环戊烷与氘在蒸发镍铜合金薄膜上的交换反应

E. Mcmahon, P. F. Carr, J. Clarke
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引用次数: 6

摘要

镍铜合金膜对环戊烷-氘交换的催化作用一直保持在低(4原子%)镍含量。当镍含量大于约24原子%镍时,可测量的活化能和产物分布模式是恒定的,但低于此值时,总体活化能显着增加,并且出现偶数分布模式(四氘和六氘产物的最大值)。后一特征归因于双键中间体,描述为ααββ-和ααββ βγ -吸附。这些物种被认为是在纯镍上发现的严重自我中毒的罪魁祸首。它们的吸附强度随着铜含量的增加而降低,导致初始自中毒程度降低,最终出现偶数氘环戊烷交换产物。这些特征在组成和纹理变化方面进行了讨论。
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Exchange reaction between cyclopentane and deuterium on evaporated nickel–copper alloy films
The catalysis of cyclopentane–deuterium exchange by nickel–copper alloy films persists to low (4 atom %) nickel content. Activation energies where measurable and product distribution patterns are constant for nickel contents greater than ca. 24 atom % nickel, but below this value there is a marked increase in over-all activation energy and an even-numbered distribution pattern (maxima for tetra- and hexa-deuterio-products) develops. The latter feature is ascribed to doubly bonded intermediate described as ααββ- and ααββγγ-adsorbed. These are the species believed to be responsible for the severe self-poisoning found on pure nickel. The strength of their adsorption decreases with the increasing fraction of copper, causing initially a decrease in the extent of self-poisoning and ultimately the appearance of the even-numbered deuteriocyclopentane exchange products. These features are discussed in terms of compositional and texture changes.
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