Computational mechanistic study of the unimolecular dissociation of ethyl hydroperoxide and its bimolecular reactions with atmospheric species

A detailed computational study of the atmospheric reaction of the simplest Criegee intermediate CH2OO with methane has been performed using the density functional theory (DFT) method and high-level calculations. Solvation models were utilized to address the effect of water molecules on prominent reaction steps and their associated energies. The structures of all proposed mechanisms were optimized using B3LYP functional with several basis sets: 6-31G(d), 6-31G (2df,p), 6-311++G(3df,3pd) and at M06-2X/6-31G(d) and APFD/6-31G(d) levels of theory. Furthermore, all structures were optimized at the B3LYP/6-311++G(3df,3pd) level of theory. The intrinsic reaction coordinate (IRC) analysis was performed for characterizing the transition states on the potential energy surfaces. Fifteen different mechanistic pathways were studied for the reaction of Criegee intermediate with methane. Both thermodynamic functions (ΔH and ΔG), and activation parameters (activation energies Ea, enthalpies of activation ΔHǂ, and Gibbs energies of activation ΔGǂ) were calculated for all pathways investigated. The individual mechanisms for pathways A1, A2, B1, and B2, comprise two key steps: (i) the formation of ethyl hydroperoxide (EHP) accompanying with the hydrogen transfer from the alkanes to the terminal oxygen atom of CIs, and (ii) a following unimolecular dissociation of EHP. Pathways from C1 → H1 involve the bimolecular reaction of EHP with different atmospheric species. The photochemical reaction of methane with EHP (pathway E1) was found to be the most plausible reaction mechanism, exhibiting an overall activation energy of 7 kJ mol−1, which was estimated in vacuum at the B3LYP/6-311++G(3df,3pd) level of theory. All of the reactions were found to be strongly exothermic, expect the case of the sulfur dioxide-involved pathway that is predicted to be endothermic. The solvent effect plays an important role in the reaction of EHP with ammonia (pathway F1). Compared with the gas phase reaction, the overall activation energy for the solution phase reaction is decreased by 162 and 140 kJ mol−1 according to calculations done with the SMD and PCM solvation models, respectively

Chlorine Fixing Ability of Electric Arc Furnace Dust During the Thermal Degradation of Polyvinyl Chloride under Oxidative Conditions

Electric arc furnace dust (EAFD) and polyvinyl chloride (PVC) are two hazardous wastes that are accumulated world-wide at an alarming rate. Utilising these two wastes simultaneously towards a sustainable recycling loop can greatly mitigate their environmental impact. Herein, EAFD was studied as a potential emission fixator of evolved gaseous HCl generated from the thermal decomposition of PVC under different operational conditions: EAFD-PVC mass ratio, solid reactants geometry, O2 partial pressure, holding temperature, holding time and heating rate. The highest chlorine fixation percentage was calculated to be 78.9% and was obtained at an EAFD-PVC mass ratio of 1:1 (thin disks geometry), while the rest escaped in the form of HCl/Cl2. No significant variation was observed on the percentage of fixed chlorine when the thermal treatment was performed using different geometries: long cylinder, thin disks, and powder forms with a maximum difference in fixation of only 5.6% between extremities. Increasing O2 partial pressure positively affected the chlorine fixation percentage increasing it from 39.9 to 48.4% at 0 and 21 kPa partial pressures, respectively. Increasing both the holding temperature and holding time under oxidative conditions negatively affected the percentage of fixed chlorine due to oxidation of formed FeCl2 back to Fe2O3. The heating rate did not show any significant effect on the amount of fixed HCl, suggesting that the speed of chlorination reactions can be identical to or faster than the decomposition rate of PVC. Overall, EAFD is believed to be an excellent candidate for capturing HCl contained in PVC upon thermal degradation

Hydrostatic bath synthesis of conductive polypyrrole/reduced graphene oxide aerogel as compression sensor

A conductive and elastic polypyrrole/reduced graphene oxide aerogel (PGA) was synthesized through a hydrostatic bath method followed by freeze-drying. Through this method, the self-agglomeration and oxidative polymerization of rGO and polypyrrole occurred synergistically in a controlled environment, which resulted in a 3D conductive aerogel matrix. The optical spectroscopy, including FT-IR and XPS, showed the distinguished vibration band of polypyrrole and π-π interaction, which evidenced the successful polymerization of the pyrrole monomer through the synergistic assembly process. The presence of flexible rGO nanosheets as an aerogel backbone provided a strong mechanical support and deposition sites for polypyrrole nanoparticles, which contributed to the overall elasticity. Furthermore, the polypyrrole nanoparticles not only addressed the stacking issue of rGO but further enhanced the reactive surface area by eight times of magnitude compared to pure graphene aerogel (GA) produced by the same technique. Molecular modeling estimates adsorption energies for the polypyrrole molecule over the rGO surface and further predict the dominant functional group that involve in the formation of PGA. The as-synthesized PGA provide a significant electrical resistance changes (>80%) before and after compression, which responded exceptionally well upon compression by lighting up LEDs that were arranged in parallel in an electrical circuit

