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This contribution demonstrates density functional theory calculations on the optoelectronic properties of monoclinic CuO under high pressures up to 15 GPa. In this account, the experimentally measured indirect band gap energy value of 1.41 eV has theoretically been predicted by tuning the Hubbard parameter (U) values for the partial electronic states. The values of the Hubbard parameter correspond to UCu-3d = 8 eV and UO-2p = 4.5 eV. The electronic and optical characteristics were examined under applied pressure and the results reveal development in the band gap values with increasing pressure from 1.41 to 2.01 eV. Total and projected density of states for the adopted pressures have been provided and displayed that the major contribution in the valance and conduction bands comes from O-2p and Cu-3d electronic states, respectively. The plotted reflectivity data suggest high optical reflectivity magnitudes relatively in the ultraviolet area. The investigated systems under variant pressures manifest rather an excellent absorption coefficient in the ultraviolet area, pushing them to be employed in solar cell technologies. Our analyzed results of the wavelength-dependent electrical conductivity of the investigated materials confirm the absorptivity behavior in the ultraviolet and small part of visible region of electromagnetic waves (EMW). Finally and most importantly, our obtained results of loss functions for the entire surveyed systems reveal a slight energy loss in a range of EMW, including ultraviolet and visible regions. [ABSTRACT FROM AUTHOR]

Porous carbon derived from grape marc (GM) was synthesized via carbonization and chemical activation processes. Extrinsic nitrogen (N)-dopant in GM, activated by KOH, could render its potential use in supercapacitors effective. The effects of chemical activators such as potassium hydroxide (KOH) and zinc chloride (ZnCl2) were studied to compare their activating power toward the development of pore-forming mechanisms in a carbon electrode, making them beneficial for energy storage. GM carbon impregnated with KOH for activation (KAC), along with urea as the N-dopant (KACurea), exhibited better morphology, hierarchical pore structure, and larger surface area (1356 m2 g−1) than the GM carbon activated by ZnCl2 (ZnAC). Moreover, density functional theory (DFT) investigations showed that the presence of N-dopant on a graphite surface enhances the chemisorption of O adsorbates due to the enhanced charge-transfer mechanism. KACurea was tested in three aqueous electrolytes with different ions (LiOH, NaOH, and NaClO4), which delivered higher specific capacitance, with the NaOH electrolyte exhibiting 139 F g−1 at a 2 mA current rate. The NaOH with the alkaline cation Na+ offered the best capacitance among the electrolytes studied. A multilayer perceptron (MLP) model was employed to describe the effects of synthesis conditions and physicochemical and electrochemical parameters to predict the capacitance and power outputs. The proposed MLP showed higher accuracy, with an R2 of 0.98 for capacitance prediction. [ABSTRACT FROM AUTHOR]

The efficient separation and utilization of intrinsic carriers in photocatalyst, as well as the adsorption and elimination of target pollutants, are two critical challenges in the development of photocatalytic oxidation technology. Herein, the different crystal facet of Cu (111), Cu (100), Cu (111 +100) were engineered and coupled with Poly (heptazine imide) (PHI) as an emerging photocatalyst for CH 3 SH elimination under simulated solar light (SSL). Cu (111)/PHI exhibited 87.8% elimination efficiency after 30 min of illumination, significantly higher than that of pure PHI (60.4%), Cu (100)/PHI (71.5%), and Cu (111 +100)/PHI (70.4%). Besides, the photocatalytic performance was maintained at 83.3% after a prolonged reaction time of up to 450 min, indicating that Cu (111)/PHI has good stability and reusability. A comprehensive characterizations study confirmed that Cu (111) exhibited the enhanced surface electron pump effect compared to Cu (100) and Cu (111 +100), facilitating the accelerated extraction and transfer of photogenerated charge carriers. Density functional theory (DFT) calculations revealed that Cu (111) surface active sites can effectively adsorb H 2 O, O 2 , and CH 3 SH due to unsaturated pairing of d-orbital electrons, thus prompting the activation of H 2 O, O 2 into reactive oxygen species (•OH/•O 2 −/1O 2) for the eliminating of adjacent CH 3 SH. This study presents a new facet engineering approach for the rational design of highly efficient photocatalysts for the elimination of S-VOCs. [Display omitted] • Novel Cu (111)/PHI catalysts has efficiently photocatalytic elimination of CH 3 SH. • Cu (111) NCs with enhanced electron pump effect accelerates the transfer of photogenerated electrons. • Cu (111)/PHI has good adsorption and activation capacity for H 2 O and O 2. • Unsaturated electron filling of the antibonding energy levels enhances the catalytic activity. [ABSTRACT FROM AUTHOR]

