Density functional theory study of the hydrogen evolution reaction in haeckelite boron nitride quantum dots

To satisfy arising energy needs and to handle the forthcoming worldwide climate transformation, the major research attention has been drawn to environmentally friendly, renewable and abundant energy resources. Hydrogen plays an ideal and significant role is such resources, due to its non-carbon based energy and production through clean energy. In this work, we have explored catalytic activity of a newly predicted haeckelite boron nitride quantum dot (haeck-BNQD), constructed from the infinite BN sheet, for its utilization in hydrogen production. Density functional theory calculations are employed to investigate geometry optimization, electronic and adsorption mechanism of haeck-BNQD using Gaussian16 package, employing the hybrid B3LYP and wB97XD functionals, along with 6–31G(d,p) basis set. A number of physical quantities such as HOMO/LUMO energies, density of states, hydrogen atom adsorption energies, Mulliken populations, Gibbs free energy, work functions, overpotentials, etc., have been computed and analysed in the context of the catalytic performance of haeck-BNQD for the hydrogen-evolution reaction (HER). Based on our calculations, we predict that the best catalytic performance will be obtained for H adsorption on top of the squares or the octagons of haeck-BNQD. We hope that our prediction of most active catalytic sites on haeck-BNQD for HER will be put to test in future experiments.     

Recent insights in synthesis and energy storage applications of porous carbon derived from biomass waste: A review

In the last few decades, global warming, environmental pollution, and an energy shortage of fossil fuel may cause a severe economic crisis and health threats. Storage, conversion, and application of regenerable and dispersive energy would be a promising solution to release this crisis. The development of porous carbon materials from regenerated biomass are competent methods to store energy with high performance and limited environmental damages. In this regard, bio-carbon with abundant surface functional groups and an easily tunable three-dimensional porous structure may be a potential candidate as a sustainable and green carbon material. Up to now, although some literature has screened the biomass source, reaction temperature, and activator dosage during thermochemical synthesis, a comprehensive evaluation and a detailed discussion of the relationship between raw materials, preparation methods, and the structural and chemical properties of carbon materials are still lacking. Hence, in this review, we first assess the recent advancements in carbonization and activation process of biomass with different compositions and the activity performance in various energy storage applications including supercapacitors, lithium-ion batteries, and hydrogen storage, highlighting the mechanisms and open questions in current energy society. After that, the connections between preparation methods and porous carbon properties including specific surface area, pore volume, and surface chemistry are reviewed in detail. Importantly, we discuss the relationship between the pore structure of prepared porous carbon with surface functional groups, and the energy storage performance in various energy storage fields for different biomass sources and thermal conversion methods. Finally, the conclusion and prospective are concluded to give an outlook for the development of biomass carbon materials, and energy storage applications technologies. This review demonstrates significant potentials for energy applications of biomass materials, and it is expected to inspire new discoveries to promote practical applications of biomass materials in more energy storage and conversion fields.     

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.     

Effect of aluminium acetyl acetonate on the hydrogen and nitrogen permeation of carbon molecular sieves membranes

With a growing interest in hydrogen as energy carrier, the efficient purification of hydrogen from gaseous mixtures is very important. This paper addresses the separation of hydrogen using Carbon Molecular Sieves Membranes (CMSM), which show an attractive combination of high permeability, selectivity and stability. Supported CMSM containing various amounts of aluminium have been prepared from novolac and aluminium acetyl acetonate (Al(acac)₃) as carbon and alumina precursors. The thickness of the CMSM layers depend on the content of Al(acac)₃ in the dipping solution, which also has influence in the pore size and pore size distribution of the membranes. The permeation properties of the membranes against the Al content in the membrane follows a volcano shape, where the membrane containing 4 wt (%) of Al(acac)₃ has the best properties and was stable during 720 h for hydrogen at 150 °C and 6 bar pressure difference. All the CMSM have permeation properties well above the Robeson Upper limit.     

Ammonia production using iron nitride and water as hydrogen source under mild temperature and pressure

Ammonia generation was studied in the reaction between water and nitrogen-containing iron at 323 K and atmospheric pressure. Similar to metallic Fe, the interstitial compound Fe₃N reduced water through Fe oxidation to produce hydrogen gas, while the N combined with atomic hydrogen to produce ammonia as a byproduct. The addition of carbon dioxide to this system accelerated the reaction with concomitant consumption of carbon dioxide. The promoted ammonia production upon addition of carbon dioxide can be attributed to the generation of atomic hydrogen from the redox reaction of carbonic acid and Fe, as well as removal of used Fe from the reaction system through the formation of a soluble carbonato complex. When carbonate was added to the reaction system, the production rates of ammonia and hydrogen increased further. The results here confirmed that ammonia can be synthesized from iron nitride under mild conditions by utilizing carbon dioxide.     

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).     

Wear and corrosion properties of wollastonite and boron nitride doped,hydroxyapatite-based HAp-Wo-BN composite coatings prepared by pulsed laser deposition

In this study, hydroxyapatite-based hydroxyapatite-wollastonite-boron nitride (HAp-Wo-BN) composite film was formed on the surface of Ti6Al4V by pulsed laser deposition (PLD). Based on a survey in scientific literature, it is presumed that this is the first time such a process is being undertaken. The wear and corrosion resistance of this film were analyzed comparatively in simulated body fluid (SBF) to simulate the human body environment. In the coating, HAp was used to form a bone-like layer, wollastonite was to enhance bone-tissue regeneration and BN was used for its bone-tissue healing and anti-bacterial properties. The results showed that the wear as well as the corrosion resistance of all samples after PLD treatment increased. Relatively the best wear resistance was achieved from boron nitride and wollastonite doped hydroxyapatite layers, where the best corrosion resistance was from the ones that consisted of only hydroxyapatite.     

Epitaxial Growth of 2D Materials on High-Index Substrate Surfaces

Recently, the successful synthesis of wafer-scale single-crystal graphene, hexagonal boron nitride (hBN), and MoS₂ on transition metal surfaces with step edges boosted the research interests in synthesizing wafer-scale 2D single crystals on high-index substrate surfaces. Here, using hBN growth on high-index Cu surfaces as an example, a systematic theoretical study to understand the epitaxial growth of 2D materials on various high-index surfaces is performed. It is revealed that hBN orientation on a high-index surface is highly dependent on the alignment of the step edges of the surface as well as the surface roughness. On an ideal high-index surface, well-aligned hBN islands can be easily achieved, whereas curved step edges on a rough surface can lead to the alignment of hBN along with different directions. This study shows that high-index surfaces with a large step density are robust for templating the epitaxial growth of 2D single crystals due to their large tolerance for surface roughness and provides a general guideline for the epitaxial growth of various 2D single crystals.     

异种铁素体耐热钢接头界面组织及其影响

综述了铁素体与铁素体异种金属焊缝（dissimilar metal welds，DMWs）接头界面组织及其影响。结果表明，在焊后热处理或运行温度下的铁素体钢DMWs接头的不均匀界面组织中，通常会形成脱碳层和增碳层。在铁素体钢DMWs焊接接头界面组织影响因素中，焊缝金属的化学成分有重要影响；焊后热处理规范（温度和时间）、工作温度下运行时间的影响较为突出；焊接工艺参数的影响亦不可忽略。异种钢接头界面处近缝区裂纹的产生，以及接头的蠕变强度随Larson Miller 参数增大而下降等不利影响，均为异种钢界面碳迁移行为所导致。焊缝成分控制法是接头界面组织控制或改善的必要条件，而脱碳层部位转移法能有效防止裂纹发生，亦是接头安全运行的重要工艺措施之一。