Detection of catalytic intermediates at an electrode surface during carbon dioxide reduction by an earth-abundant catalyst
Detection of catalytic intermediates at an electrode surface during carbon dioxide reduction by an earth-abundant catalyst
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DOI：
10.1038/s41929-018-0169-3
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发表时间：
2018-12-01
期刊：
影响因子：
37.8
通讯作者：
Cowan, Alexander J.
中科院分区：
文献类型：
--
作者：
Neri, Gaia;Walsh, James. J.;Cowan, Alexander J.
CO2的电催化还原提供了一条可持续的途径来生产社会所依赖的许多碳燃料和原料。[fac-Mn（bpy）（CO）（3）Br]（bpy，2，2-bipyridine）是最有前途和研究最深入的CO2还原电催化剂之一。然而，催化机理仍然未经实验证实，原型催化剂的许多关键中间体尚未观察到。在这里，我们报告使用振动和频发生光谱研究催化中间体在CO2还原过程中在电极表面原位。我们探讨了复杂的应用电位和酸依赖性的机制途径，并提供了理论推导的机制的证据。证明检测仅瞬时存在于电极表面的关键物质的能力是重要的，因为需要改进的机理理解是整个分子电催化领域的共同主题。
The electrocatalytic reduction of CO2 offers a sustainable route to the many carbon fuels and feedstocks that society relies on. [fac-Mn(bpy)(CO)(3)Br] (bpy, 2,2-bipyridine) is one of the most promising and intensely studied CO2 reduction electrocatalysts. However, the catalytic mechanism remains experimentally unproven and many key intermediates of the prototypical catalyst have not been observed. Here we report the use of vibrational sum-frequency generation spectroscopy to study the catalytic intermediates during CO2 reduction in situ at the electrode surface. We explore the complex applied-potential and acid-dependent mechanistic pathways and provide evidence of the theoretically derived mechanisms. Demonstrating the ability to detect the key species that are only transiently present at the electrode surface is important as the need for an improved mechanistic understanding is a common theme throughout the field of molecular electrocatalysis.