担载的Co_2(CO)_6(PBu_3)_2络合物的表面化学

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红外光谱表明当Co_2(CO)_6(PBu_3)_2羰基络合物担载于不同的氧化物上后,其羰基振动频带位置的波数顺序为:络合物/SiO_2(?)络合物/TiO_2>络合物/Al_2O_3>络合物/ZrO_2。当这四种担载络合物在真空中加热脱羰基时,以ZrO_2和Al_2O_3为载体者出现相当于桥式配位羰基的振动频带,分别至300℃和200℃时羰基完全脱去。以TiO_2和SiO_2为载体者,基本没有出现桥羰基的频带,而且在较低的温度下羰基即可脱去。紫外漫反射光谱表明担载络合物与担载前相比其表征Co-Co键和Co—Co配位键性质的特征带仍然存在,脱羰基后出现相当于Co~(+2)或Co_3O_4的特征谱带。程序升温分解反应发现在H_2气氛中有表面加氢反应发生。 Infrared spectra showed that the wavenumber order of the carbonyl vibration frequency band of Co_2 (CO) _6 (PBu_3) _2 carbonyl complex was as follows: complex / SiO_2 (?) Complex / TiO_2 > Complex / Al 2 O 3> complex / ZrO 2. When these four supported complexes were heated and decarbonylated in vacuum, the vibrational bands corresponding to the bridged coordination carbonyls appeared with ZrO_2 and Al_2O_3 as supports, respectively. At 300 ℃ and 200 ℃, the carbonyl groups were completely removed. With TiO 2 and SiO 2 as carrier, there is almost no bridge carbonyl band, and at lower temperatures carbonyl can be removed. Ultraviolet diffuse reflectance spectroscopy indicates that the characteristic bands of the Co-Co bond and the Co-Co bond still exist in the supported complex compared with those before loading. After decarbonylation, the characteristic bands corresponding to Co ~ (+2) or Co_3O_4 The characteristic band. The temperature-programmed decomposition reaction showed that surface hydrogenation occurred in H 2 atmosphere.
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