Energetic stability of boron nitride nanostructures doped with one carbon atom

We have investigated, using first‐principles calculations, the role of a substitutional carbon atom on the geometric stability of boron nitride monolayers, nanotubes, and nanocones. It is shown that the formation of energy depends on the number of atoms for the monolayers and on the diameter for the tubes. It is also found, for the carbon‐doped boron nitride nanotubes, that the value for the strain energy approaches the one obtained for nondoped tubes with increasing diameter. For the structural stability, we have verified that the doping, which introduces an excess of nitrogen or boron, makes each structure more favorable in its reverse atmosphere, i.e., excess of nitrogen is more stable in a boron‐rich growth environment, whereas excess of boron is preferred in a nitrogen‐rich condition. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

用于高性能锂-硫电池的氮化硼纳米片/碳纤维改性隔膜

通过静电纺丝、热亚胺化和碳化过程,将氮化硼纳米片(BNNSs)负载在碳纤维(CFs)表面,组成用于修饰商业聚丙烯(PP)隔膜的氮化硼纳米片/碳复合纤维(BNNSs/CFs)复合材料。BNNSs和CFs的协同作用为电池提供了额外的导电路径,并将可溶性多硫化锂固定在正极区域。结果表明,采用10BNNSs/CFs-PP隔膜的电池在0.05C下的初始放电容量高达1 295.7 mAh·g^-1,当电流密度增加到1C时,以10BNNSs/CFs-PP为隔膜的电池也具有良好的长期循环稳定性,在400次循环后最终容量高达568.1mAh·g^-1,每次循环容量衰减0.073%。     

用于高性能锂-硫电池的氮化硼纳米片/碳纤维改性隔膜

通过静电纺丝、热亚胺化和碳化过程,将氮化硼纳米片(BNNSs)负载在碳纤维(CFs)表面,组成用于修饰商业聚丙烯(PP)隔膜的氮化硼纳米片/碳复合纤维(BNNSs/CFs)复合材料。BNNSs和CFs的协同作用为电池提供了额外的导电路径,并将可溶性多硫化锂固定在正极区域。结果表明,采用10BNNSs/CFs-PP隔膜的电池在0.05C下的初始放电容量高达1 295.7 mAh·g^-1,当电流密度增加到1C时,以10BNNSs/CFs-PP为隔膜的电池也具有良好的长期循环稳定性,在400次循环后最终容量高达583.1mAh·g^-1,每次循环容量衰减0.069%。     

用于高性能锂-硫电池的氮化硼纳米片/碳纤维改性隔膜

通过静电纺丝、热亚胺化和碳化过程,将氮化硼纳米片(BNNSs)负载在碳纤维(CFs)表面,组成用于修饰商业聚丙烯(PP)隔膜的氮化硼纳米片/碳复合纤维(BNNSs/CFs)复合材料。BNNSs和CFs的协同作用为电池提供了额外的导电路径,并将可溶性多硫化锂固定在正极区域。结果表明,采用10BNNSs/CFs-PP隔膜的电池在0.05C下的初始放电容量高达1 295.7 mAh·g^-1,当电流密度增加到1C时,以10BNNSs/CFs-PP为隔膜的电池也具有良好的长期循环稳定性,在400次循环后最终容量高达568.1mAh·g^-1,每次循环容量衰减0.073%。     

Recent advances in carbon nanostructures prepared from carbon dioxide for high-performance supercapacitors

