Nanostructured carbide-derived carbon synthesized by chlorination of tungsten carbide

Nanostructured carbide-derived carbons were synthesized from α-tungsten carbide (WC-CDC) powder via gas phase chlorination within the temperature range from 700 to 1100 °C. Analysis of X-ray diffraction results showed that WC-CDC are mainly amorphous consisting of relatively small graphitic crystallites and the apparent crystallite size along the a- and c-directions of graphite structure L_a ≈ 4 nm and L_c ≈ 1.5 nm were calculated. The first-order Raman spectra showed the graphite-like absorption peak at ∼1590 cm⁻¹ and the disorder-induced peak at ∼1350 cm⁻¹. The low-temperature N₂ sorption experiments were performed and a specific micropore surface area up to 1550 m² g⁻¹ and total pore volume up to 0.89 cm³ g⁻¹ were obtained for WC-CDC synthesized at T = 1100 °C. High-resolution transmission electron microscopy and electron energy loss spectroscopy studies revealed that WC-CDC prepared at 800 °C correspond to the highly disordered carbon material but WC-CDC prepared at 1100 °C showed partial graphitization.     

Synthesis of nanoporous carbide-derived carbon by chlorination of titanium silicon carbide

Synthesis of nanoporous carbide-derived carbon, CDC, by extraction of titanium and silicon from Ti₃SiC₂ by chlorine is discussed in this work. Thermodynamic simulations using a Gibbs free energy minimization program provided general guidelines to the experimental design. Raman spectroscopy, X-ray diffraction, and electron microscopy studies showed that the structure of CDC depends on the chlorination temperature. The low temperature synthesis resulted in an amorphous CDC structure. Noticeable graphite formation starts above 800 °C and well ordered graphite ribbons of 1-3 nm in thickness form at 1200 °C. The macroscopic volume and shape of Ti₃SiC₂ preform were preserved during the transformation. However, the chlorination resulted in the formation of cracks between the former grains of the polycrystalline Ti₃SiC₂ preform. These cracks are believed to be caused by a contraction in the direction perpendicular to the basal planes of Ti₃SiC₂. The synthesized nanoporous carbon demonstrated excellent sorption properties. Energy dispersive X-ray spectroscopy studies showed that Ti₃SiC₂ material chlorinated at 400 °C is capable of trapping over 40 wt.% of Cl₂.     

Synthesis and characterisation of nanoporous carbide-derived carbon by chlorination of vanadium carbide

Nanoporous carbide-derived carbon (CDC) was synthesised from vanadium carbide (VC) powder via gas phase chlorination in the temperature range from 500 to 1100 °C. The XRD analysis of nanoporous carbon powder samples was carried out to investigate the structural changes (graphitisation) of nanoporous carbons synthesised. The first-order Raman spectra showed the absorption peak at ∼1582 cm⁻¹ and the disorder-induced (D) peak at ∼1345 cm⁻¹. The low-temperature N₂ adsorption experiments were performed and a specific surface area up to 1305 m² g⁻¹ and total pore volume up to 0.66 cm³ g⁻¹ were obtained.     

Effective control of the microstructure of carbide-derived carbon by ball-milling the carbide precursor

A microstructure control strategy for carbide-derived carbon (CDC) by ball-milling the metal carbide precursor prior to CDC synthesis is investigated. This work explores the effect of chlorination temperature and ball-milling time on the microstructure, specific surface area (SSA) and the pore size distribution. It is found that the degree of order of CDC obtained from the milled titanium carbide (TiC) is obviously high and can be well tuned by controlling the ball-milling time at a lower chlorination temperature (400–800 °C). As the chlorination temperature rises to 1000 °C, an obvious decrease in the degree of order is observed and many cubic diamond-like carbon nanoparticles with larger d-spacing are formed. In addition, the produced CDC has a high SSA with both micro- and meso-pores. The effect of ball-milling TiC precursor on the microstructure of CDC can be attributed to the iron (Fe) in the TiC from the milling balls and jar to a great extent. The Fe promotes the formation of the better-organised carbon at lower chlorination temperature and the formation of the nano-diamond at higher temperature.     

