Synthesis and characterization of graphite-like B–C–N materials of composition CNx(BN)y(x≪ 1, y≦ 1)
Synthesis and characterization of graphite-like B–C–N materials of composition CNx(BN)y(x≪ 1, y≦ 1)
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DOI：
10.1039/b107419a
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发表时间：
2002-04
影响因子：
--
通讯作者：
T. Komatsu;A. Goto
中科院分区：
文献类型：
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作者：
T. Komatsu;A. Goto
在硼氢化物与七氮杂非那烯衍生物、N-酰亚胺、胺类、腈类和氰胺类等含氮化合物的前驱体热解体系中，合成了各种类石墨B-C-N材料。所得到的材料用CNx（BN）y和CBx（BN）y的分子式描述，所述分子式由CNx和（BN）y段组成。结合化学分解和结构分析，证实了CNx（BN）y的链段结构中含有（-CC-）n-N、B-N-C和B-N对的局部键，但不含C-B键。通过与杂化材料的类比，提出了一种可互溶的共混结构模型。原料的组成和产率与原料的化学反应性质、析氮性质和石墨化程度密切相关。特别地，具有高BN含量的B-C-N材料由七氮杂非那烯聚合物以少量制备，并且具有低BN含量的材料由四氰基乙烯以接近100%的产率制备。材料在500 °C至950 °C下氧化成氧化硼，然而，在惰性气氛下，它们在至少1200 °C下是稳定的。
Various graphite-like B–C–N materials were synthesized in the precursor pyrolysis system of boron trichloride and nitrogen-containing materials such as heptaazaphenalene derivatives, carbodiimides, amines, nitriles and cyanamides. The materials obtained were described with a formula of CNx(BN)y and CBx(BN)y consisting of CNx and (BN)y segments. A combination of chemical decomposition and structural analysis elucidated that the segment structure of CNx(BN)y contains local bonds of (–CC–)n–N, B–N–C and B–N pairs but no C–B bonds. A miscible blend structure model was expected by analogy with hybrid materials. Compositions and yields of the materials were closely related to the properties of chemical reaction, nitrogen evolution and graphitization of the starting materials. In particular, B–C–N materials with high BN content were prepared in small quantities from the heptaazaphenalene polymers, and the materials with low BN content were produced from teteracyanoethylene in nearly 100% yield. The materials were oxidized to boron oxide from 500 °C to 950 °C, however, under an inert atmosphere they were stable to at least 1200 °C.