CO在负载型Ru、Co和Ru－Co金属簇催化剂上的脱附及表面加H_2反应  

DESORPTION AND HYDROGENATION OF CO ON SUPPORTED Ru,Co AND Ru-Co CLUSTER CATALYSTS

作　　者：徐慧珍[1] 施介华[1] 过中儒[1] 

机构地区：[1]浙江工学院化工系

出　　处：《燃料化学学报》1994年第1期70-76,共7页Journal of Fuel Chemistry and Technology

基　　金：国家自然科学基金

摘　　要：担载于Ａｌ＿２Ｏ＿３和ＺｒＯ＿２上的三种金属羰基络合物在Ｈｅ气中进行程序升温分解（ＴＰＤＥ）时，其羰基发生表面歧化反应生成ＣＯ＿２能力的次序为ＮａＲｕＣｏ＿３（ＣＯ）＿（１２）＞＞Ｒｕ＿３（ＣＯ）＿（１２）＞＞Ｃ＿３Ｈ＿７ＣＣｏ＿３（ＣＯ）＿９。吸附于担载Ｒｕ＿３和Ｃｏ＿３上的ＣＯ在Ｈｅ气中进行程序升温脱附（ＴＰＤ）时发生表面歧化反应生成ＣＯ＿２。在Ｈ＿２气中，吸附于担载Ｒｕ＿３上的ＣＯ力Ｈ＿２生成ＣＨ＿４，吸附于担载Ｃｏ＿３上的ＣＯ却生成Ｃｏ＿２，在担载ＲｕＣｏ＿３上的ＣＯ几乎完全力Ｈ＿２生成ＣＨ＿４。以ＺｒＯ＿２为载体的Ｒｕ＿３、Ｃｏ＿３和ＲｕＣｏ＿３催化剂上的ＣＯ吸附和反应能力均大于以Ａｌ＿２Ｏ＿３为载体者。吸附于以ＺｒＯ＿２为载体的ＲｕＣｏ＿３催化剂上的ＣＯ在ＴＰＤ和ＩＲ谱上并不显示ＣＯ物种的存在，分析了Ｃ＿（ａｄｓ）和Ｏ＿（ａｄｓ）物种存在的原因。根据实验结果还讨论了金属、载体对催化性能的影响和表面反应机理。TPDE-GC results show that the ability for disproportionation of carbonylgroups in three metal carbonyls supported on Al_2O_3 and ZrO_2 follows the follwing order :NaRuCo_3(CO)_(12)》Ru_3(CO)_(12)》C_3H_7CCo_3(CO)_9.During the TPD of CO adsorbed on Ru_3and Co_3 catalysts prepared from supported complexes in He stream,the desorbed productwas CO_2.It is obvious that the CO_2 was formed from the surface disproportionation of COadsorbed on both catalysts,During the TPSR of CO in H_2 stream,the CO adsorbed on sup-ported Ru_3 catalysts was mainly hydrogenated to CH_4.However,the reaction product of COadsorbed on supported Co_3 catalysts was composed essentially of CO_2.It is noticed that theadsorbed species of CO on RuCo_3/ZrO_2 was not observed in TPD-GC profile and IR spectra.Nevertheless,during the TPSR of CO in H_2 stream,Iarge amount of CH_4 in reaction productwas observed. It seems that the CO on RuCo_3/ZrO_2 catalyst prepared from NaRuCo_3(CO)_(12)complex is easily dissociated to C_(ads)and O_(ads) due to the common action of Na￣+ and ZrO_2.TP-SR-GC results show that the abilities for adsorption and reaction of CO on Ru_3, Co_3 andRuCo_3 supported on ZrO_2 are higher than those with as the support Al_2O_3.The selectivity tomethane in the conversion of CO on supported RuCo_3 is higher than that on supported Ru.

关 键 词：一氧化碳 钌 钴 催化剂 脱附 加氢 

分 类 号：O613.71[理学—无机化学]