化学学报 ›› 2004, Vol. 62 ›› Issue (8): 775-782. 上一篇    下一篇

研究论文

水对氩气中催化法分解甲烷制备单壁碳纳米管的影响

刘霁欣, 任钊, 段连运, 谢有畅   

  1. 北京大学化学与分子工程学院, 北京, 100871
  • 投稿日期:2003-07-11 修回日期:2003-12-25 发布日期:2014-02-18
  • 通讯作者: 谢有畅,E-mail:yxie@pku.edu.cn E-mail:yxie@pku.edu.cn
  • 基金资助:
    国家重点基础研究发展规划(No.G2000077503)、国家自然科学基金(No.20273003)资助项目.

Effects of H2O on Preparation of Single-wall Carbon Nanotubes (SWCNT) by Catalytic Decomposition of CH4 in Ar

LIU Ji-Xin, REN Zhao, DUAN Lian-Yun, XIE You-Chang   

  1. College of Chemistry and Molecular Engineering, Peking University, Beijing 100871
  • Received:2003-07-11 Revised:2003-12-25 Published:2014-02-18

用"柠檬酸法"制备W-Fe-MgO和Mo-Fe-MgO催化剂,以Ar为载气,在1273 K催化分解CH4制单壁碳纳米管(SWCNTs),发现原料气中加水和不加水对产物的影响极大.不加水时,产物中SWCNTs含量极低,以无定形碳和多壁碳纳米管(MWCNTs)为主;加少量水时,产物绝大部分是直径在1~3 nm左右SWCNTs形成的管束.在1273 K下,H2O分压在0.67~2.0 kPa时得到SWCNTs含量较高的产物,100 mg催化剂上的碳产量为40~52 mg.进一步增加原料气中的水分压到2.7 kPa,则无碳产物生成.通过对比实验、粗产物XRD分析和对反应尾气质谱检测,可得如下结论:在Mo-Fe-MgO和W-Fe-MgO催化剂中的金属氧化物和碳化物是CH4分解为无定形碳的活性相,Fe-Mo合金相是CH4分解得SWCNTs的主要活性相.当反应气中无水时,CH4在催化剂中的氧化物和碳化物上生成的无定形碳起决定作用,而Fe-Mo合金上生成SWCNTs的反应相对减少,使产物中SWCNTs含量很低;反应气中有少量水时,水抑制了催化剂中氧化物和碳化物上无定形碳的生成,使CH4在Fe-Mo合金上分解生成SWCNTs成为主反应,此时产物中SWCNTs含量较高;水量过大时,催化剂中氧化物不能被还原为金属,故无SWCNTs生成,而此时水也抑制了无定形碳的生成,因而无任何碳产物生成.

关键词: SWCNTs, 水, 氧化物, Fe-Mo合金

W-Fe-MgO and Mo-Fe-MgO catalysts were prepared by the "citric acid" method. CH4 (60 mL/min) was decomposed on these catalysts in a small fluidized bed reactor, at 1273 K and normal pressure with Ar (200 mL/min) as carrier gas. It was found that adding small amount of water into the feed gas significantly affected the SWCNT content in the products. Using dry feed gas, the products of CH4 decomposition on the catalysts were mainly amorphous carbon and multi-wall carbon nanotubes (MWCNT). Whereas, when the feed gas contained small amount of water (partial pressure 0.67 to 2.0 kPa), the products of CH4 catalytic decomposition were mainly bundles of single-wall carbon nanotubes (1~3 nm diameter for single tube), and the carbon yield was 40~52 mg/100 mg catalyst. But, when the partial pressure of water increased to 2.7 kPa, no carbon product can be obtained. By XRD, MS analysis and comparison of experimental results, the following conclusion can be deduced: The metal oxides and carbides in Mo-Fe-MgO and W-Fe-MgO catalysts are the active phases for CH4 decomposition to amorphous carbon; the Mo-Fe alloys are the active phases for producing SWCNT. With dry feed gas, CH4 decomposition to amorphous carbon on metal oxides and carbides were dominant and the produced SWCNT on Mo-Fe alloys was relatively small, so products are mainly amorphous carbon and MWCNT with very little SWCNT. Adding a little water (partial pressure 0.67~2.0 kPa) into the feed gas, the decomposition of CH4 to amorphous carbon on oxides and carbides were hindered, so the main products are SWCNT. But adding more water (partial pressure higher or equal to 2.7 kPa) would keep the catalysts all at oxide state with no alloy, so SWCNT could not be formed and no other carbon product either.

Key words: SWCNT, H2O, oxide, Mo-Fe alloy