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Electrocatalysis plays a crucial role in realizing the transition towardsgreen energy, driving research directions from hydrogen generation to carbondioxide reduction. Understanding electrochemical reactions is crucial toimprove their efficiency and to bridge the gap toward a sustainable zero-carbonfuture. Surface-enhanced infrared absorption spectroscopy (SEIRAS) is asuitable method for investigating these processes because it can monitor withchemical specificity the mechanisms of the reactions. However, it remainsdifficult to detect many relevant aspects of electrochemical reactions such asshort-lived intermediates. Here, we develop and experimentally realize anintegrated nanophotonic-electrochemical SEIRAS platform for the in situinvestigation of molecular signal traces emerging during electrochemicalexperiments. Specifically, we implement a platinum nano-slot metasurfacefeaturing strongly enhanced electromagnetic near fields and spectrally targetit at the weak vibrational bending mode of adsorbed CO at ~2033 cm-1.Crucially, our platinum nano-slot metasurface provides high molecularsensitivity. The resonances can be tuned over a broad range in the mid-infraredspectrum. Compared to conventional unstructured platinum layers, ournanophotonic-electrochemical platform delivers a substantial improvement of theexperimentally detected characteristic absorption signals by a factor of 27,enabling the detection of new species with weak signals, fast conversions, orlow surface concentrations. By providing a deeper understanding of catalyticreactions, we anticipate our nanophotonic-electrochemical platform to openexciting perspectives for electrochemical SEIRAS, surface-enhanced Ramanspectroscopy, and the study of reactions in other fields of chemistry such asphotoelectrocatalysis.

Improved in-situ characterization of electrochemical interfaces using metasurface-driven surface-enhanced infrared absorption spectroscopy