Applying Nuclear Forward Scattering as In Situ and Operando Tool for the Characterization of FeN₄ Moieties in the Hydrogen Evolution Reaction

Abstract

Nuclear forward scattering (NFS) is a synchrotronbased technique relying on the recoil-free nuclear resonance effect similar to Mossbauer spectroscopy. In this work, we introduce NFS for in situ and operando measurements during electrocatalytic reactions. The technique enables faster data acquisition and better discrimination of certain iron sites in comparison to Mossbauer spectroscopy. It is directly accessible at various synchrotrons to a broad community of researchers and is applicable to multiple metal isotopes. We demonstrate the power of this technique with the hydrogen evolution mechanism of an immobilized iron porphyrin supported on carbon. Such catalysts are often considered as model systems for iron−nitrogen-carbon (FeNC) catalysts. Using in situ and operando NFS in combination with theoretical predictions of spectroscopic data enables the identification of the intermediate that is formed prior to the rate-determining step. The conclusions on the reaction mechanism can be used for future optimization of immobilized molecular catalysts and metal−nitrogen−carbon (MNC) catalysts.