Structure,electronic and magnetic properties of hexagonal boron nitride sheets doped by 5d transition metal atoms: First-principles calculations and molecular orbital analysis

A first-principles calculation based on density functional theory is carried out to reveal the geometry, electronic structures and magnetic properties of hexagonal boron nitride sheets (h-BNSs) doped by 5d transitional mental atoms (Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au and Hg) at boron-site (B_5d) and nitrogen-site (N_5d). Results of pure h-BNS, h-BNS with B vacancy (V_B) and N vacancy (V_N) are also given for comparison. It is shown that all the h-BNSs doped with 5d atoms possess a C_3v local symmetry except for N_Lu and N_Hg which have a clear deviation. For the same 5d dopant, the binding energy of B_5d is larger than that of N_5d, which indicates the substitution of a 5d atom for B is preferred. The total densities of states are presented, where impurity energy levels exist. Besides, the total magnetic moments (TMMs) change regularly with the increment of the 5d atomic number. Theoretical analyses by molecular orbital under C_3v symmetry explain the impurity energy levels and TMMs.     

A microfabricated graphitic carbon column for high performance liquid chromatography

We report the first development of a novel, planar, microfluidic, graphitic carbon separations column utilizing an array of graphitic micropillars of diamond cross-section as the chromatographic stationary phase. 795 nm femtosecond laser ablation was employed to subtractively machine fluidic architectures and a micropillared array in a planar, graphitic substrate as a monolithic structure. A sample injector was integrated on-chip, together with fluid-flow distribution architectures to minimize band-broadening and ensure sample equi-distribution across the micro-pillared column width. The separations chip was interfaced directly to the ESI probe of a Thermofisher Surveyor mass spectrometer, enabling the detection of test-mixture analytes following their differential retention on the micro-pillared graphitic column, thus demonstrating the exciting potential of this novel separations format. Importantly, unlike porous, graphitic microspheres, the temperature and pressure resilience of the microfluidic device potentially enables use in subcritical H(2)O chromatography.     

Reduced Graphene Sheets Modified Electrodes for Electrochemical Detection of Sulfide

This paper describes a new electrochemical sensor based on reduced graphene sheets (RGSs) modified glassy carbon electrodes for rapid detection of sulfide. The morphology and electrochemical properties of the RGSs are characterized by atomic force microscopy and cyclic voltammetry. The effects of the scan rates and pH are investigated to evaluate the oxidation processes. Analytical performances of RGSs modified electrodes for direct determination of sulfide in phosphate buffer solutions (PBSs) are also assessed. The RGSs are shown to be viable potential material for sulfide detection as shown by their electrochemical performance.     

Simulations of the bending rigidity of graphene

Molecular mechanics simulations for graphene bending rigidity are reported through calculations of the strain energy for graphene sheets subjected to a point loading. The rigidity is found to be dependent on the size and the shape of graphene sheets. Moreover, dependence of the rigidity on the deflection is found.     

Electrospun one-dimensional graphitic carbon nitride-coated carbon hybrid nanofibers (GCN/CNFs) for photoelectrochemical applications

Coupling of graphitic carbon nitride (GCN) with electrospun carbon nanofibers (CNFs) enhanced the photoelectrochemical (PEC) performance of a pristine GCN photoanode. Polyacrylonitrile (PAN) was electrospun to form fibers that were then carbonized to form one-dimensional (1D) CNFs, which were then used to fabricate the GCN structure. The optimum GCN/CNFs hybrid structure was obtained by controlling the amount of GCN precursors (urea/thiourea). The surface morphology of the hybrid structure revealed the coating of GCN on the CNFs. Additionally, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and X-ray diffraction confirmed the phases of the GCN/CNFs hybrids. PEC results showed a higher photocurrent of 3 μA for the hybrid compared with that of 1 μA for the pristine GCN. The high photocurrent for the hybrid structures indicated the formation of heterojunctions that resulted from a lower recombination rate of charge carriers. Moreover, UTh_0.075 (0.075 g of urea and 0.075 g of thiourea) hybrid sample showed the highest performance of hydrogen generation with its numerical value of 437 μmol/g, compared to those of UTh_0.1(0.1 g of urea and 0.1 g of thiourea) and UTh_0.05 (0.05 g of urea and 0.05 g of thiourea) composite samples. This higher hydrogen production could be explained again with successful formation of heterojunctions between GCN and CNFs. Overall, we report a new approach for obtaining 1D hybrid structures, having better PEC performance than that of pristine GCN. These hybrids could potentially be used in energy-related devices.     