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This contribution aims to investigate volume-dependent thermal and mechanical properties of the two most studied phases of molybdenum nitride (c-MoN and h-MoN) by means of the quasi-harmonic approximation approach (QHA) via first-principles calculations up to their melting point and a pressure of 12 GPa. Lattice constants, band gaps, and bulk modulus at 0 K match corresponding experimental measurements well. Calculated Bader's charges indicate that Mo-N bonds exhibit a more ionic nature in the cubic MoN phase. Based on estimated Gibbs free energies, the cubic phase presents thermodynamic stability higher than that detected for hexagonl, with no phase transition observed in the selected T- P conditions as detected experimentally. The elastic stiffness coefficients of MoN in hexagonal structure revealed that it is stable elastically; in contrast to the cubic structure. The temperature dependence on the bulk modulus is more profound on the dense cubic phase than on the hexagonal phase. Overall, the two considered structures of molybdenum nitride display very minimal harmonic effects, evidenced by the slight variation of thermal and mechanical properties with the increase of pressure and temperature. The optical conductivity of both phases near a zero photon energy coincides well with their metallic character inferred by their corresponding DOS curves. It is expected that the thermo-elastic properties of saturated molybdenum nitrides reported in this study will aid in the continuous pursuit to enhance their catalytic and mechanical utilizations. [ABSTRACT FROM AUTHOR]

Polyvinyl chloride (PVC) plastics constitute a large fraction of buildings, packaging and electronic devices, whereas, the annual emission electric arc furnace dust (EAFD) from steel manufacturing operations has recently peaked at nearly 6 Mt. Co-pyrolysis of PVC with EAFD currently represents a focal abatement technology for both categories of pollutants. However, despite of several experimental investigations; the mechanisms underlying interaction between EAFD and PVC remain largely speculative. Herein, we examine theoretically reactions of major products from thermal degradation of PVC with nanoclusters of iron (III) oxide, α -Fe 2 O 3 (hematite) as a representative model for the various metal oxides in EAFD. The facile nature for the H-Cl bond fission over hematite is in line with experimental findings, pointing out to formation of iron chlorides from pyrolysis of Fe 2 O 3 -PVC mixtures. Interaction of selected chlorinated C 1 -C 3 cuts with the hematite structure preferentially proceeds via a dissociative adsorption pathway. Results from this study shall be instrumental to understand, on a precise molecular basis, fixation of halogens on transitional metal oxides; a viable thermal recycling approach for polymeric materials laden with halogenated constituents. [ABSTRACT FROM AUTHOR]

Sol-gel derived CuCo-oxide coatings as solar selective surfaces, synthesized onto aluminium substrates at various annealing temperatures, are analysed by correlating their structural, chemical bonding states, and surface morphological topographies. As the annealing progressed, all the coatings displayed a Cu 0.56 Co 2.44 O 4 (ICSD 78-2175) phase with preferential orientation along (400) reflection plane. Rietveld refinement of X-ray diffraction (XRD) data indicate that residual stress and microstrains developed around the coating surfaces are reduced resulting in mechanically stable thin films. Enhancement of the crystallite size and preferred orientation of the surface were confirmed via XRD, field emission scanning electron microscopy (FESEM), and atomic force microscopy (AFM) analysis. X-ray photoelectron spectroscopy (XPS) analysis shows tetrahedral, octahedral and mixed states of Cu and Co ions with a stable atomic ratio of Co/Cu, and an increase of O and C contents but no metal-carbon bonding on the surface of materials. Optical reflectance investigations indicated that solar selectivity of the coatings increased from 3.81 to 24 as the annealing temperature reached up to 500 °C. [ABSTRACT FROM AUTHOR]

