Beh Eugene S, Basun Sergey A, Feng Xiaofeng, Idehenre Ighodalo U, Evans Dean R, Kanan Matthew W
Department of Chemistry , Stanford University , 337 Campus Drive , Stanford , California 94305 , USA . Email:
Air Force Research Laboratory , Materials and Manufacturing Directorate , Wright-Patterson Air Force Base , Ohio 45433 , USA.
Chem Sci. 2017 Apr 1;8(4):2790-2794. doi: 10.1039/c6sc05032h. Epub 2017 Feb 6.
The local environment at polarized solid-liquid interfaces provides a unique medium for chemical reactions that could be exploited to control the selectivity of non-faradaic reactions. Polarized interfaces are commonly prepared by applying a voltage to an electrode in an electrolyte solution, but it is challenging to achieve high surface charge densities while suppressing faradaic reactions. Ferroelectric materials have permanent surface charge densities that arise from the dipole moments of ferroelectric domains and can be used to create polarized solid-liquid interfaces without applying a voltage. We studied the effects of ferroelectric oxides on the selectivity of a Rh porphyrin-catalyzed carbene rearrangement. The addition of ferroelectric BaTiO nanoparticles to the reaction solution changed the product ratio in the same direction and by a similar magnitude as performing the reaction at an electrode-electrolyte interface polarized by a voltage. The results demonstrate that colloidal suspensions of BaTiO nanoparticles act as a dispersible polarized interface that can influence the selectivity of non-faradaic reactions.
极化固液界面处的局部环境为化学反应提供了一种独特的介质，可用于控制非法拉第反应的选择性。极化界面通常通过在电解质溶液中对电极施加电压来制备，但在抑制法拉第反应的同时实现高表面电荷密度具有挑战性。铁电材料具有由铁电畴的偶极矩产生的永久表面电荷密度，可用于在不施加电压的情况下创建极化固液界面。我们研究了铁电氧化物对卟啉铑催化的卡宾重排反应选择性的影响。向反应溶液中添加铁电钛酸钡纳米颗粒，产物比例的变化方向与在由电压极化的电极 - 电解质界面上进行反应相同，且变化幅度相似。结果表明，钛酸钡纳米颗粒胶体悬浮液可作为一种可分散的极化界面，影响非法拉第反应的选择性。
