使用PCET介质使Ni-HER电催化剂能够作为化物递送剂
Joseph Derosa1, Pablo Garrido-Barros1, Mengdi Li1
1Division of Chemistry and Chemical Engineering, California Institute of Technology (Caltech), Pasadena, California 91125, United States.
Journal of the American Chemical Society
|October 20, 2022
概括
研究人员重新使用了催化剂来电催化降解不和基质. 这种方法使用质子合电子转移介质来控制化物中间体,使选择性基质减少和高立体选择性成为可能.
科学领域:
- 电催化
- 有机金属化学
- 催化剂
背景情况:
- 降解电催化中的金属介质通常产生演化反应 (HER).
- 由于选择性问题,将化物中间体用于减少不和基质是具有挑战性的.
研究的目的:
- 将素支持的Ni-HER催化剂用于不和基质的电催化还原.
- 通过使用质子合电子转移 (PCET) 媒介来控制化物中间反应性来实现选择性基质减少.
主要方法:
- 电化学分析以控制和研究Ni-化物中间生成潜力.
- 用光谱和理论方法阐明涉及PCET和化物转移的反应机制.
- 用各种不和基质测试催化剂系统,包括甲基和α,β不和.
主要成果:
- 一个Ni-HER催化剂成功地通过Ni (II) -H中间体进行电催化降解.
- 用一种金属衍生PCET调解剂来产生对HER具有阳性的Ni (II) -H,从而提高选择性.
- 该机制涉及PCET从介质到Ni(II) 生成Ni(III) -H,随后还原到Ni(II) -H进行基质还原.
- 使用-预催化剂和乙烯-2-酸获得高立体选择性 (> 20:1 Z/ E).
- 协同生成PCET介导的化物有效降低α,β不和.
结论:
- 双重质子合电子转移 (PCET) 介导的化物生成为选择性电催化降解不和基质提供了一种新的策略.
- 这种方法成功地将常见的电催化剂,如Ni-HER催化剂的反应性转向有价值的有机转化.
- 开发的方法证明了高立体选择性和广泛适用于减少各种不和化合物.
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