Improved In Situ Characterization of Electrochemical Interfaces Using Metasurface‐Driven Surface‐Enhanced IR Absorption Spectroscopy

Abstract Electrocatalysis plays a crucial role in realizing the transition toward a zero‐carbon future, driving research directions from green hydrogen generation to carbon dioxide reduction. Surface‐enhanced infrared absorption spectroscopy (SEIRAS) is a suitable method for investigating electrocatalytic processes because it can monitor with chemical specificity the mechanisms of the reactions. However, it remains difficult to detect many relevant aspects of electrochemical reactions such as short‐lived intermediates. Herein, an integrated nanophotonic‐electrochemical SEIRAS platform is developed and experimentally realized for the in situ investigation of molecular signal traces emerging during electrochemical experiments. A platinum nano‐slot metasurface featuring strongly enhanced electromagnetic near fields is implemented and spectrally targets the weak vibrational mode of the adsorbed carbon monoxide at ≈2033 cm⁻¹. The metasurface‐driven resonances can be tuned over a broad range in the mid‐infrared spectrum and provide high molecular sensitivity. Compared to conventional unstructured platinum films, this nanophotonic‐electrochemical platform delivers a 27‐fold improvement of the experimentally detected characteristic absorption signals, enabling the detection of new species with weak signals, fast conversions, or low surface concentrations. By providing a deeper understanding of catalytic reactions, the nanophotonic‐electrochemical platform is anticipated to open exciting perspectives for electrochemical SEIRAS, surface‐enhanced Raman spectroscopy, and other fields of chemistry such as photoelectrocatalysis.