The burgeoning global economy during the past decades gives rise to the continuous increase in fossil fuels consumption and rapid growth of CO₂ emission,which demands an urgent exploration into green and sustainable devices for energy storage and power management.Supercapacitors based on activated carbon electrodes are promising systems for highly efficient energy harvesting and power supply,but their promotion is hindered by the moderate energy density compared with batteries.Therefore,scalable conversion of CO₂ into novel carbon nanostructures offers a powerful alternative to tackle both issues:mitigating the greenhouse effect caused by redundant atmospheric CO₂ and providing carbon materials with enhanced electrochemical performances.In this tutorial review,the techniques,opportunities and barriers in the design and fabrication of advanced carbon materials using CO₂ as feedstock as well as their impact on the energy-storage performances of supercapacitors are critically examined.In particular,the chemical aspects of various Cv2 conversion reactions are highlighted to establish a detailed understanding for the science and technology involved in the microstructural evolution,surface engineering and porosity control of CO₂-converted carbon nanostructures.Finally,the prospects and challenges associated with the industrialization of CO₂ conversion and their practical application in supercapacitors are also discussed.     

Boron nitride/epoxy resin nanocomposites: development,characterization and functionality

Journal of Thermal Analysis and Calorimetry - Polymer matrix composites with embedded ceramic nanoparticles receive not only enhanced scientific but also technological interest, due to their...     

Quantum-chemical calculations on graphitic carbon nitride (g-C3N4) single-layer nanostructures: polymeric slab vs. quantum dot

Graphitic carbon nitride (g-C₃N₄) has been the focus of enormous attention in recent years for its fantastic in-plane and surface properties. Several periodic and cluster models of g-C₃N₄ including a quantum dot have been investigated using density functional theory (DFT) at the HSE06/Def2-TZVP level. The quantum dot with side triazine rings in nearly perpendicular alignment to the central ring was (by 98.40 kcal/mol) more stable than any other cluster, including its planar analogue—a metastable phase of carbon nitride. The g-C₃N₄ quantum dot showed the largest deviation (3.27 eV, 7.9%) from the bandgap of the polymeric material. On the other hand, the unrelaxed symmetrical cluster had the smallest deviation (+?0.03 eV, 1.0%) from the reference bandgap (and also in terms of global hardness), indicating that it could be taken as a replacement cluster for modeling of a polymeric surface in such explorations. The plots of the density of states (DOS) revealed the inherent instabilities of the planar models compared to the quantum dot. Furthermore, the g-C₃N₄ quantum dot showed the highest chemical hardness among the models investigated. The electronic band structures of the g-C₃N₄ quantum dot implied its relatively better photoabsorption ability referenced to the polymeric surface. However, the structural changes had significant effects on the orbital and charge distributions in the C₃N₄ models.

     

Ultrafast electrodeposition of amorphous carbon nitride films from fullerene derivative

Amorphous carbon nitride films with good photoluminescence could be ultrafastly fabricated by liquid-phase electrochemical decomposition of fullerene derivative, C₆₀[(NH₂)₂CNCN]₅. The structure of the as-prepared films, characterized by transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy, was consisted of sp² hybrid C, sp³ hybrid C, C–N, CN and CN bands. Further study showed that the thickness of the films increased with the increase of the deposition time and the concentration of C₆₀[(NH₂)₂CNCN]₅. The optical tests indicated that the as-obtained films have distinct photoluminescence, no obvious decrease was observed more than one month later.     

Tailored core-shell-shell nanostructures: sandwiching gold nanoparticles between silica cores and tunable silica shells

Size tunable and structure tailored core-shell-shell nanospheres containing silica cores, gold nanoparticle shells, and controlled thicknesses of smooth, corrugated, or porous silica shells over the gold nanoparticles have been synthesized. The synthesis involved the deposition of gold nanoparticles on silica cores, followed by sol-gel processing of tetraethoxysilane (TEOS) or sodium silicate to form dense or porous silica shells, respectively, over the gold nanoparticles. The structures and sizes of the resulting core-shell-shell nanospheres were found to heavily depend on the sizes of the core nanoparticles, the relative population of the gold nanoparticles on each core, and the concentration of TEOS. While a higher TEOS concentration resulted in thicker and more uniform silica shells around individual larger silica cores (approximately > or =250 nm in diameter), the same TEOS concentration resulted in aggregated and twin core-shell-shell nanostructures for smaller silica cores (approximately < or =110 nm in diameter). The thinner silica shells were synthesized by using a lower TEOS concentration. By using sodium silicate (Ung et al. J. Phys. Chem. B 1999, 103, 6770), the porous silica shells were synthesized. Controlled chemical etching of the core-shell-shell nanoparticles with an aqueous KCN solution resulted in corrugated silica shells around the gold nanoparticles or corrugated silica nanospheres with few or no gold nanoparticles. This has allowed synthesis of new types of core-shell-shell nanoparticles with tailored corrugated shells. The nanoporous silica shells provided accessible structures to the embedded metal nanoparticles as observed from the electrochemical response of the gold nanoparticles.     

