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电子丰富的基介质通过针复合物提高了电催化醇氧化的热力性能
Conor M Galvin1, Robert M Waymouth1
1Department of Chemistry, Stanford University, Stanford, California 94305, United States.
Journal of the American Chemical Society
|November 3, 2020
概括
富含电子的作为有效的电化学媒介,显著降低了由复合物催化的酒精氧化开始的潜力. 这种经过介导的电催化反应对酒精氧化反应具有很高的效率和化学选择性.
科学领域:
- 电化学
- 有机金属化学
- 催化剂
背景情况:
- 复合物是众所周知的各种化学转换的催化剂.
- 酒精的电化学氧化提供了可持续的合成途径.
- 介导电催化可以提高反应效率和选择性.
研究的目的:
- 研究使用富含电子的作为酒精氧化的电化学媒介.
- 使用介质阐明催化酒精氧化的机制.
- 评估介导电催化系统的效率和选择性.
主要方法:
- 使用胺二化合物的电化学氧化 ((PNP) Ir ((H) 2,IrN 1).
- 添加富含电子的介质 (例如α-rac-tocopherol,2,4,6-tri-tert-butylphenol,化-toluene)
- 机理研究包括同位素标记和潜在发病测量.
- 大量氧化实验和法拉第效率的确定.
主要成果:
- 与Fc+/ 0相比,醇调解剂使酒精氧化开始的潜力从- 0. 65V降低到- 1. 07V.
- 催化循环涉及两个连续的原子转移 (HAT) 从复合物到短暂的基.
- 周转频率高达14.6s-1的平均法拉第效率为93%.
- 在2-propanol和1,2-benzenedimethanol的氧化中,中介系统表现出极好的化学选择性.
结论:
- 富含电子的是催化酒精氧化的有效电化学媒介.
- 该机制涉及从复合物转移到基.
- 介导系统为酒精氧化提供了高效和化学选择性的方法.
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