High temperature thermal-mechanical stability of tribological thin coatings is extremely important to a large number of applications in modern industries. DC magnetron sputtering of single metallic element (Cr, Si) and alloy (Ni:Cr) targets formed transition metal nitrides film coatings, CrSiN and CrNiN onto M2 steel. High temperature in-situ synchrotron X-ray diffraction, in the range 25 °C–700 °C, obtained experimental data for a range of structural and mechanical properties. Furthermore, experimental room temperature Nanoindentation measurements, made before and after the in-situ heating cycle, provided corresponding hardness and shear modulus results. The structural results identified microstructure and phase transformation changes, while the mechanical results identified microstrain, hardness, elastic modulus and deformation resistance properties of the coatings. Density functional theory (DFT) and quasi-harmonic approximation (QHA) modelled the high temperature thermal and mechanical properties such as: Young's modulus, shear modulus and thermal expansion coefficients (populated up to 1200 °C). Estimates of hardness are made by correlating the bulk phase hardness and shear modulus, of the CrN and Ni phases, as a function of temperature. Results indicate that Si doping enhances the hardness of the CrN framework, increasing from 29 to 36 GPa and improves the coatings elastic modulus, and resistance to deformation. However the addition of Ni reduced these properties. Furthermore, formation of (Cr,Si)N and Ni(Cr) solid solutions is inferred from DFT, Rietveld and lattice constant analysis.

In this work, the physicochemical properties of palm oil fuel ash (POFA) based geopolymers with the addition of graphene oxide (GO) were investigated. Geopolymer composites were prepared by mixing the treated POFA, sand, NaOH, Na 2 SiO 3 , and GO. The mixtures were then cast in mortar molds to form the geopolymer composites, with different GO proportions and curing temperatures applied to the composites. Compressive strength, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) analyses, as well as density functional theory (DFT) calculations, have been performed. The compressive test results showed that the compressive strength increased proportionally with the increase of GO content and decreased when there was an excess of GO. The excessive GO and the limited amount of NaOH activator solution inhibited the formation of reduced graphene oxide (rGO) via an in-situ reduction mechanism. The FTIR and SEM analyses revealed that the excess GO tended to promote the formation of epoxy groups on the GO, which eventually confined the formation of dense agglomeration and led to a decrease in compressive strength. The DFT calculations confirmed the significance of the epoxy group stretching. Overall, the ratio of NaOH to GO is a crucial factor in determining the mechanical properties of geopolymers-GO composites. [ABSTRACT FROM AUTHOR]

CrN, one of the most investigated transition metal nitrides, is noted for its wear, corrosion, and oxidation resistance. It also has many other unique chemical and mechanical properties. In the present study, we conducted a density functional theory (DFT) analysis to probe the structural, electronic, and optical properties of pristine and Mo-doped CrN structures in non-crystalline phases using different combinations in which one or two Cr and/or N atoms were substituted by Mo. This study found that the Cr 4 Mo 2 N 2 structure was chemically and energetically the most stable species among the six considered clusters (Cr 4 N 4 , Cr 3 Mo 2 N 3 , Cr 4 Mo 2 N 2 , Cr 2 Mo 2 N 4 , Cr 4 MoN 3 , and Cr 3 MoN 4). The DFT-derived electronic structure predicted that the Cr 3 Mo 2 N 3 and Cr 4 MoN 3 clusters possess magnetic susceptibility. Computed infrared (IR), Raman, and ultraviolet–visible (UV–Vis) analyses indicated that the Cr 4 N 4 and Cr 4 Mo 2 N 2 clusters were naturally stable. This should enable these clusters to serve as light-harnessing materials for strategic applications in solar selective surfaces. [ABSTRACT FROM AUTHOR]

