隔离的Ni2+作为热石中1-丁烯二聚化活性中心
Laura Löbbert1, Abelina Ellert1, Mengjie Zhou1
1Department of Chemistry and Catalysis Research Center, Technical University of Munich, Garching 85748, Germany.
齐奥利特中分离的酸催化了1-布二聚化. 像FAU这样的大孔泽奥利特由于过渡状态的更好的稳定性而表现出更高的活性,尽管对线性八烯的选择性较低.
科学领域:
- 不同质的催化剂.
- 热带石的化学结构
- 有机金属化学 有机金属化学
背景情况:
- 热质石被广泛用作石油化学过程中的催化剂.
- 基于的催化剂对烯酸转化是有效的.
- 了解活性部位和反应机制对于催化剂设计至关重要.
研究的目的:
- 为了确定Ni交换热石中的1-丁烯二元化活性位点.
- 为了研究热带石框架拓对催化性能的影响.
- 阐明反应机制和控制活性和选择性的因素.
主要方法:
- 2+的离子交换成CHA,MFI和FAU热带石框架.
- 在超临界条件下的1-丁烯二聚化反应.
- 对反应产物的分析以确定选择性和转化.
- 动力学研究以确定旋转频率和激活能量.
主要成果:
- 在Al-对位点上的孤立的Ni2+是活性中心.
- 线性八烯的选择性随着地石孔径的增加而降低 (CHA ≈ MFI > FAU).
- 营业额的频率随着孔径大小显著增加,FAU显示最高的活动 (约. 两个数量级高于CHA/MFI).
结论:
- 1-丁烯二聚化通过涉及Ni-丁烯复合物的Cossee-Arlman型机制进行.
- 泽奥利特孔径大小通过反应剂和过渡状态的差异稳定影响反应性.
- FAU的较大的孔隙增强了C-C合,导致了更高的二元化活性.
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