Metal–organic frameworks (MOFs) have emerged as promising candidates in electrocatalysis, particularly for the electrochemical reduction of carbon dioxide (CO2RR). Despite advances in enhancing catalytic activity and selectivity, the long-term electrocatalytic stability of MOFs remains insufficiently understood. In this study, we examine the stability and structural evolution of Zn-ZIF-8, a prototypical MOF catalyst, under CO2RR conditions. Using both batch and flow cell configurations, we assessed catalytic performance over time and observed that stability is strongly dependent on the applied electrochemical potentials. To elucidate degradation mechanisms, we conducted in-situ X-ray absorption near-edge structure (XANES) and in-situ X-ray diffraction (XRD) analyses. In-situ XANES revealed evolutions in the Zn–N4 coordination environment of the active sites, while in-situ XRD indicated bulk transformations in the long-range crystalline structure of Zn-ZIF-8 during electrolysis. These findings provide critical mechanistic insights into the structural dynamics governing MOF catalyst stability and inform the rational design of more durable MOF-based electrocatalysts for CO2RR applications.