• Very-few-layer graphene (VFLG) can be produced using facile and green process. • VFLG consists of 1–3 layers which is dominated by single layer graphene. • VFLG has edge chirality of armchairs and zigzag with mean lateral size of ~375.4 nm. • DFT calculations provided pertinent optical/electronic properties of graphene. A defect-free graphene with 1–3 layers (very-few-layer graphene, VFLG) has been successfully produced using a facile and environmentally friendly two-step shear exfoliation method in rotating-blade mixer (kitchen blender) and in high shear rotor–stator mixer. An aqueous solution containing an inexpensive and safe anionic surfactant of sodium lauryl sulphate (SLS) was deployed as the working fluid. Raman spectroscopy (RS) and Raman imaging (RI), density functional theory (DFT) simulation, transmission electron microscopy and high-resolution transmission electron microscopy (TEM-HRTEM), as well as Fourier-transform infrared spectroscopy (FTIR) analyses were used to characterize the samples. Some configurations of mixer setting were applied, and the exfoliation mechanisms were discussed. RS analysis revealed that the exfoliation process in rotating-blade mixer continued by high shear in rotor–stator mixer for 3 h had produced VFLG dominated by a single layer of graphene. The Lorentzian peak fitting of 2D band was well-fitted by a single Lorentzian component at Raman shift of 2651.317 cm−1. The produced VFLG endured the lowest peak intensity ratio of D and G bands (I D /I G) of 0.146 which corresponded with the highest lateral size. RI analysis showed that produced VFLG had edge chirality of armchairs and zigzag terminations. TEM-HRTEM confirmed the presence of VFLG with the highest mean lateral size of ~375.4 nm. DFT calculations provided pertinent optical/electronic properties of graphene in terms of Raman Spectra, density of states (DOS) curve and nuclear magnetic resonance (NMR) shielding tensor. FTIR analysis showed that the exfoliation process did not cause any oxidation, sulphonation, or functional defects on the VFLG. The turbulence and hydrodynamic force in liquid were the critical factors in the exfoliation processes. High-quality VFLG, with a facile, inexpensive, and environmentally friendly synthesis process, rendered this process to be a promising route for large-scale high-quality graphene production. [ABSTRACT FROM AUTHOR]

The elevated metaldehyde (a toxic molluscicide) concentrations in UK and EU water bodies are a major concern among water treatment professionals and related stakeholders. The difficulty of removing metaldehyde using conventional water treatment methods has motivated researchers to develop more effective treatment solutions. In this contribution, we have utilized density functional theory (DFT) to fundamentally investigate the adsorptive interactions (e.g. binding energy) between metaldehyde and sulfonic functional group in an ion exchange resin. Adsorption of the cationic metaldehyde on deprotonated sulfonic group is substantial with a binding energy amounting to 130.9 kcal/mol. Preliminary results on an experimental study involving adsorption of metaldehyde on ion exchange resin are also reported. Our findings would complement the existing body of knowledge on metaldehyde removal. Unlabelled Image • We study adsorptive interactions between metaldehyde and sulfonic functional group. • This occurs in an ion exchange resin. • Adsorption (binding) energies are calculated using density functional theory. • Binding energy of cationic metaldehyde-deprotonated sulfonic group = 130.9 kcal/mol. [ABSTRACT FROM AUTHOR]

Co-pyrolysis of brominated flame retardants (BFRs) with polymeric materials prevails in scenarios pertinent to thermal recycling of bromine-laden objects; most notably the non-metallic fraction in e-waste. Hydro-dehalogenation of aromatic compounds in a hydrogen-donating medium constitutes a key step in refining pyrolysis oil of BFRs. Chemical reactions underpinning this process are poorly understood. Herein, we utilize accurate density functional theory (DFT) calculations to report thermo-kinetic parameters for the reaction of solid polyethylene, PE, (as a surrogate model for aliphatic polymers) with prime products sourced from thermal decomposition of BFRs, namely, HBr, bromophenols; benzene, and phenyl radical. Facile abstraction of an ethylenic H by Br atoms is expected to contribute to the formation of abundant HBr concentrations in practical systems. Likewise, a relatively low energy barrier for aromatic Br atom abstraction from a 2-bromophenol molecule by an alkyl radical site, concurs with the reported noticeable hydro-debromination capacity of PE. Pathways entailing a PE-induced bromination of a phenoxy radical should be hindered in view of high energy barrier for a Br transfer into the para position of the phenoxy radical. Adsorption of a phenoxy radical onto a Cu(Br) site substituted at the PE chain affords the commonly discussed PBDD/Fs precursor of a surface-bounded bromophenolate adduct. Such scenario arises due to the heterogeneous integration of metals into the bromine-rich carbon matrix in primitive recycling of e-waste and their open burning. Image 1 • Hydro-dehalogenation of aromatic compounds constitutes a key step in refining pyrolysis oil of BFRs. • We describe the interaction of a bromphenoxy radical with a PE-Cu(Br) configuration. • Such a scenario arises in primitive recycling of e-waste and their open burning. • Computed parameters are useful for understanding the combustion chemistry of BFRs-polymers blends. [ABSTRACT FROM AUTHOR]