Developing Online ICP-MS Methodology for Examining Catalyst Degradation Dynamics during Electrochemical CO₂ Reduction

The electrochemical CO 2 reduction reaction (CO 2 RR) provides a path towards sustainable production of carbon-based fuels and chemicals, using renewable electricity to drive the conversion of CO 2 into products such as ethylene, ethanol, and methane. A challenge limiting the implementation of CO 2 RR is catalyst stability during operation, and greater fundamental understanding is needed to uncover the governing physical, chemical, and electrochemical factors, as well as degradation mechanisms, operative under reducing conditions. One tool that can be used for conducting such fundamental studies is online inductively coupled plasma mass spectrometry (ICP-MS). In this study, an experimental framework was developed for using online ICP-MS for time-resolved degradation studies during CO 2 RR conditions. Using a customized flow cell setup, we coupled an ICP-MS to a potentiostat to simultaneously apply a potential or current while evaluating dynamics and degradation for both Au and Cu catalysts. Both ionic dissolution and degradation in the form of nanoparticle detachment can be detected and analyzed. The presence of nanoparticles is indicated by spikes in ICP-MS data. The intensity of the spikes is directly related to particle size. We used ICP-MS to determine particle mass, size distribution, and cumulative mass loss over time. We found the use of ICP-MS to obtain particle size distribution gave comparable results to transmission electron microscopy (TEM) determination of particle size distribution. Au foil as the CO 2 reduction catalyst was used as a model system for detecting and quantifying degradation in situ using ICP-MS. We found Au degradation to occur in the form of nanoparticle detachment, with increasingly negative applied potential (0 V vs RHE to -1 V vs. RHE) in the presence of CO 2 leading to increased number of nanoparticles in the electrolyte; however, no ionic dissolution was observed. In comparison, when the electrolyte was saturated with N 2 , nanoparticles detached from the electrode at a lower rate than in CO 2 -saturated conditions. We also examined Cu degradation under the same conditions as the Au system. Cu degradation occurs as both ionic dissolution and nanoparticle detachment, but under all conditions, Cu has less nanoparticle detachment and cumulative mass loss due to nanoparticles than Au. The developed experimental framework in this study would be translatable to a variety of electrocatalytic reactions and environments. Examination of catalyst degradation behavior in situ , including non-traditional degradation mechanisms such as nanoparticle detachment from bulk materials, can be used to obtain greater fundamental understanding of degradation mechanisms and rational design of materials with improved stability.