担载Ru_3（CO）_（12）－Fe_2（CO）_9混合簇的脱羰基作用和表面加氢反应  

DECARBONYLATION AND SURFACE HYDROGENATION OF SUPPORTED Ru_3 (CO)_(12)-Fe_2(CO)_9 MIXED CLUSTER

作　　者：徐慧珍[1] 过中儒[1] 施介华[1] 陈幼芳[1] 王群[1] 汪海有[1] 林种玉[1] 

机构地区：[1]浙江工业大学化工系,厦门大学固体表面物理化学国家重点实验室

出　　处：《Chinese Journal of Catalysis》1995年第5期353-358,共6页催化学报（英文）

基　　金：国家自然科学基金;厦门大学固体表面物理化学国家重点实验室资助

摘　　要：担载于ＺｒＯ２上的Ｒｕ３（ＣＯ）１２－Ｆｅ（ＣＯ）９混合簇的红外光谱表明，Ｒｕ３（ＣＯ）１２以Ｒｕ（ＣＯ）２Ｏ２表面络合物存在．混合族在真空中随温度升高而发生脱羰基作用，５００℃左右羰基完全脱掉；以Ａｌ２Ｏ３为载体者其羰基不易脱除，升高温度出现多种羰基带．混合簇中的Ｆｅ２－（ＣＯ）９极易脱羰基．担载混合簇在Ａｒ气中进行ＴＰＤＥ时，低温时以脱羰基为主，高于１５０℃时发生表面歧化反应而生成ＣＯ２；在Ｈ２气中，低温时仍以脱羰基为主，高于１５０℃时发生表面加氢反应而生成ＣＨ４．混合簇的脱羰基和表面反应能力与Ｒｕ／Ｆｅ比及载体有关．担载混合簇在ＣＯ加氢反应中以Ｒｕ（ＣＯ）２Ｏ２和分散Ｆｅ存在，还出现－ＣＨｘ多种表面物种．The decarbonylation and the surface reaction of mixed cluster Ru3(CO)12-Fe2 (CO)9 supported on ZrO2 or Al2O3 have been studied by IR spectroscopy and TPDE-GC technique.IR spectra show that the Fe2(CO)9 in the mixed cluster easily desorbs its carbonyls and disperses on the carrier in Fe form. on ZrO2, the carbonyl bands of Ru3 (CO)12 disappear and the characteristic bands corresponding to Ru (CO)2O2 appear, and the carbonyl bands fully vanish at about 500℃ in vacuum. On Al2O3, the carbonyl bands are hardly removed. TPDE-GC rasults show that the weaker carbonyls in the mixed cluster are desorbed at lower temperature, and the stronger ones are disproportionated to CO2 in Ar and hydrogenated to CH4 in H2 at higher temperature. It is also found that the TPDE character of the supported mixed cluster is similar to that of supported Ru3 (CO)12 cluster. During CO hydrogenation at 250℃, three C- H stretching bands corresponding to various-CHxspecies and the characteristic carbonyl bands of Ru (CO)2O2 surface complex are observed by in silu FT-IR spectroscopy.

关 键 词：羰基钌 羰基铁 脱羰基 一氧化碳 加氢反应 催化 

分 类 号：TQ426.92[化学工程] O613.71[理学—无机化学]