Directing Selectivity of Electrochemical Carbon Dioxide Reduction Using Plasmonics
Directing Selectivity of Electrochemical Carbon Dioxide Reduction Using Plasmonics
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DOI：
10.1021/acsenergylett.9b00515
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发表时间：
2019-05-01
影响因子：
22
通讯作者：
McCloskey, Bryan D.
中科院分区：
文献类型：
--
作者：
Creel, Erin B.;Corson, Elizabeth R.;McCloskey, Bryan D.
用于在水性电解质中电化学还原二氧化碳的催化剂存在高能量输入要求、与水还原析氢的竞争以及低产物选择性等问题。理论表明，可以调整等离子体催化剂以选择性地降低一组竞争反应中特定反应的能垒，但几乎没有实验证据证明复杂的多电子电化学过程中等离子体驱动的选择性。在这里，等离子体活性银薄膜电极在小阴极电位下的光活性选择性地产生一氧化碳，同时抑制氢气的产生。在较大的阴极电位下，光活性促进甲醇和甲酸盐的产生。仅在光照下观察到甲醇的产生，在黑暗条件下观察不到。等离激元活性对二氧化碳还原的偏好优于氢气释放，以及通过电压调节等离激元活性的能力表明，等离激元提供了一种有前途的方法来促进复杂的电化学反应而不是其他竞争反应。
Catalysts for electrochemical carbon dioxide reduction in aqueous electrolytes suffer from high energy input requirements, competition with hydrogen evolution from water reduction, and low product selectivity. Theory suggests that plasmonic catalysts can be tuned to selectively lower the energy barrier for a specific reaction in a set of competitive reactions, but there has been little experimental evidence demonstrating plasmon driven selectivity in complicated multielectron electrochemical processes. Here, the photoactivity at a plasmonically active silver thin film electrode at small cathodic potentials selectively generates carbon monoxide while simultaneously suppressing hydrogen production. At larger cathodic potentials, the photoactivity promotes production of methanol and formate. Methanol production is observed only under illumination, not in dark conditions. The preference of the plasmonic activity for carbon dioxide reduction over hydrogen evolution and the ability to tune plasmonic activity with voltage demonstrates that plasmonics provide a promising approach to promote complex electrochemical reactions over other competing reactions.