Polymer-precursor-derived (am-) SiC/TiC composites for resistive heaters in large volume multi-anvil high pressure/high-temperature apparatus

(Amorphous-)SiC/TiC composites for resistive tubular heaters in HP/HT experiments were obtained via a polymer-precursor process. A slurry consisting of a commercial SiC-precursor polymer (allylhydridopolycarbosilane, AHPCS) and TiC powder as conductive filler was applied to the inner walls of zirconia insulation tubes, using a centrifugation-casting method. Resistive coatings with homogeneous thickness of ～200 μm were obtained. The heaters were tested in octahedral multi-anvil assemblies at ～10 GPa with simultaneous recording of heating voltage and current. Up to a maximum temperature of ～1800°C they showed temperature vs. power characteristics reproducible from batch to batch, with resistance decreasing from 0.08 to 0.02 Ω during heating. Microstructural characterization using SEM/EDX was carried out on the recovered SiC/TiC composite material, as well as on pristine resistive heaters directly after coating and curing to 230°C, and after additional pyrolysis at 900°C in argon. In all cases, a stable composite microstructure of an interpenetrating network of TiC particles with either silicon carbide polymer precursor or an amorphous SiC phase were found. The composites were characterized by XRD and thermogravimetry. Further improvement of coating procedure and materials combination (precursor/filler/insulator substrate) may result in advanced coatings, operational well beyond 2000°C.     

Synergistic Effect of Boron Nitride and Carbon Domains in Boron Carbide Nitride Nanotube Supported Single-Atom Catalysts for Efficient Nitrogen Fixation

Developing the low-cost and efficient single-atom catalysts (SACs) for nitrogen reduction reaction (NRR) is of great importance while remains as a great challenge. The catalytic activity, selectivity and durability are all fundamentally related to the elaborate coordination environment of SACs. Using first-principles calculations, we investigated the SACs with single transition metal (TM) atom supported on defective boron carbide nitride nanotubes (BCNTs) as NRR electrocatalysts. Our results suggest that boron-vacancy defects on BCNTs can strongly immobilize TM atoms with large enough binding energy and high thermal/structural stability. Importantly, the synergistic effect of boron nitride (BN) and carbon domains comes up with the modifications of the charge polarization of single-TM-atom active site and the electronic properties of material, which has been proven to be the essential key to promote N₂ adsorption, activation, and reduction. Specifically, six SACs (namely V, Mn, Fe, Mo, Ru, and W atoms embedded into defective BCNTs) can be used as promising candidates for NRR electrocatalysts as their NRR activity is higher than the state-of-the art Ru(0001) catalyst. In particular, single Mo atom supported on defective BCNTs with large tube diameter possesses the highest NRR activity while suppressing the competitive hydrogen evolution reaction, with a low limiting potential of −0.62 V via associative distal path. This work suggests new opportunities for driving NH₃ production by carbon-based single-atom electrocatalysts under ambient conditions.     

Carbon Dynamics on the Molybdenum Carbide Surface during Catalytic Propane Dehydrogenation

The effect of the gas‐phase chemical potential on surface chemistry and reactivity of molybdenum carbide has been investigated in catalytic reactions of propane in oxidizing and reducing reactant mixtures by adding H₂, O₂, H₂O, and CO₂ to a C₃H₈/N₂ feed. The balance between surface oxidation state, phase stability, carbon deposition, and the complex reaction network involving dehydrogenation reactions, hydrogenolysis, metathesis, water‐gas shift reaction, hydrogenation, and steam reforming is discussed. Raman spectroscopy and a surface‐sensitive study by means of in situ X‐ray photoelectron spectroscopy evidence that the dynamic formation of surface carbon species under a reducing atmosphere strongly shifts the product spectrum to the C₃‐alkene at the expense of hydrogenolysis products. A similar response of selectivity, which is accompanied by a boost of activity, is observed by tuning the oxidation state of Mo in the presence of mild oxidants, such as H₂O and CO₂, in the feed as well as by V doping. The results obtained allow us to draw a picture of the active catalyst surface and to propose a structure–activity correlation as a map for catalyst optimization.     

