sensitizer and triethanolamine acting as a sacrificial agent. The MoSSe/BP nanocomposite exhibits the maximum photocatalytic HER activity of 5718 µmol h−1 g−1, greater than the bare MoSSe nanostructure. [ABSTRACT FROM AUTHOR]

Ribavirin (RBV), which is extensively used to treat viral diseases such as COVID-19, is considered one of the major emerging contaminants due to its long-term existence and health risk in the aqueous environmental system. However, research on effective removal of RBV still remains insufficient. In this study, we investigated the RBV degradation kinetics and mechanism in UV/chlorine/Fe(II) process. The degradation rate constant kobs-RBV of RBV was 2.52 × 10−4 s−1 in UV/chlorine/Fe(II) process, which increased by 1.6 times and 1.3 times than that in chlorine alone and UV/chlorine process, respectively. Notably, trace amount Fe(II) promoted RBV degradation in UV/chlorine system through Fe2+/Fe3+ cycles, enhancing the yield of reactive species such as HO· and certain species reactive chlorine radicals (RCS). The contributions of HO· and RCS toward RBV degradation were 53.91% and 16.11%, respectively. Specifically, Cl·, ClO·, and Cl2·− were responsible for 8.59%, 2.69%, and 4.83% of RBV removal. The RBV degradation pathway indicated that the reactive species preferentially attacked the amide moiety of RBV, which cleaved the ether bond and the hydroxyl group. The toxicity evaluation of RBV degradation products elucidated that UV/chlorine/Fe(II) process was beneficial for RBV detoxification. [ABSTRACT FROM AUTHOR]

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Aluminum (Al) ion implantation is one of the most important technologies in SiC device manufacturing processes due to its ability to produce the p-type doping effect, which is essential to building p–n junctions and blocking high voltages. However, besides the doping effect, defects are also probably induced by the implantation. Here, the impacts of Al ion implantation-induced defects on 4H-SiC MOSFET channel transport behaviors are studied using a multiscale simulation flow, including the molecular dynamics (MD) simulation, density functional theory (DFT) calculation, and tight-binding (TB) model-based quantum transport simulation. The simulation results show that an Al ion can not only replace a Si lattice site to realize the p-doping effect, but it can also replace the C lattice site to induce mid-gap trap levels or become an interstitial to induce the n-doping effect. Moreover, the implantation tends to bring additional point defects to the 4H-SiC body region near the Al ions, which will lead to more complicated coupling effects between them, such as degrading the p-type doping effect by trapping free hole carriers and inducing new trap states at the 4H-SiC bandgap. The quantum transport simulations indicate that these coupling effects will impede local electron transports, compensating for the doping effect and increasing the leakage current of the 4H-SiC MOSFET. In this study, the complicated coupling effects between the implanted Al ions and the implantation-induced point defects are revealed, which provides new references for experiments to increase the accepter activation rate and restrain the defect effect in SiC devices. [ABSTRACT FROM AUTHOR]

Single‐atom catalysts hold significance in the field of electrocatalysis. In this study, cobalt nitride (CoN), known for its semiconductor characteristics, is selected as the substrate, on which single gold (Au) atoms are loaded, to synthesize the catalyst Au SAC CoN@NF with Au single atoms anchored on CoN catalysts and grown on nickel foam. The introduction of single Au atoms results in an exceptional double‐layer capacitance (1425.7 mF cm−2), which offers immense possibilities for the applications of zinc–air batteries based on Au SAC CoN@NF. The zinc–air batteries demonstrated remarkable performance metrics, including a power density of 161.94 mW cm−2, a specific capacity of 813.80 mAh g−1, and a cycling stability of more than 260 h at 10 mA cm−2. In addition, these batteries show an outstanding round‐trip efficiency of 65.1%. Density functional theory calculations reveal that Au SAC CoN@NF can optimize the adsorption energies of intermediates for oxygen evolution reaction and promote single Au atoms in transporting electrons to the OH− species at an Au–N active site for oxygen reduction reaction. The proposed electronic metal‐support interaction strategy offers fresh insights for designing single‐atom catalysts to enhance electrocatalysis efficiency, thereby expanding the practical application prospects of zinc–air batteries. [ABSTRACT FROM AUTHOR]