Novel organotin-containing diblock copolymer with tunable nanostructures: Synthesis, self-assembly and morphological change

Interesting self-assembly behavior and morphological change of a novel organotin-containing diblock copolymer were firstly reported. The organotin-containing diblock copolymer, poly(methyl methacrylate)-block-poly(acetoxydibutyltin methacrylate) (PMMA-b-PADBTMA), was prepared via RAFT polymerization of ADBTMA with PMMA as the macroCTA and AIBN as the initiator in toluene. Both the FT-IR and TG analysis revealed an incorporation of both co-monomers in the resulted polymer backbone. The ratio of two segments was determined indirectly by TG analysis, gravimetric method and derivative process. All results from the different methods were well matched. And it was found that the morphology of the diblock copolymer could be changed easily from vesicles to nano-particle or cross-linked nano-composite under the ultrasonication or additional Ph₂SnCl₂, respectively. All the morphologies were analyzed by SEM, TEM and DLS. The self-assembly and the morphological change attributed to the strong coordination action between tin atoms and the carbonyl groups among PADBTMA segments.     

Amorphous carbon nitride a-CNx microelectrode: Fabrication and characterization

Fabrication and characterization of amorphous carbon nitride a-CN_x microelectrodes are reported. These electrodes were prepared by DC-sputtering of a thin carbon layer on sharpened glass tip. The kinetic parameters (k⁰ and α) and the diffusion coefficient of the ferri-ferrocyanide redox probe were determined by steady-state voltammetry (CV) and by electrochemical impedance spectroscopy (EIS), and were used for characterizing both the electrochemical sensitivity of microelectrodes and their dimensions. The cathodic activation procedure of the electrode resulted in an increase of the electron rate constant. This procedure provides a new way for the fabrication of carbon microelectrodes for local electrochemical measurements.     

Mesoporous graphitic carbon nitride materials: synthesis and modifications

Graphitic carbon nitride (g-C₃N₄), as a kind of polymeric semiconductor that has unique electronic structure and excellent chemical stability, has attracted increasing attention of researchers. Moreover, the raw materials for the preparation of g-C₃N₄ are various and easily accessible. All of these have provided favorable advantages for the fast development of g-C₃N₄. Compared to bulk g-C₃N₄, mesoporous g-C₃N₄ has more prominent natures, such as high specific surface area, large pore volume, and the increased amount of surface active sites. Therefore, great efforts have been devoted to develop mesoporous g-C₃N₄ (MCN). Up to now, many methods have been explored for the synthesis of MCN, such as hard-template method, soft-template method, template-free method, sol–gel method, and so on. Among these methods, the hard template method is used most widely. In this paper, the recent research on the synthesis of MCN was reviewed. In addition, the modifications to the obtained MCN, which lead to performance enhancement of the MCN for better applications, were also summarized.     