Photodecomposition properties of brominated flame retardants (BFRs)

This study investigates the geometric and electronic properties of selected BFRs in their ground (S0) and first singlet excited (S1) states deploying methods of the density functional theory (DFT) and the time-dependent density functional theory (TDDFT). We estimate the effect of the S0 → S1 transition on the elongations of the C–Br bond, identify the frontier molecular orbitals involved in the excitation process and compute partial atomic charges for the most photoreactive bromine atoms. The bromine atom attached to an ortho position in HBB (with regard to C–C bond; 2,2ʹ,4,4ʹ,6,6ʹ-hexabromobiphenyl), TBBA (with respect to the hydroxyl group; 2,2ʹ,6,6ʹ-tetrabromobisphenol A), HBDE and BTBPE (in reference to C–O linkage; 2,2ʹ,4,4ʹ,6,6ʹ-hexabromodiphenylether and 1,2-bis(2,4,6-tribromophenoxy)ethane, respectively) bears the highest positive atomic charge. This suggests that, these positions undergo reductive debromination reactions to produce lower brominated molecules. Debromination reactions ensue primarily in the aromatic compounds substituted with the highest number of bromine atoms owing to the largest stretching of the C–Br bond in the first excited state. The analysis of the frontier molecular orbitals indicates that, excitations of BFRs proceed via π→π*, or π→σ* or n→σ* electronic transitions. The orbital analysis reveals that, the HOMO-LUMO energy gap (EH−L) for all investigated bromine-substituted aromatic molecules falls lower (1.85–4.91 eV) than for their non-brominated analogues (3.39–8.07 eV), in both aqueous and gaseous media. The excitation energies correlate with the EH−L values. The excitation energies and EH−L values display a linear negative correlation with the number of bromine atoms attached to the molecule. Spectral analysis of the gaseous-phase systems reveals that, the highly brominated aromatics endure lower excitation energies and exhibit red shifts of their absorption bands in comparison to their lower brominated congeners. We attained a satisfactory agreement between the experimentally measured absorption peak (λmax) and the theoretically predicted oscillator strength (λmax) for the UV–Vis spectra. This study further confirms that, halogenated aromatics only absorb light in the UV spectral region and that effective photodegradation of these pollutants requires the presence of photocatalysts.This study has been supported by the Australian Research Council (ARC), and grants of computing time from the National Computational Infrastructure (NCI), Australia as well as the Pawsey Supercomputing Centre. A.S. and K.S. thanks Murdoch University, Australia, for a postgraduate research scholarship

Thermal analysis on the pyrolysis of tetrabromobisphenol A (TBBPA) and Electric Arc Furnace Dust mixtures

The pyrolysis of Tetrabromobisphenol A (TBBPA) mixed with Electric Arc Furnace Dust (EAFD) was studied using thermogravimetric analysis (TGA) and theoretically analysed using thermodynamic equilibrium calculations. Mixtures of both materials with varying TBBPA loads (1:1, and 1:3) were prepared and pyrolyzed in a nitrogen atmosphere under dynamic heating conditions at heating rates of 5 and 10 ⁰C/min. The mixtures degraded through several steps including decomposition of TBBPA yielding mainly HBr, bromination of metal oxides, followed by their evaporation in the sequence of CuBr3, ZnBr2, PbBr2, FeBr2, MnBr2, KBr, NaBr, CaBr2 and MgBr2, and finally reduction of the remaining metal oxides by the char formed from decomposition of TBBPA. Thermodynamic calculations suggest the possibility of selective bromination of zinc and lead followed by their evaporation leaving iron in its oxide form, while the char formed may serve as a reduction agent for iron oxides into metallic iron. However, at higher TBBPA volumes, iron bromide forms, which can be also evaporated at a temperature higher than those of ZnBr2 and PbBr2. Results from this work provide practical insight into selective recovery of valuable metals from EAFD while at the same time recycling the hazardous bromine content in TBBPA

