Lai Yungchieh, Watkins Nicholas B, Rosas-Hernández Alonso, Thevenon Arnaud, Heim Gavin P, Zhou Lan, Wu Yueshen, Peters Jonas C, Gregoire John M, Agapie Theodor
Division of Engineering and Applied Science, Liquid Sunlight Alliance, California Institute of Technology, Pasadena, California 91125, United States.
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
ACS Cent Sci. 2021 Oct 27;7(10):1756-1762. doi: 10.1021/acscentsci.1c00860. Epub 2021 Oct 14.
Boundary conditions for catalyst performance in the conversion of common precursors such as N, O, HO, and CO are governed by linear free energy and scaling relationships. Knowledge of these limits offers an impetus for designing strategies to alter reaction mechanisms to improve performance. Typically, experimental demonstrations of linear trends and deviations from them are composed of a small number of data points constrained by inherent experimental limitations. Herein, high-throughput experimentation on 14 bulk copper bimetallic alloys allowed for data-driven identification of a scaling relationship between the partial current densities of methane and C products. This strict dependence represents an intrinsic limit to the Faradaic efficiency for C-C coupling. We have furthermore demonstrated that coating the electrodes with a molecular film breaks the scaling relationship to promote C product formation.
在诸如N、O、HO和CO等常见前驱体转化过程中，催化剂性能的边界条件受线性自由能和标度关系的支配。了解这些限制为设计改变反应机制以提高性能的策略提供了动力。通常，线性趋势及其偏差的实验证明由受固有实验限制约束的少量数据点组成。在此，对14种块状铜双金属合金进行的高通量实验使得能够通过数据驱动识别甲烷和C产物的部分电流密度之间的标度关系。这种严格的依赖性代表了C-C偶联法拉第效率的内在限制。我们还证明，用分子膜涂覆电极会打破标度关系，从而促进C产物的形成。
