固体酸表面吸附分子相互作用的共振拉曼光谱研究

Lucia Kiyomi Noda
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摘要

许多酸位非常强的固体酸,如某些沸石、过渡金属交换蒙脱石、硫化金属氧化物等,已知具有氧化能力,这可能与这些材料的催化活性有关。这些固体酸与芳香分子的相互作用可以产生几种氧化产物。与强固体酸相互作用形成的芳香族分子中间种,如自由基阳离子,证明了固体的氧化能力。除了自由基阳离子外,固体酸和芳香族分子之间还可以形成电荷转移配合物。这些自由基阳离子和电荷转移配合物通常在可见光区显示吸收带,这为用共振拉曼光谱(RRS)研究这些物质提供了可能。吸附在固体酸上的苯和取代苯、吩噻嗪、t-二苯乙烯是RRS研究过的分子。由于发色团的振动模式的优先增强,用适当的辐射激发光谱,即使在其浓度较低的情况下,也可以观察到感兴趣的物质的RRS。综述了固体酸吸附分子的RRS研究进展。事实证明,RRS在表征自由基阳离子或在固体酸上形成的电荷转移配合物等中间物质方面是有价值的。
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Resonance Raman Spectroscopy Investigation of the Interaction of Molecules Adsorbed on Solid Acid Surfaces
Many solid acids with very strong acid sites, as some zeolites, transition metal exchanged montmorillonites, sulfated metallic oxides, are known to have the oxidizing ability, which can be related to the catalytic activity of these materials. The interaction of these solid acids with aromatic molecules can give rise to several oxidation products. Intermediate species of aromatic molecules formed by interaction with strong solid acids had been reported, as radical cations, proving the oxidizing ability of the solids. Besides radical cations, charge transfer complexes between the solid acids and aromatic molecules can be formed. These radical cations and charge transfer complexes usually show absorption bands in the visible region, opening the possibility of studying these species by Resonance Raman Spectroscopy (RRS). Benzene and substituted benzenes, phenothiazine, t-stilbene, adsorbed on solid acids, are examples of molecules that had been investigated by RRS. Exciting the spectrum with suitable radiation makes it possible to observe the RRS of the species of interest even when its concentration is low, because of the preferential enhancement of the vibrational modes of the chromophore. A review of RRS studies of molecules adsorbed on solid acids is presented. RRS proved valuable in characterizing intermediate species as radical cations or charge transfer complexes formed on the solid acids.
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