Vadakkayil Aravind, Dunlap-Shohl Wiley A, Joy Meera, Bloom Brian P, Waldeck David H
Chemistry Department, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.
ACS Catal. 2024 Nov 11;14(23):17303-17309. doi: 10.1021/acscatal.4c04477. eCollection 2024 Dec 6.
The oxygen evolution reaction (OER) remains an important bottleneck for widespread implementation of a hydrogen economy. While improvements in the OER can be realized by spin polarizing the reaction intermediates, these methods often rely on applying external magnetic fields to ferromagnetic catalysts or by adsorbing chiral molecules onto the catalyst. Here, we show that the addition of chiral additives to the conductive binder supporting the catalysts enhances the selectivity for O formation and results in exceedingly high mass activities. The results are explained within the context of a statistical model in which the additives are hypothesized to act as a localized chiral bias that enhances radical intermediate coupling. More broadly, these studies illustrate a flexible design motif for improving OER catalysis that persists under different pH conditions, is independent of the choice of catalyst, and can be extrapolated to other chemical reactions.
析氧反应（OER）仍然是氢经济广泛应用的一个重要瓶颈。虽然通过使反应中间体自旋极化可以实现OER的改进，但这些方法通常依赖于对铁磁催化剂施加外部磁场或通过将手性分子吸附到催化剂上。在这里，我们表明，在负载催化剂的导电粘合剂中添加手性添加剂可提高生成O的选择性，并导致极高的质量活性。在一个统计模型的背景下对结果进行了解释，在该模型中，添加剂被假定为作为一种局部手性偏差，增强自由基中间体耦合。更广泛地说，这些研究说明了一种用于改善OER催化的灵活设计模式，该模式在不同pH条件下持续存在，与催化剂的选择无关，并且可以外推到其他化学反应。
