Naƒon®负载型阳离子钯配合物催化剂(II)

Q4 Chemical Engineering 分子催化 Pub Date : 1994-11-27 DOI:10.1016/S0304-5102(94)87038-1
Andrew J. Seen , Kingsley J. Cavell , Alastair M. Hodges , Albert W.-H. Mau
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引用次数: 8

摘要

利用固定在Naƒon-H +中的[Pd(1,10-phen)2]2+,对Naƒon影响催化反应的能力进行了全面的研究。研究了催化剂负载、溶剂、底物、温度和压力对催化活性的影响。我们发现,虽然均匀的[Pd(1,10-phen)2][p- toyl - so3]2模型配合物使乙烯和丙烯二聚,并使1-丁烯异构,但Naƒon负载的[Pd(1,10-phen)2]2+有效地只使乙烯二聚。负载型催化剂的乙烯二聚化活性高度依赖于催化剂负载和溶剂。在极低的催化剂负载下,可以克服速率限制,并获得与均相活性相同或更高的活性。乙烯在反应溶剂中的溶解度、乙烯通过Naƒon、Naƒon形态的扩散以及高负载时催化剂可能受到的空间限制似乎是重要的因素。使用水作为反应溶剂导致负载催化剂活性的急剧增加,并且增加了正离子-阴离子分离和非配位阴离子是使用阳离子Pd(II)催化的重要方面的论点。以丙烯和1 -丁烯为进料的试验表明,负载催化剂的活性受到这些底物在Naƒon中的扩散的限制。
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Naƒon® supported cationic palladium complexes as catalysts (II)

A comprehensive investigation of the ability of Naƒon to influence catalytic reactions has been undertaken using the [Pd( 1,10-phen)2]2+ species immobilized in Naƒon—H+. The effects of catalyst loading, solvent, substrate, temperature and pressure on catalytic activity have been studied. We have found that whilst the homogeneous [Pd(1,10-phen)2][p-tolyl-SO3]2 model complex dimerizes ethene and propene, and isomerizes 1-butene, Naƒon supported [Pd(1,10-phen)2]2+ effectively dimerizes ethene only. The ethene dimerization activity of the supported catalyst has been found to be highly dependent on catalyst loading and solvent. Rate limitations are overcome at very low catalyst loadings and activities as high or higher than homogeneous activities were obtained. It appears likely that ethene solubility in the reaction solvent, ethene diffusion through Naƒon, Naƒon morphology, and possible steric constraints on the catalyst at high loadings are important factors. The use of water as the reaction solvent resulted in a dramatic increase in the activity of the supported catalyst and adds weight to the argument that cation-anion separation and a non-coordinating anion are important aspects of catalysis using cationic Pd(II) species. Tests with propene and 1 -butene as the feed indicate that the activity of the supported catalyst is limited by the diffusion of these substrates in Naƒon.

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来源期刊
分子催化
分子催化 Chemical Engineering-Catalysis
CiteScore
1.50
自引率
0.00%
发文量
2959
期刊介绍:
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Author index Subject index Hydrolysis of sucrose by dealuminated Y-zeolites Synthesis and application of organophilic polystyrene-montmorillonite supported onium salts in organic reactions Effect of the reduction temperature on the selectivity of the high temperature reaction of acetone and hydrogen over alumina and titania supported nickel and cobalt catalysts
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