Monatomic reactions with single vacancy monolayer h-BN: DFT studies

Hexagonal boron nitride (h-BN) has been widely utilized in various strategic applications. Fine-tuning properties of BN towards the desired application often involves ad-atom adsorption of modifying its geometries through creating surface defects. This work utilizes accurate DFT computations to investigate adsorption of selected 1st and 2nd row elements (H, Li, C, O, Al, Si, P, S) of the periodic table on various structural geometries of BN. The underlying aim is to assess the change in key electronic properties upon the adsorption process. In addition to the pristine BN, B and N vacancies were comprehensively considered and a large array of properties (i.e., atomic charges, adsorption energies, density of states) were computed and contrasted among the eight elements. For instance, we found that the band gap to vary between 0.33 eV (in case of Li) and 4.14 eV (in case of P). Likewise, we have illustrated that magnetic contribution to differ substantially depending on the adatom adsorbents. Results from this work has also lays a theoretical foundation for the use of decorated and defected BN as a chemical sensor for CO gase

Development of Organo-Dispersible Graphene Oxide via Pseudo-Surface Modification for Thermally Conductive Green Polymer Composites

Graphene has attracted lots of researchers attention because of its remarkable conductivity in both electrically and thermally. However, it has poor dispersibility in organic solvents which limited its applications. Polymers with aromatic end group which act as an intercalator were prepared by ring-opening polymerization with ε-caprolactone by utilizing 1-naphthalene methanol (1-NM) as an initiator. These intercalators will exist between graphene oxide (GO) sheets to prevent aggregation via interactions. The attachment of 1-NM on polymer chains was supported by ultraviolet–visible spectra, size exclusion chromatography profiles, and 1H nuclear magnetic resonance spectra. Exfoliated structured functionalized GO (fGO)/polycaprolactone (PCL) (synthesized fGO) nanocomposites that dispersed well in acetone, chloroform, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, and toluene were successfully synthesized. This agreed well with the enlarged interlayer spacing in the optimized fGO as compared to that of GO from density functional theory simulations using the DMol3 module that implemented in the Materials Studio 6.0. Furthermore, its potential to be applied as green electronics in electronics, aerospace, and automotive industries was presented, by trailering the thermal conductivity enhancement from the incorporation of fGO/PCL with commercialized biodegradable polymers, PCL, and poly[(R)-3-hydroxybutyric acid]

Co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants

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

CO2 capture and ions removal through reaction with potassium hydroxide in desalination reject brine: Statistical optimization

Previous studies have investigated the overall performance of the modified Solvay process based on a new alkaline compound, namely, KOH. Preliminary results have confirmed its high reactivity and effectiveness in capturing CO2 and managing reject brine. In this study, parametric sensitivity analysis has been carried out to optimize the operating conditions and thereby maximize CO2 capture and ions removal from high-salinity brines. Response surface methodology (RSM) analysis using the central composite design (CCD) approach was implemented to statistically determine the impact of important operating conditions, including KOH concentration (30–110 g/l), CO2 gas flow rate (400–1600 ml/min), gauge pressure (1–3 barg), and temperature (10–50 °C) on key response process output variables, such as CO2 uptake and ions reduction. The importance of these parameters and their interactions were confirmed by employing analysis of variance (ANOVA) approach at a confidence level of 95% (p < 0.05). These analyses demonstrated that under the optimized conditions of a temperature of 10 °C, gauge pressure of 2.1 barg, CO2 gas flow rate of 848.5 ml/min, KOH concentration of 110 g/l, and an inert mixing particle volume fraction of 15%, a maximum CO2 uptake value of 0.58 g/g KOH, maximum sodium (Na+) removal of 44.1%, chloride (Cl−) removal of 40.1%, calcium (Ca2+) removal of 100%, and magnesium (Mg2+) removal of 99.8% were achieved. The characterization of the collected solid products at optimum conditions revealed the production of valuable and useful products, particularly sodium and potassium bicarbonates, in addition to KCl.Open Access funding is provided by the Qatar National Library.Scopu

Phenol Dissociation on Pristine and Defective Graphene

Phenol (C6H5O‒H) dissociation on both pristine and defective graphene sheets in terms of associated enthalpic requirements of the reaction channels was investigated. Here, we considered three common types of defective graphene, namely, Stone-Wales, monovacancy and divacancy configurations. Theoretical results demonstrate that, graphene with monovacancy creates C atoms with dangling bond (unpaired valence electron), which remains particularly useful for spontaneous dissociation of phenol into phenoxy (C6H5O) and hydrogen (H) atom. The reactions studied herein appear barrierless with reaction exothermicity as high as 2.2 eV. Our study offers fundamental insights into another potential application of defective graphene sheets