【摘要】 采用恒电位电解方法,分别在酸性和碱性两种饱和乙炔的水介质中,探讨了乙炔在铜/石墨阴极上(石墨上电沉积铜和石墨一铜层状嵌入物)的电催化还原和电引发聚合行为。电极对乙炔还原成乙烯表现较高活性和很高选择性(～99％,对气相产物)。对电极上活性组份Cu~0(或Cu′)与乙炔分子可能发生的σ—π活化作用和加氢方式进行了讨论。本文还运用现场与非现场Raman光谱技术,考察了在乙快还原的同时,电极表面上形成聚乙炔复盖物的情况,提出了一种电引发聚合机理,能较好地解释实验事实。更多还原

【Abstract】 With the method of potentiestatic electorlysis, behaviours of the electro-catalytic reduction and electroinitiated polymerization of acetylene on copper/graphite cathodes, which were prepared by the electrodeposition of copper on graphite or the intercalation of copper in the layers of graphite, have been investigated in the acidic and basic solutions saturated with acetylene respectively. It has been shown that the electrodes have a relatively high activity and very high selectivity for the electrocatalytic reduction of acetylene toethylene. The possible σ-π interaction between acetylene and Cu(0)[or Cu ( I )] on the electrodes and the pathways of cathodic hydrogenation are discussed. The formation of polyacetylene on the electrodes has been studied by both in-situ and ex-situ Raman spectroscopic techniques. A mechanism of electroinitiated polymerization is proposed, which can give a reasonable explaination for the experimental results.更多还原