连接剂有所影响! 在乙烯聚合过程中对CrVI/SiO2菲利普斯催化剂的分子洞察
Caterina Barzan1, Alessandro Piovano1, Luca Braglia1,2
1Department of Chemistry, NIS Interdepartmental Center and INSTM Reference Center, University of Turin , Via G. Quarello 15A, Turin I10135, Italy.
Journal of the American Chemical Society
|August 23, 2017
概括
这项研究揭示了与氧化副产品相互作用的双价 (Cr) 离子是菲利普斯催化剂中的活性位点,挑战了以前的理论.
科学领域:
- 不同质的催化
- 聚合化学
- 材料科学
背景情况:
- 菲利普斯催化剂 (Cr/SiO2) 在乙烯聚合过程中至关重要.
- 了解活性 (Cr) 位点及其协调是优化催化剂性能的关键.
- 之前的模型建议"裸体"或低协调的Cr物种作为活性场所.
研究的目的:
- 在乙烯聚合过程中使用操作敏感光谱检查 CrVI/SiO2的Cr位的分子结构变化.
- 通过乙烯减少Cr和随后的聚合过程进行区分.
- 确定负责催化活动的特定Cr物种和协调环境.
主要方法:
- 使用操作敏感的光谱技术来监测Cr位点.
- 精心控制的实验参数来分离染色体减少和聚合事件.
- 分析了Cr位点与聚合副产品的相互作用.
主要成果:
- 在六倍协调中确定了双价作为乙烯聚合的主要活性位点.
- 观察到这些活性位点与氧化副产品相互作用,主要是甲基甲酸盐.
- 在聚合过程中发现未减少的CrVI和观众CrII/CrIII物种.
结论:
- 挑战了"裸体"物种假设,相反提出活性位点是与外部氧化配体协调的离子.
- 突出了这些灵活的氧化的重要作用,类似于同质催化中的辅助.
- 对菲利普斯催化剂的乙烯聚合提供了新的机械洞察力.
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