过渡金属原子对掺杂g-CN单层作为高效氮电催化剂性能

由于氨是药物、肥料和树脂等领域的基础,氨合成一直广受关注.工业中主要通过Haber-Bosch反应制备氨,反应需要在高温高压下进行.因此,探索其它氨合成技术对减轻能源消耗和缓解温室效应具有重大意义.在溶液条件下,采用水作为氢质子源,电化学还原氮合成氨方法受到了极大关注.然而,大多数电催化剂难以活化氮气分子且电催化氮气还...     

Ultrasonic-assisted synthesis of porous S-doped carbon nitride ribbons for photocatalytic reduction of CO2

A series of porous S-doped carbon nitride ribbons (PSCN) were prepared by one-pot hydrothermal and sonochemical synthesis techniques. The morphologies and nanostructures of the catalysts were characterized by SEM, XRD and IR, which confirmed the pristine graphitic structures of carbon nitrides retained in the products. Due to sonication treatment, PSCN has porous structures in the thin ribbon and larger specific surface areas (PSCN 43.5 m²/g, SCN 26.6 m²/g and GCN 6.5 m²/g). XPS and elemental mappings verified that sulfur atoms were successfully introduced into the carbon nitride framework. Diffuse reflectance spectroscopy (DRS) results showed S-doping in the carbon nitride reduced the bandgap energy and enhanced their capability of the utilization of visible light, which contributed to higher photo-generated current. Photoluminescence (PL) analysis indicates the recombination of photogenerated carriers was suppressed in PSCN. Moreover, the photocatalytic performance showed that S-doping and porous and thin ribbon nanostructures may effectively boost the CO₂ reduction rate (to as much as 5.8 times of GCN) when illuminated by visible light (>420 nm) without the need of sacrificial materials. The preliminary mechanisms of the formation of PSCN and its applications in photocatalytic CO₂ reduction are proposed. It highlights the potential of the current technique to produce effective, nonmetal-doped carbon nitride photocatalysts.     

石墨相氮化碳量子点的简易水热制备和荧光性能

本文以线状石墨相氮化碳(Lg-CN)为原料,在无需强酸加入的情况下,利用简单的纯水中的水热反应成功制得了氮化碳量子点(CN QDs),并利用傅里叶变换红外光谱、X射线粉末衍射、透射电镜、X射线光电子能谱等对所得量子点的形貌和结构进行了表征,进而解释了量子点的形成机理;利用紫外-可见吸收光谱和荧光光谱对其光学性质进行了研...     

Tuning of graphitic carbon nitride (g-C3N4) for photocatalysis: A critical review

Graphitic carbon nitride (g-C₃N₄) is a remarkable semiconductor catalyst that has attracted widespread attention as a visible light photo-responsive, metal-free, low-cost photocatalytic material. Pristine g-C₃N₄ suffers fast recombination of photogenerated electron-hole pairs, low surface area, and insufficient visible light absorption, resulting in low photocatalytic efficiency. This review presents the recent progress, perspectives, and persistent challenges in the development of g-C₃N₄-based photocatalytic materials. Several approaches employed to improve the visible light absorption of the materials including metal and non-metal doping, co-doping, and heterojunction engineering have been extensively discussed. These approaches, in general, were found to decrease the material’s bandgap, increase the surface area, reduce charge carrier recombination, and promote visible light absorption, thereby enhancing the overall photocatalytic performance. The material has been widely used for different applications such as photocatalytic hydrogen production, water splitting, CO₂ conversion, and water purification. The work has also identified various limitations and weaknesses associated with the material that hinders its maximum utilization under visible illumination and presented state-of-the-art solutions that have been reported recently. The summary presented in this review would add an invaluable contribution to photocatalysis research and facilitate the development of efficient visible light-responsive semiconducting materials.