Enhanced anode performance of micro/meso-porous reduced graphene oxide prepared from carbide-derived carbon for energy storage devices

Micro/meso-porous reduced graphite oxide (MMRGO) nanosheets were produced using precursor carbide-derived carbon (CDC), which was produced at a high temperature of 1200 °C, through a massive wet chemistry synthetic route involving graphite oxidation and microwave reduction. X-ray diffraction (XRD) and transmission electron microscopy (TEM) show that the MMRGO nanosheets were fabricated with 2–3 layers and ripple-like corrugations. N₂ sorption isotherms confirmed that micro/meso-pores coexisted in the RGO sample from CDC. In the anode application of Li-ion batteries, this RGO sample had an enhanced capacity performance at the 0.1 C rate and 1 C rate, with ∼1200 mAh g⁻¹ at the 100th cycle and ∼1000 mAh g⁻¹ at the 200th cycle, respectively.     

In-situ thermal activation of carbide-derived carbon

Microporous carbons attract high interest due to their application as a medium for gas storage, catalyst support or electrode material in lithium ion batteries or supercapacitors. Carbide-derived carbons (CDC) produced by halogenation of carbides exhibit a narrow pore size distribution and a tunable pore and microstructure by choosing the appropriate carbide precursor and chlorination temperature. However, the pore volume is limited by the amount of metal in the carbide structure, and the variation of pore size by varying the process conditions is not possible for all carbides. With an in-situ thermal activation in CO₂ parallel to the chlorination, the porosity of the CDC materials can be further increased. This improved carbide-derived carbon process also allows producing novel pore structures which vary in the meso- to micropore ratio from the outside to the center of the particle. Thereby also the boarder case of shell-like carbon structures showing different pore size distributions in the shells can be produced. For this in-situ activation and chlorination of carbides the influence of the processing, the concentration of CO₂ and activation time on the pore structure of CDC was studied.     

Formation of encapsulated molybdenum carbide particles by annealing mechanically activated mixtures of amorphous carbon with molybdenum

The investigation of morphological and structural changes during high-energy ball milling and thermal annealing of mixtures of amorphous carbon and molybdenum demonstrated that the activation leads to the formation of a nano-size carbide Mo₂C phase. Morphological characteristics of the annealed, mechanically activated amorphous carbon-molybdenum samples depend on the time of preliminary mechanical activation. Annealing of amorphous carbon-molybdenum samples after preliminary mechanical activation, at a temperature of 860 °C, caused the formation of nano-sized encapsulated particles of molybdenum carbide Mo₂C. The surface of the Mo₂C nanoparticles was coated with a shell composed of hexagonal polyaromatic carbon 5-20 nm thick. The size of the encapsulated particles varies within a rather broad range from 10 to 20 nm to several hundred nanometers.     

Early stages of carbon film growth: carbide interface formation on molybdenum

In this study we present an investigation of the carbide formation and early stages of carbon film growth using a low energy carbon beam to supply the growth species. Carbon is supplied through electron beam evaporation of graphite and between 0.1 and 40 ML are deposited on a molybdenum substrate (substrate temperature 400 °C). Photoelectron spectroscopy in the ultraviolet and X-ray regime was employed to characterize the surface and observe the carbide and carbon film formation. Two regimes, with respect to the surface composition, can be identified: firstly, the carbide formation, and, secondly the growth of a pure carbon overlayer. A carbide interface with Mo₂C stoichiometry is created, and the formation of a pure amorphous carbon layer is observed for carbon coverages exceeding about 3.4 ML. But even after the onset of carbon film growth, the carbide interface growth is not terminated, and the extension of the carbide region into the bulk continues to increase. Diffusion through the carbide interface is still present and a dynamic rather than static interfacial layer exists. The diffusion of carbon through the metal carbide dominates the interface formation, which is also evidenced by a delayed onset of carbon film formation at 600 °C. Apart from the observation of interface formation, this experiment also enabled us to observe the valence band spectrum of molybdenum carbide (Mo₂C) for the first time. The sequential deposition of carbon was shown to be a suitable method to produce clean carbide surfaces.     