Oriented morphogenesis of ZnO nanostructures from water-soluble zinc salts under environmentally mild conditions and their optical properties

Herein, we report a bottom-up, mineralization strategy, which borrows key principles from biomineralization processes, to synthesize nanostructured materials. A long-chain polyamine simultaneously mineralizes and assembles ZnO nanoparticles directly from water-soluble zinc salts under sustainable synthesis conditions. These thus-generated oriented structures undergo interesting morphogenesis that is controlled by changing the ratio of polyamine/Zn(2+) ions. As the ratio increases, the morphology changes from a spherical shape to oval-, dumbbell-, and finally hexagonal-rod-shaped structures that contain unique hollow rod structures. Using XPS, XRD, FT-IR, Raman spectroscopy, DLS, and confocal fluorescence microscopic analysis, we elucidate the mechanism of structural evolution; this mechanism involves the initial formation of a zinc/amine complex that is furnished with polyamine chains. These chains facilitate the condensation process to form ZnO nanoparticles and their assembly in aqueous medium at neutral pH. Further, the presence of defects in the thus-morphogenized ZnO structures leads to blue luminescence and efficient photoinduced activity, assisted by the surface-hole-trapping effect of polyamines.     

Two-dimensional polymeric carbon nitride: structural engineering for optimizing photocatalysis

As a two-dimensional (2D) material, polymeric carbon nitride (g-C₃N₄) nanosheet holds great potentials in environmental purification and solar energy conversion. In this review, we summarized latest progress in the optimization of photocatalytic performance in 2D g-C₃N₄. Some of the latest structural engineering methods were summed up, where the relevant influences on the behaviors of photoinduced species were emphasized. Furthermore, the construction strategies for band structure modulation and charge separation promotion were then discussed in detail. A brief discussion on the opportunity and challenge of 2D g-C₃N₄-based photocatalysis are presented as the conclusion of this review.     

Noncovalent functionalization of multiwalled carbon nanotubes: application in hybrid nanostructures

We developed a reproducible, noncovalent strategy to functionalize multiwalled carbon nanotubes (MWNTs) via embedding nanotubes in polysiloxane shells. (3-Aminopropyl)triethoxysilane molecules adsorbed to the nanotube surfaces via hydrophobic interactions are polymerized simply by acid catalysis and form a thin polysiloxane layer. On the basis of the embedded MWNTs, negatively charged gold nanoparticles are anchored to the nanotube surfaces via electrostatic interactions between the protonated amino groups and the gold nanoparticles. Furthermore, these gold nanoparticles can further grow and magnify along the nanotubes through heating in HAuCl4 aqueous solution at 100 degrees C; as a result these nanoparticles are joined to form continuous gold nanowires with MWNTs acting as templates.     

Boron nitride nanocluster as a carrier for lomustine anticancer drug delivery: DFT and thermodynamics studies

Monatshefte für Chemie - Chemical Monthly - Previous reports were shown that boron nitride nanostructures can be biocompatible and nontoxic. Therefore, interaction of lomustine as an...     

Production of water-soluble sugar from cellulose and corn stover via molten salt hydrate impregnation and separation

Cellulose - Saccharification of cellulose into glucose is a key step for the utilization of lignocellulose. Molten salt hydrate (MSH) is unique in selective hydrolysis of cellulose into glucose but...     

Polymeric graphitic carbon nitride as a heterogeneous organocatalyst: from photochemistry to multipurpose catalysis to sustainable chemistry

Polymeric graphitic carbon nitride materials (for simplicity: g-C(3)N(4)) have attracted much attention in recent years because of their similarity to graphene. They are composed of C, N, and some minor H content only. In contrast to graphenes, g-C(3)N(4) is a medium-bandgap semiconductor and in that role an effective photocatalyst and chemical catalyst for a broad variety of reactions. In this Review, we describe the "polymer chemistry" of this structure, how band positions and bandgap can be varied by doping and copolymerization, and how the organic solid can be textured to make it an effective heterogenous catalyst. g-C(3)N(4) and its modifications have a high thermal and chemical stability and can catalyze a number of "dream reactions", such as photochemical splitting of water, mild and selective oxidation reactions, and--as a coactive catalytic support--superactive hydrogenation reactions. As carbon nitride is metal-free as such, it also tolerates functional groups and is therefore suited for multipurpose applications in biomass conversion and sustainable chemistry.