Rh基催化剂上CO加氢制C_2含氧化物的原位红外光谱研究  

In-Situ- FT-IR Study of CO Hydrogenation to C_2 Oxygenates over Rh-Based Catalysts

作　　者：尹红梅[1] 丁云杰[1] 罗洪原[1] 何代平[1] 熊建民[1] 陈维苗[1] 潘振栋[1] 林励吾[1] 

机构地区：[1]中国科学院大连化学物理研究所,辽宁大连116023

出　　处：《催化学报》2004年第7期547-550,共4页

基　　金：国家重点基础研究发展规划资助项目 (G19990 2 2 40 4)

摘　　要：用原位红外光谱考察了Rh Mn Li Fe/SiO2 和Rh/SiO2 催化剂表面上CO的吸附态及CO加氢反应过程中吸附物种的变化 .结果表明 ,CO在Rh/SiO2 催化剂上仅有线式吸附态存在 ,而CO在Rh Mn Li Fe/SiO2 催化剂上既有线式吸附态存在 ,又有孪生吸附态存在 .这说明Rh Mn Li Fe/SiO2 催化剂中Rh的分散度较高 .经CO加氢反应 (3 0MPa ,5 93K)后 ,在Rh Mn Li Fe/SiO2 催化剂上可观测到C2 含氧化物前驱物种的吸收谱带 ,而在Rh/SiO2 催化剂上未观测到相应的谱带 ;CO在这两种催化剂上主要以线式吸附态存在 ,孪生吸附态基本消失 .结合催化剂对CO加氢的催化性能 ,可以认为线式吸附的CO对生成C2 含氧化物有贡献 .Rh Mn Li Fe/SiO2 催化剂的高活性是由于助剂的存在削弱了其表面吸附CO的C O键 ,促进了CO的活化 ,从而有利于C2In situ FT IR technique was employed to investigate CO adsorption and the changes of adsorbed species on the surface of Rh based catalysts during CO hydrogenation. The result showed that only the linear CO was observed on Rh/SiO 2, while linear CO and twin CO appeared on Rh Mn Li Fe/SiO 2, indicating that Rh dispersion on Rh Mn Li Fe/SiO 2 was higher than that on Rh/SiO 2. In the IR spectra of CO hydrogenation under the conditions of 593 K and 3 0 MPa, the bands at 1?716 , 1?566 , 1?442 , and 1?343 cm -1 , which were attributed to C 2 oxygenate precursors, were observed for Rh Mn Li Fe/SiO 2, while no band was detected for Rh/SiO 2. CO was adsorbed mainly as linear CO on both the catalysts during CO hydrogenation. Correlating the FT IR results with the CO hydrogenation performance suggested that the linear CO might be mainly responsible for the formation of C 2 oxygenates. The high activity of Rh Mn Li Fe/SiO 2 was due to the fact that the existence of promoters weakened the C O bond of adsorbed CO on the catalyst, promoted CO activation and favored the formation of C 2 oxygenate intermediates under the reaction conditions.

关 键 词：铑基催化剂 一氧化碳 加氢 碳二含氧化物 原位红外光谱 

分 类 号：O643[理学—物理化学]