A facile pathway to prepare molybdenum boride powder from molybdenum and boron carbide

Molybdenum boride is an ideal hard and wear-resistant material. In this study, a new method is proposed for preparing molybdenum boride, by which Mo first reacts with B₄C to generate the mixture of molybdenum boride and C, and then the product is decarburized by molten Ca to generate CaC₂. Pure molybdenum boride could be obtained after acid leaching to remove the by-product CaC₂. According to the experimental and thermodynamic calculation results, it is concluded that the single-phase MoB could be successfully prepared, while Mo₂B, Mo₂B₅, and MoB₄ could not be synthesized by this method. Moreover, it was found that the particle size of finally prepared MoB is determined by particle size of raw Mo powder. The residual carbon content of the product could be decreased to 0.10 wt% after first reaction at 1673 K for 6 hours and then decarburization reaction at 1673 K for 6 hours.     

自牺牲模板法制备氮掺杂碳化钼/碳析氢电催化剂

采用g-C3N4为自牺牲模板和氮源,葡萄糖为碳源,钼酸铵为钼源,制备具有二维纳米结构的氮掺杂碳化钼修饰碳纳米片(N-Mo₂C/C),并评价其电催化析氢性能。利用X射线衍射仪(XRD)、场发射扫描电镜(FESEM)、透射电镜(TEM)、拉曼(Raman)等测试手段对N-Mo₂C/C的组成、形貌及结构进行分析。结果表明,氮掺杂的Mo₂C纳米颗粒均匀分散在二维碳纳米片上,粒径主要分布在3～5 nm。利用电化学工作站测试N-Mo₂C/C的电催化析氢性能,在1 mol/L KOH溶液中,电流密度为10 mA/cm²时其对应的过电势为185 mV,Tafel斜率为69 mV/dec,经20 h循环可维持稳定的析氢电势。     

Fabrication of molybdenum carbide catalysts over multi-walled carbon nanotubes by carbothermal hydrogen reduction

Molybdenum carbide catalysts were successfully prepared using original multi-walled carbon nanotubes (MWCNTs) and nitric acid treated ones as support and carbon source by carbothermal hydrogen reduction from 580 °C to 700 °C. Ammonium heptamolybdate was used as Mo precursor and the effects of oxygen functional groups on MWCNT surface were investigated. TEM and XRD results show that oxygen functional groups act as anchor sites to interact with the Mo oxyanion species during impregnation, which promote the dispersion of Mo precursors. Due to the relatively strong interaction between Mo precursors and MWCNTs, the agglomeration of Mo carbide particles is prevented even when the treatment temperature is as high as 700 °C. Moreover, as the support, modified MWCNTs exhibit better thermal resistances. The temperature (580 °C) for Mo₂C formation over MWCNTs is much lower than that over conventional carbon supports using carbothermal hydrogen reduction. The methylcyclohexane dehydrogenation was used as a probe reaction to test the catalytic performances of the Mo₂C catalysts obtained.     

Open-celled silicon carbide foams with high porosity from boron-modified polycarbosilanes

Open-Celled silicon carbide (SiC) foams were prepared from a mixture of a boron-modified polycarbosilane as a preceramic polymer and poly(methymetacrylate) (PMMA) microbeads as sacrificial agents. The process consists in the cross-linking of the liquid allylhydridopolycarbosilane (AHPCS, SiC precursor) with borane dimethylsulfide (BDMS, boron source) to form a solid boron-modified polycarbosilane with an adjusted cross-linking degree. The latter is mixed with PMMA microbeads (25 μm) in a 20:80 ratio and the mixture is warm-pressed at 120 °C forming consolidated green bodies to be pyrolyzed at 1000 °C under argon and to deliver open-celled SiC foams with an interconnected porosity of 73.4 _vol%. These foams combine a low density with a compressive strength of 3.49 ± 0.56 MPa and a thermal and mechanical stability under argon up to 1300 °C. Ageing and microfiltration tests in the conditions of a primary loop of coolant in a Pressurized Water Reactor (PWR) showed that foams display a relatively high stability while retaining particles of 5 μm in diameter making these materials as appropriate candidates to work in separation techniques under harsh environments.     

