UV-Vis operando spectroelectrochemistry for (photo)electrocatalysis: Principles and guidelines

Electrocatalytic and photoelectrocatalytic technologies are key players in the transition to a circular economy. In order to rationally design the new generation of efficient (photo)elec-trocatalysts it is critical to establish which performance bottle-necks must be overcome during the complex catalytic transformations. Obtaining such detailed mechanistic and ki-netic knowledge requires the use of operando spectroscopic techniques that are capable of probing the system under operating conditions. Of all the methods available UV-Vis spectroelectrochemistry stands out for its versatility and experimental simplicity which enables the systematic study of samples under a wide range of reaction conditions. From a mechanistic viewpoint, this technique allows us to quantify the accumulation of reactive species at the catalyst-electrolyte interface and, through a kinetic population model, opens the door to characterising the kinetics of the rate determining step of catalysis. Here, we review the different information that can be extracted from UV-Vis spectroelectrochemistry and how it can be used to understand catalytic mechanisms in solid (photo)electrodes.

Automated summary

Electrocatalytic and photoelectrocatalytic technologies play crucial roles in the transition to a circular economy. UV-Vis spectroelectrochemistry is a versatile and simple experimental technique that allows for detailed mechanistic and kinetic understanding of catalytic transformations, facilitating the rational design of efficient (photo)electrocatalysts.