Synthesis of Nanocarbon Capsules by Vapor Detonation of Pentacarbonyl Iron
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摘要: 采用气相爆轰法，以乙炔气体、氧气和五羰基铁为原料成功地合成了比表面积为253.857 m2/g的胶囊状碳纳米材料。对反应的前置实验九羰基二铁的热分解反应的研究表明，在60~140℃之间，九羰基二铁热分解为五羰基铁和十二羰基三铁。对爆轰产物进行了XRD、TEM和BET物理吸附实验，结果表明：产物XRD图谱石墨峰明显，产物主要为具有石墨化倾向的薄层胶囊状无定形碳结构；实验产物比表面积为253.857 m2/g，孔体积为0.940 cm3/g，平均孔径为2.731 nm；吸附-脱附曲线回滞环类型为H3型，孔结构主要为颗粒堆积而形成的狭缝孔；爆轰产物比表面积较大，具有较强的吸附能力。证实了同样采用铁作为触媒，乙炔在不添加惰性气体作为缓冲剂的情况下，由于爆速过高而无法用于合成碳纳米管。Abstract: In this study, the capsular carbon nanomaterials with large specific surface area are synthesized using gas phase detonation method doped with acetylene gas, oxygen and pentacarbonyl iron.The pre-experimental of the reaction for the thermal decomposition reaction of carbonyldiiron showed that the iron octacarbonyl diketones were thermally decomposed according to nine carbonyldiiron decomposed into iron pentacarbonyl and tricarbonyl dodecylcarbonyl between 60 and 140℃.The morphology and components of the synthesized nanoparticles were characterized through X-ray diffraction studies, transmission electron microscopy and physical adsorption instrument analyses.Results showed that the graphite peaks can be clearly observed in XRD pattern and the product is mainly with a structure that capsular amorphous carbon with thin layer which has graphitization tendency.The experimental product has a specific surface area of 253.857 m2/g, a pore volume of 0.940 cm3/g and an average pore size of 2.731 nm, type of the hysteresis loop of the adsorption & desorption curve is H3.The pore structure is mainly formed by the accumulation of granules and has a large specific surface area and a strong adsorption capacity.The article confirms that iron is also used as a catalyst.Acetylene cannot be used to synthesize carbon nanotubes without adding an inert gas as a buffering agent due to its high detonation velocity.
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Key words:
- gaseous detonation synthesis /
- nanomaterials /
- capsular carbon /
- specific surface area
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图 1 气相爆轰管的示意图
Figure 1. Schematic of gaseous detonation tube
1.Heating system; 2.Explosion gas; 3.Oil inlet; 4.Sealed flange; 5.Filling port; 6.Oil outlet; 7.Vacuometer; 8.Intake valve; 9.Vacuum valve; 10.Main valve; 11.Ignition plug; 12.Reactor of iron pentacarbonyl
图 4 产物吸附-脱附等温线和其相应的孔径分布图
Figure 4. Adsorption-desorption isotherms of product and their corresponding pore size distributions
表 1 实验的主要参数
Table 1. Major experimental parameters
Experiment No. Initial temperature/K n(C2H2):n(O2) Partial pressure of acetylene/kPa Partial pressure of oxygen/kPa Mass of Fe2(CO)9/g 1 400 4:1 40 10 0.5 2 400 3:1 45 15 0.5 3 400 2:1 40 20 0.5 4 400 3:1 60 20 0.5 
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表 2 九羰基二铁分解实验参数
Table 2. Various parameters in the experiment of nonacarbonyldiiron decomposition
Experiment No. Mass of Fe2(CO)9/g Initial reading/kPa Final reading/kPa Pressure change Δp0/kPa 1 2 2.00 4.11 2.11 2 4 2.00 6.29 4.29 3 8 2.00 10.52 8.52 4 12 2.00 14.44 12.44
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表 3 实验爆轰参数
Table 3. Detonation parameters of experiments
Experiment No. Qe/(kJ·g-1) D/(m·s-1) pJ/MPa T/K 1 10.3 2 751.33 1.43 4 295.47 2 10.6 2 799.19 1.79 4 498.55 3 11.2 2 874.60 1.92 4 815.61 4 10.6 2 799.19 2.39 4 498.55
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