Electrical double-layer characteristics of novel carbide-derived carbon materials

A variety of nanoporous carbide-derived carbon materials possessing improved pore size distributions were synthesised from a mixture of titanium carbide and titanium dioxide. It was observed that TiO₂ caused partial oxidation of the carbon particles created during high-temperature chlorination of the TiC/TiO₂ mixture. The resulting carbon powder is characterised by narrow pore size distribution with a peak pore size of around 8 Å and a noticeably smaller amount of pores below 6-7 Å compared to the carbon derived from pure TiC. Electrochemical and electrical double-layer characteristics of novel carbon materials in the acetonitrile solution of triethylmethylammonium tetrafluoroborate were obtained by using cyclic voltammetry and constant current methods. Carbon electrode materials of this study were tested over the temperature range from −10 °C to +60 °C. Results of this study affirmed a great potential of the synthesised advanced carbide-derived carbon, whose specific double-layer capacitance reaches approximately 90 F cm⁻³ and 125 F g⁻¹.     

Energy and power performance of electrochemical double-layer capacitors based on molybdenum carbide derived carbon

Cyclic voltammetry, constant current charge/discharge, and electrochemical impedance spectroscopy have been applied to establish the electrochemical characteristics for electric double-layer capacitor (EDLC) consisting of the 1 M (C₂H₅)₃CH₃NBF₄ electrolyte in acetonitrile and micro/mesoporous carbon electrodes prepared from Mo₂C, noted as C(Mo₂C). The N₂ sorption (total BET specific surface area (S_BET ≤ 1855 m² g⁻¹), micropore area (S_micro ≤ 1823 m² g⁻¹), total pore volume (V_tot ≤ 1.399 m³ g⁻¹) and pore size distribution (average NLDFT pore width d_NLDFT ≥ 0.89 nm) values obtained have been correlated with the electrochemical characteristics for EDLCs (region of ideal polarizability (ΔV = 3.0 V), characteristic time constant (τ_R = 1.05 s), gravimetric capacitance (C_m ≤ 143 F g⁻¹)) dependent strongly on the C(Mo₂C) synthesis temperature. High gravimetric energy (35 Wh kg⁻¹) and gravimetric power (237 kW kg⁻¹) values, normalised to the total active mass of both C(Mo₂C) electrodes, synthesised at T_synt = 800 °C, have been demonstrated at cell voltage 3.0 V and T = 20 °C.     

Zeolite Beta with hierarchical porosity prepared from organofunctionalized seeds

Beta zeolite with hierarchical porosity has been obtained by a new synthesis strategy, based on perturbing the growth of the zeolite crystals by functionalization of the zeolitic seeds with organosilanes in order to hinder and prevent their further aggregation and agglomeration. As a consequence, a secondary porosity in the supermicropore region has been generated in zeolite Beta, leading to a considerable increase in both the total surface area and the pore volume of the material. The enhancement of the textural properties can be controlled by changing the silanization agent molecular size and its quantity added to the synthesis medium. This type of hierarchical Beta zeolites presents interesting applications as catalysts in reactions involving bulky molecules. Thus, their catalytic activity in the catalytic cracking of LDPE has been found to be strongly enhanced compared to a standard Beta zeolite sample, due to the higher accessibility to the acid sites caused by the presence of the secondary porosity.     

Slow diffusion of methane in ultra-micropores of silicon carbide-derived carbon

We investigate macroscopic uptake kinetics of CH₄ in silicon carbide-derived carbon (SiC-DC). Ultra-microprosity in SiC-DC is found based on CO₂ adsorption at 273 K, but which has poor accessibility to Ar at 87 K. The adsorption kinetics of CH₄ is found to follow a bidisperse pore structure model, considering relatively rapid particle scale diffusion in large micropores, and a much slower local grain (or microparticle) scale diffusion in ultra-micropores. The grain scale activation energies are comparable with values for carbon molecular sieves, and consistent with values expected for the size range of the ultra-micropores, while the activation energies for transport in the larger particle scale micropores are comparable to those for conventional activated carbons. The particle scale diffusivities compare well with the results of equilibrium molecular dynamics simulations using a hybrid reverse Monte Carlo simulation constructed model of SiC-DC, with similar activation energy. On the other hand microscopic quasi-elastic neutron scattering measurements are found to probe only short-range barriers with lower activation energy. It is anticipated that ultra-micropores will not make a significant contribution to the transport in any membrane or adsorption-based process based on SiC-DC, due to the extremely slow transport in these ultra-micropores and their small pore volume.     

