Mechanistic understanding of electrochemical nitrogen reduction reaction on hybrid plasmonic nanostructures using operando surface-enhanced Raman spectroscopy
Mechanistic understanding of electrochemical nitrogen reduction reaction on hybrid plasmonic nanostructures using operando surface-enhanced Raman spectroscopy
复制标题
使用操作表面增强拉曼光谱了解混合等离子体纳米结构上电化学氮还原反应的机理
DOI：
10.1021/scimeetings.1c00710
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
El-Sayed, Mostafa
中科院分区：
文献类型：
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作者：
Nazemi, Mohammadreza;El-Sayed, Mostafa
用于氨合成的电化学氮气还原反应(NRR)可以为资本和碳密集型热化学反应(Haber-Bosch)提供一种清洁、可持续和分散的方法，如果该过程耦合到可再生能源的话。电化学氨合成的挑战之一是寻找在环境条件下或接近环境条件下具有合适活性的催化剂来断裂N_2三键。需要改进电催化剂、电解液和电化学池的设计，以克服电化学NRR的选择性和活性障碍。原位和远距离表面增强拉曼光谱(SERS)是一种非常适合于探测固-液(电极/电解液)界面电化学反应的技术。Operando SERS允许即使在低丰度的情况下也能检测到中间物种，并通过结合光谱学和电化学来使用杂化等离子体纳米结构(例如，Au-Pd)来深入了解NRR机制。恒电位仪被用来在SERS活性衬底上施加电位，然后通过光谱的变化进行监测。研制了光谱电化学池，用于探测电极/电解液界面上可能产生的NH3和可能的中间物种的痕量。这项工作将有助于理解反应机理，并最终设计出更有效的电化学能量转换催化剂。本材料基于国家科学基金会1904351号拨款资助的工作。
Electrochemical nitrogen reduction reaction (NRR) for ammonia synthesis might offer an alternative means to the capital- and carbon-intensive thermochemical process (Haber-Bosch) in a clean, sustainable, and decentralized way if the process is coupled to renewable electricity sources. One of the challenges in electrochemical ammonia synthesis is finding catalysts with a suitable activity for breaking N2 triple bonds at or near ambient conditions. Improving the design of electrocatalysts, electrolytes, and electrochemical cells is required to overcome the selectivity and activity barrier in electrochemical NRR. In-situ and operando surface-enhanced Raman spectroscopy (SERS) is a well-suited technique to probe electrochemical reactions at the solid-liquid (electrode/electrolyte) interface. Operando SERS allows for the detection of intermediate species even in low abundance and is used to provide insights into NRR mechanisms using hybrid plasmonic nanostructures (e.g., Au-Pd) by combining spectroscopy and electrochemistry. A potentiostat is used to apply potential on a SERS active substrate that is then monitored by changes in a spectrum. The spectroelectrochemical cell is developed to operando probe the trace of NH3 and possible intermediate species produced at the electrode/electrolyte interface. This work would aid in understanding the reaction mechanism and ultimately designing more efficient catalysts for electrochemical energy conversion systems. This material is based upon work supported by the National Science Foundation under grant no. 1904351.