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研究了担载C_3H_7CCo_3(CO)_9络合物的脱羰基过程,发现担载于Al_2O_3上的络合物在真空或CO中均出现相当于Co(CO)_4表面络合物的特征羰基吸收带,其强度随温度的升高而增强,相应地相当于原来担载络合物的特征羰基带逐渐变弱,在300℃左右可以完全脱羰基。担载于ZrO_2和ZnO上者易于脱羰基,尤以ZnO为载体者更甚。担载络合物在He中的TPDE-GC谱表明主要以CO形式脱附,并有少量CO_2逸出,在高温下以ZrO_2为载体者出现CH_4。脱羰基样品中钴以Co~(2+)形式存在于载体上。还研究了C0在担载Co催化剂上的吸脱附及其表面反应,讨论了载体对催化剂的吸附和表面加氢反应机理的影响。
The decarbonylation of C_3H_7CCo_3 (CO) _9 complex was studied. It was found that the complex carbonyl supported on Al_2O_3 showed the characteristic carbonyl absorption band corresponding to the surface of Co (CO) _4 complex in vacuum or CO , Its intensity increases with the increase of temperature, correspondingly equivalent to the original carrying complex carbonyl band gradually weakened, at about 300 ℃ can completely decarbonylation. Supported on ZrO_2 and ZnO on the easy decarbonylation, especially ZnO as a carrier even more. The TPDE-GC spectra of the supported complexes in He showed that they desorbed mainly in the form of CO with a small amount of CO 2 escaping, and that CH 4 appeared in the presence of ZrO 2 at high temperatures. Cobalt in the decarbonylation sample exists in the form of Co ~ (2+) on the support. The adsorption and desorption of C0 on Co-supported catalyst and its surface reaction were also studied. The effects of support on the catalyst adsorption and surface hydrogenation reaction mechanism were also discussed.