Pyrolytically prepared carbon from fluorine-GIC

Formation mechanism, crystallinity, porosity and chemical reactivity were studied on the carbon prepared by pyrolysis of single phase, stage-1 fluorine-graphite intercalation compound (fluorine-GIC; C_xF). The stage-1 C_2.5F directly decomposes to fluorocarbon gases and carbon above 650 K, without forming higher stage compounds. The pyrocarbon prepared from C_2.5F gives hkl diffraction peaks indicating graphite-like stacking order of graphene layers. This carbon possesses average crystallite sizes along the c- and a-axes (L_c and L_a) of about 5 and 50 nm, respectively. The specific surface area of the pyrocarbon (about 40 m² g⁻¹) is only twice as large as that of the original crystalline graphite. Chemical behavior of the pyrocarbon as an intercalation host for sodium and potassium is similar to that of crystalline graphite, but it is easily fluorinated by elemental fluorine even at 573 K to give poly(carbon monofluoride) [(CF)_n] probably due to the small crystallite size and the mesopores formed by formation/decomposition processes of C_2.5F.     

电石渣制备碳酸钙微粉的晶型转变

为了提高电石渣的附加值,在未使用晶型诱导剂的情况下,研究盐酸的用量、提取温度和二氧化碳的流量对电石渣合成碳酸钙形貌的影响。用XRD、FT-IR 表征了合成的产物,用扫描电子显微镜（SEM）观察研究了产物粒子的形状,结果表明,盐酸的用量和提取温度均会对碳酸钙的晶型和形状有影响。随着盐酸用量的增大,碳酸钙由不规则的方解石型转变为部分规则的球状结构,当浸取剂完全是盐酸的时候,碳酸钙的晶型从方解石型完全转变为球霰石型结构,颗粒粒径为4~5 μm。另外,当提取温度从18 ℃升高到30 ℃以上后,碳酸钙由方解石和球霰石两种晶体结构并存的状态转变为单一的球霰石型结构。     

Comparison of molybdenum carbide and tungsten carbide for the hydrodesulfurization of dibenzothiophene

The molybdenum and tungsten carbides (Mo₂C and W₂C) were synthesized, characterized and tested in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The phase purity of these catalysts was established by X-ray diffraction (XRD), and the surface properties were determined by N₂ BET specific surface area (Sg) measurements, CO chemisorption and high-resolution transmission electron microscopy (HRTEM). The activities of catalysts were determined during the HDS of DBT at a temperature of 613 K and under a 6 MPa total pressure. Both molybdenum and tungsten carbides were active in HDS of DBT. The reactivity studies showed that molybdenum carbide was more active than tungsten carbide related to weight. However, W₂C was shown to possess stronger hydrogenating properties.     

Comparison between tungsten carbide and molybdenum carbide for the hydrodenitrogenation of carbazole

The activity of molybdenum and tungsten carbides in hydrodenitrogenation (HDN) of carbazole was studied. Transition metal carbides (Mo₂C and W₂C) were synthesized using the temperature-programmed reaction of the appropriate oxide precursor (MoO₃ and WO₃) with the following gas mixture: 10 vol.% CH₄/H₂. The structure of the catalysts was characterized using X-ray diffraction, CO chemisorption, high resolution transmission electron microscopy (HRTEM) and BET surface area measurements. From the HRTEM analysis, it could be concluded that the tungsten carbide was thioresistant in our operating conditions (50 ppm of S, pressure = 6 MPa, 553 < T < 653 K, H₂/feed volumic ratio = 600). In the case of Mo₂C, molybdenum sulphide was observed as single slabs. The activity of catalysts was determined during the hydrodenitrogenation of carbazole at the wide range of temperature (553–653 K) and under a 6 MPa total pressure of H₂. The comparison of tungsten carbide and molybdenum carbide has shown higher activity of Mo₂C than W₂C at the same condition. However, W₂C leads to higher amount of isomers of main products, and have higher hydrogenation activity.