Lueking Angela D, Pan Ling, Narayanan Deepa L, Clifford Caroline E B
Department of Energy and Geo-Environmental Engineering, The Energy Institute, and The Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802, USA.
J Phys Chem B. 2005 Jul 7;109(26):12710-7. doi: 10.1021/jp0512199.
A graphite exfoliation technique, using intercalation of a concentrated sulfuric/nitric acid mixture followed by a thermal shock, has successfully exfoliated a herringbone graphite nanofiber (GNF). The exfoliated GNF retains the overall nanosized dimensions of the original GNF, with the exfoliation temperature determining the degree of induced defects, lattice expansion, and resulting microstructure. High-resolution transmission electron microscopy indicated that the fibers treated at an intermediate temperature of 700 degrees C for 2 min had dislocations in the graphitic structure and a 4% increase in graphitic lattice spacing to 3.5 A. The fibers treated at 1000 degrees C for 36 h were expanded along the fiber axis, with regular intervals of graphitic and amorphous regions ranging from 0.5 to >50 nm in width. The surface area of the starting material was increased from 47 m(2)/g to 67 m(2)/g for the 700- degrees C treatment and to 555 m(2)/g for the 1000- degrees C treatment. Hydrogen uptake measurements at 20 bar indicate that the overall hydrogen uptake and operative adsorption temperature are sensitive to the structural variations and graphitic spacing. The increased surface area after the 1000- degrees C treatment led to a 1.2% hydrogen uptake at 77 K and 20 bar, a 3-fold increase in hydrogen physisorption of the starting material. The uptake of the 700- degrees C-treated material had a 0.29% uptake at 300 K and 20 bar; although low, this was a 14-fold uptake over the starting material and higher than other commonly used pretreatment methods that were tested in parallel. These results suggest that selective exfoliation of a nanofiber is a means by which to control the relative binding energy of the hydrogen interaction with the carbon structure and thus vary the operative adsorption temperature.
一种石墨剥离技术,通过插入浓硫酸/硝酸混合物然后进行热冲击,成功地剥离了人字形石墨纳米纤维(GNF)。剥离后的GNF保留了原始GNF的整体纳米尺寸,剥离温度决定了诱导缺陷的程度、晶格膨胀以及由此产生的微观结构。高分辨率透射电子显微镜表明,在700℃的中间温度下处理2分钟的纤维在石墨结构中存在位错,石墨晶格间距增加4%至3.5埃。在1000℃下处理36小时的纤维沿纤维轴膨胀,石墨和非晶区域的规则间隔宽度从0.5到>50纳米不等。对于700℃的处理,起始材料的表面积从47平方米/克增加到67平方米/克,对于1000℃的处理增加到555平方米/克。在20巴下的氢吸附测量表明,总的氢吸附量和有效吸附温度对结构变化和石墨间距敏感。1000℃处理后表面积的增加导致在77K和20巴下氢吸附量为1.2%,是起始材料氢物理吸附量的3倍。700℃处理材料在300K和20巴下的吸附量为0.29%;虽然较低,但这是起始材料的14倍吸附量,高于并行测试的其他常用预处理方法。这些结果表明,纳米纤维的选择性剥离是一种控制氢与碳结构相互作用的相对结合能从而改变有效吸附温度的方法。