The influence of carbon atom distribution in precursors with 1:1 carbon to silicon atoms ratio on structure and thermal evolution of obtained silicon oxycarbide based materials

In this work, a number of precursors with 1:1 silicon to carbon atoms ratio and various carbon atom distributions were synthesized and pyrolyzed in order to obtain silicon oxycarbide based materials. The different carbon atom distributions were obtained using both simple monomers with only one silicon atom, as well as large monomers containing either four or sixteen silicon atoms with predefined carbon atom positions. The silicon oxycarbide based materials were investigated using IR, XRD, ²⁹Si MAS NMR and elemental analysis after annealing at various temperatures, as well as TG. The research shows that carbon atom distribution has great impact on the structure of final material and can be used to tailor the material for its projected uses.     

Carbon corrosion mechanism on nitrogen-doped carbon support — A density functional theory study

In this work, density functional theory (DFT) calculations were used to investigate the mechanism of carbon corrosion on nitrogen-doped carbon support. Free energy diagrams were generated based on three proposed reaction pathways to evaluate corrosion mechanisms. The most energetically preferred mechanism on nitrogen-doped carbon was determined. The results show that the step of water dissociation to form ^#OH was the rate-determining step for gra-G-1N (graphene doped with graphitic N) and pyrr-G-1N (graphene doped with pyrrolic N). As for graphene doped with pyridinic N, the step of C^#OC^#O formation was critical. It was found that the control of nitrogen concentration was necessary for precisely designing optimized carbon materials. Abundance of nitrogen moieties aggravated the carbon corrosion. When the high potential was applied, specific types of graphitic N and pyridinic N were found to be favorable carbon modifications to improve carbon corrosion resistance. Moreover, the solvent effect was also investigated. The results provide theoretical insights and design guidelines to improve corrosion resistance in carbon support through material modification by inhibiting the adsorption of surface oxides (OH, O, and OOH).     

Phase composition,microstructure, and properties of Al4O4C–(Al2OC)1-x(AlN)x –Zr2Al3C4–Al2O3 refractories prepared at high temperatures in nitrogen

The novel Al₄O₄C–(Al₂OC)_1-x(AlN)_x–Zr₂Al₃C₄–Al₂O₃ refractories with ultra-low carbon content have been successfully prepared by constructing the core-shell structure of aluminum at 1300–1700°C in nitrogen. The phase composition, microstructure, and properties of the novel refractories are deeply investigated. The cracking temperature on the core-shell structure of aluminum is further explored and the reaction mechanism of Zr₂Al₃C₄ has also added explanation. The results show that the novel refractories have excellent physical properties and cannot be corroded by molten iron. There exist two different Al₂OC solid solutions in the novel refractories, Al₂OC-rich (Al₂OC)_1-x(AlN)_x and AlN-rich (Al₂OC)_1-x(AlN)_x. The temperatures affect their relative content. When temperatures are less than 1600°C, the relative content of Al₂OC-rich (Al₂OC)_1-x(AlN)_x is more than that of AlN-rich (Al₂OC)_1-x(AlN)_x. When temperatures are above 1700°C, the relative content of AlN-rich (Al₂OC)_1-x(AlN)_x is more than that of Al₂OC-rich (Al₂OC)_1-x(AlN)_x. The core-shell structure of aluminum fully ruptures at about 1200°C. Zr₂Al₃C₄ begins to form at about 1000°C and generates in large at 1200°C.     

Potential influence of microorganisms on the corrosion of carbon steel in the French high- and intermediate-level long-lived radioactive waste disposal context

In the context of the high-level radioactive waste disposal CIGEO, the corrosion rate due to microbially influenced corrosion (MIC) has to be evaluated. In France, it is envisaged to dispose of high- and intermediate-level long-lived radioactive waste at a depth of 500 m in a deep geological disposal, drilled in the Callovo-Oxfordian claystone (Cox) formation. To do so, a carbon steel casing will be inserted inside disposal cells, which are horizontal tunnels drilled in the Cox. A specific cement grout will be injected between the carbon steel casing and the claystone. A study was conducted to evaluate the possibility of MIC on carbon steel in the foreseeable high radioactive waste disposal. The corrosiveness of various environments was investigated at 50°C and 80°C with or without microorganisms enriched from samples of Andra's underground research laboratory. The monitoring of corrosion during the experiments was ensured using gravimetric method and real-time corrosion monitoring using sensors based on the measurements of the electrical resistance. The corrosion data were completed with microbiological analyses including cultural and molecular characterizations.     