碳化硅和碳化硼在电催化中的应用

燃料电池是具有广泛应用前景的新能源技术。碳载铂基催化剂（Pt/C）是最常用的燃料电池电极催化剂,不过Pt/C稳定性较差、且成本高昂,严重限制了燃料电池的规模化应用。共价型碳化物碳化硅和碳化硼,由于具有极强的共价键,其物化稳定性优异,成为制备高稳定性、低成本的燃料电池催化剂的重要基础材料。本文总结了相关研究成果,介绍了碳化硅和碳化硼的独特优势,讨论了相关研究的发展方向。     

熔盐电解SiO2/C直接制备SiC纳米线

采用纳米SiO₂和酚醛树脂为原料制备酚醛树脂裂解碳纳米SiO₂复合阴极(硅碳物质的量的比为1:1),直接电解PFC/SiO₂复合阴极,在900℃熔融盐CaCl₂中,恒槽压2.0V下电解,制备出碳化硅纳米线。采用场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM)、高分辨透射电子显微镜(HRTEM)及其附带的能谱仪、X射线分析衍射仪(XRD)和拉曼光谱(Raman)对产物的组成、形貌、微观结构等进行了表征。结果表明:碳化硅纳米线呈立方晶体结构,其直径为4~13nm,长可达数微米;室温下该纳米线在415nm和534nm附近有宽的发光峰。最后,讨论了碳化硅纳米线的生成机制。     

SiO2/炭泡沫和SiC/炭泡沫复合材料的制备及表征

对炭泡沫为支撑骨架的氧化硅气凝胶(SiO₂/炭泡沫)和碳化硅(SiC/炭泡沫)复合材料分别采用XRD、SEM、激光导热仪、万能力学试验机进行物相、微观结构、热学及力学性能方面的表征.结果表明:所制备的SiO₂/炭泡沫与原炭泡沫相比,具备更高的抗压强度(14.95 MPa)和更低的室温热导率(0.44 W·m^-1·K^-1).SiC/炭泡沫材料则保持了较高的抗压强度值(14.66 MPa),其在 1 200 ℃下具备极低的高温热导率(2.18W·m^-1·K^-1).热重分析表明,SiC/炭泡沫在氧化氛围中到610 ℃才发生质量的损失,而内部炭发生完全烧蚀的温度高达844 ℃,这表明该材料的抗氧化性能远好于纯的炭泡沫材料.     

Modeling and simulations of interface properties with first‐principles electronic structure computations

We report extensive first‐principles electronic structure modeling and calculations for the SiC–SiO₂ interface, a solid–solid interface formed during oxidation of silicon carbide (SiC). The interface modeling provides atomic‐scale understanding about the nature of the interface defects as well as passivation effects due to the modification of the interface bonding. In particular, simulation results show that incorporation of hydrogen and fluorine decreases the defect density, thus enhancing the performance of SiC‐based electronic devices. Copyright © 2013 John Wiley & Sons, Ltd.     

TiC/C core/shell nanowires arrays as advanced anode of sodium ion batteries

High-perfo rmance anodes of sodium ion batteries(SIBs)largely depends on rational architecture design and binder-free smart hybridization.Herein,we report TiC/C core/shell nanowires arrays prepared by a one-step chemical vapor deposition(CVD)method and apply it as the anode of SIBs for the first time.The conductive TiC core is intimately decorated with carbon shell.The as-obtained TiC/C nanowires are homogeneously grown on the substrate and show core/shell heterostructure and porous architecture with high electronic conductivity and reinforced stability.Owing to these merits,the TiC/C electrode displays good rate performance and outstanding cycling performance with a capacity of 135.3 mAh/g at 0.1 A/g and superior capacity retention of 90.14%after 1000 cycles at 2 A/g.The reported strategy would provide a promising way to construct binder-free arrays electrodes for sodium ion storage.     

Nanocomposites induced by two-dimensional titanium carbide nanosheets for highly efficient energy storage

Surface group-rich titanium carbide nanosheets (TCNSs) were successfully fabricated by simply etching Ti₃AlC₂ powders and used as dielectric fillers to promote the dielectric and energy storage performances of poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP)-based composites. The PVDF-HFP/TCNS composites realize a high dielectric constant and low dielectric loss of 16.3 and 0.034 at 10² Hz, respectively. Importantly, a high energy storage density (U_e) of 0.367 J cm⁻³ at 900 kV cm⁻¹ and a high energy storage efficiency (η ≥ 78.9%) at a TCNS content of only 0.5 wt% are obtained, which indicates that incorporating TCNS is an efficient route in enhancing U_e while maintaining a high level η of the PVDF-HFP-based composites. According to detailed characterization results, a mechanism related to the reduction of lamellar crystals in the PVDF-HFP matrix is suggested. The above mechanism restricts the movement of polymer chains near the filler-matrix interface and is proposed to be responsible for the outstanding dielectric and energy storage performances. Consequently, this work provides a simple and effective method for fabricating highly efficient energy storage nanocomposites.