We report the first use of 2D-IR spectroscopy in conjunction with electrochemistry to study an electrocatalyst, in this case, one of the most widely studied and developed rhenium-based organometallic complexes, Re(bpy)(CO)<sub>3</sub>Cl. The advantage of our approach is that we use a transmission geometry cell, which is a common and accessible method. Besides the geometry, we study an actual electrocatalyst in various oxidations states. We have obtained time-dependent dynamics information of transient intermediate species and have shown how cross-peaks enable straightforward assignment of the IR spectra of three species with overlapping low-frequency bands. This advance alone will be of particular interest to the broader catalysis community for intermediate identification. Finally, we observed dynamical and spectral differences through 2D-IR (via the temporal evolution of the frequency-fluctuation correlation function) for different electrocatalysis intermediates.

Transmission mode 2D-IR spectroelectrochemistry of <i>in situ </i>electrocatalytic intermediates

ACS Fall 2021

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Transmission mode 2D-IR spectroelectrochemistry of in situ electrocatalytic intermediates