Thermal transport and chemical conversion in single reacting sorbent particles

The effects of particle size and carbon dioxide concentration on chemical conversion in engineered spherical particles undergoing calcium oxide looping are investigated. Particles are thermochemically cycled in a furnace under different carbon dioxide concentrations. Changes in composition due to chemical reactions are measured using thermogravimetric analysis. Gas composition at the furnace exit is evaluated with mass spectroscopy. A numerical model of thermal transport phenomena developed previously is adapted to match the physical system investigated in the present study. The model is used to elucidate effects of reacting medium characteristics on particle temperature and reaction extent. Experimental and numerical results show that (1) an increase in particle size results in a decrease in carbonation extent, and (2) the carbonation step consists of fast and slow reaction regimes. The reaction rates in the fast and slow carbonation regimes increase with increasing carbon dioxide concentration. The effect of carbon dioxide concentration and the distinction between the fast and slow regimes become more pronounced with increasing particle size.     

In Silico Investigation of Potential Applications of Gamma Carbonic Anhydrases as Catalysts of CO2 Biomineralization Processes: A Visit to the Thermophilic Bacteria Persephonella hydrogeniphila,Persephonella marina,Thermosulfidibacter takaii,and Thermus thermophilus

Carbonic anhydrases (CAs) have been identified as ideal catalysts for CO₂ sequestration. Here, we report the sequence and structural analyses as well as the molecular dynamics (MD) simulations of four γ-CAs from thermophilic bacteria. Three of these, Persephonella marina, Persephonella hydrogeniphila, and Thermosulfidibacter takaii originate from hydrothermal vents and one, Thermus thermophilus HB8, from hot springs. Protein sequences were retrieved and aligned with previously characterized γ-CAs, revealing differences in the catalytic pocket residues. Further analysis of the structures following homology modeling revealed a hydrophobic patch in the catalytic pocket, presumed important for CO₂ binding. Monitoring of proton shuttling residue His69 (P. marina γ-CA numbering) during MD simulations of P. hydrogeniphila and P. marina’s γ-CAs (γ-PhCA and γ-PmCA), showed a different behavior to that observed in the γ-CA of Escherichia coli, which periodically coordinates Zn²⁺. This work also involved the search for hotspot residues that contribute to interface stability. Some of these residues were further identified as key in protein communication via betweenness centrality metric of dynamic residue network analysis. T. takaii’s γ-CA showed marginally lower thermostability compared to the other three γ-CA proteins with an increase in conformations visited at high temperatures being observed. Hydrogen bond analysis revealed important interactions, some unique and others common in all γ-CAs, which contribute to interface formation and thermostability. The seemingly thermostable γ-CA from T. thermophilus strangely showed increased unsynchronized residue motions at 423 K. γ-PhCA and γ-PmCA were, however, preliminarily considered suitable as prospective thermostable CO₂ sequestration agents.     

Iron(II) Sulfate(VI) from Titania Production as a Raw Material for Preparation of Hydrogen Sulfide Sorbents

A hybrid sorbent material for removal of hydrogen sulfide from air was developed. The material is based on activated carbon and iron compounds obtained from waste iron(II) sulfate(VI) heptahydrate. The iron salt is deposited on the carbonaceous support and subjected to oxidation (Fe²⁺ to Fe³⁺) using atmospheric oxygen under alkaline conditions. An effect of H₂O₂ addition to the process on the composition of the resultant material was also examined. X-ray diffraction (XRD) analyses confirmed easy conversion of waste FeSO₄·7H₂O to iron oxides Fe₃O₄ and FeOOH. The activated carbon supporting iron oxides revealed a higher efficiency in H₂S elimination from air compared to the commercial activated carbon, without any modification.     

Platinum nanoparticles decorated on graphitic carbon nitride-ZIF-67 composite support: An electrocatalyst for the oxidation of butanol in fuel cell applications

In the present study, we report an eco-friendly and simple route to design and synthesize novel nanocomposite catalyst based on platinum nanoparticles anchored on binary support of graphitic carbon nitride (g-C₃N₄) and cobalt-metal-organic framework (ZIF-67). For this purpose, ZIF-67 was prepared by precipitation method and g-C₃N₄ was prepared through thermal polymerization method. Later, ZIF-67 and g-C₃N₄ were hybridized through sonication to get homogeneous g–C₃N₄–ZIF-67 nanocomposite support material. Platinum nanoparticles (PtNPs) were uniformly deposited on g–C₃N₄–ZIF-67 by an electrochemical method. The as-developed nanocatalyst was characterized by morphological, structural and electrochemical techniques. The electrocatalytic activity of PtNPs@g–C₃N₄–ZIF-67 nanocatalyst towards butanol oxidation was evaluated via CV, CA, LSV and EIS in an alkaline medium. Results revealed that the proposed catalyst showed greatly enhanced electrooxidation of butanol in terms of high magnificent current density, lower oxidation potential, excellent long-term stability, large surface area, low charge transfer resistance and less toxic ability. Enhanced catalytic performance of the proposed catalyst could be ascribed to the synergistic effect of g–C₃N₄–ZIF-67 nanocomposite and PtNPs. The PtNPs@g–C₃N₄–ZIF-67 catalyst holds promising potential applications to be used as an anodic electrocatalyst for the development of high-performance alkaline fuel cells.