Exploring cost-effective and efficient catalysts for oxygen reduction reaction (ORR) poses a significant challenge, especially in the pursuit of alternatives to precious metals like platinum. Significant advancements have driven electrochemists to develop efficient ORR catalysts using abundant materials, particularly iron (Fe)-based, known for their exceptional performance in ORR. While the crucial function of Fe in boosting ORR catalytic activity is recognized, the connection between material attributes and catalytic performance remains enigmatic. Understanding the dynamic processes involved in oxygen electrocatalysis is paramount for designing precious-metals-free ORR electrocatalysts. Mössbauer spectroscopy stands out as a powerful technique for deciphering the structural characteristics of Fe species in catalysis, facilitating the identification of active sites and the clarification of catalytic mechanisms. By showcasing noteworthy case studies within this review, we demonstrate the application of in-situ/operando ⁵⁷Fe Mössbauer spectroscopy across diverse Fe-involved materials in ORR catalysis. This sheds light on various aspects of ORR catalysis, such as identifying active sites, assessing stability, and understanding the reaction mechanism. Our inquiry drives towards the opportunities and hurdles associated with Mössbauer spectroscopy, unveiling potential breakthroughs and avenues for enhancement within this pivotal research realm.

The development of highly efficient and cost-effective electrocatalysts for the sluggish oxygen evolution reaction (OER) remains a significant barrier to establish effective utilization of renewable energy storage systems and water splitting to produce clean fuel. The current status of the research in developing OER catalysts shows that NiFe-based oxygen evolution catalysts (OECs) have been proven as excellent and remarkable candidates for this purpose. But it is critically important to understand the factors that influence their activity and underlying mechanism for the development of state-of-the-art OER catalysts. Therefore, the development of in-situ/operando characterizations is urgently required to detect key intermediates along with active sites and phases responsible for OER. ⁵⁷Fe Mössbauer spectroscopy is one of the appropriate and suitable techniques for determining the phase structure of catalysts under their electrochemical working conditions, identifying the active sites, clarifying the catalytic mechanisms, and determining the relationship between catalytic activity and the coordination structure of catalysts. In this tutorial review, we have discussed the current status of research on NiFe-based catalysts with particular attention to introduce in detail the knowhow about the development and utilization of in-situ/operando ⁵⁷Fe Mössbauer-electrochemical spectroscopy for the study of OER mechanism. A brief overview using NiFe-(oxy)hydroxide catalysts, derived from ordered porous metal-organic framework (MOF) material NiFe-PBAs (Prussian blue analogues), as a typical model study case for the OER electrocatalyst and self-designed in-situ/operando ⁵⁷Fe Mössbauer-electrochemical instrument, has been provided for the better understanding of readers. Moreover, using in-situ/operando ⁵⁷Fe Mössbauer spectroscopy, the crucial role of Fe species during OER reaction has been explained very well.