Mechanisms of Stabilization and Degradation of Transition Metal Oxygen Electroreduction Catalysts with in-Situ Electrochemical Flow Cell ICP-MS
Authors: Kamat Gaurav A. , Aleman Ashton M. , Mule Aniket Sandip Sandip , Kreider Melissa E , Sun Shijing , Ye Weike , Tran Kevin , Stevens Michaela Burke , Jaramillo Thomas F. 
Published: February 2024

Proton exchange membrane hydrogen fuel cell (PEMFC) deployment is presently limited by the high material cost of oxygen reduction reaction (ORR) electrocatalysts at the cathode. Developing low-cost, earth-abundant alternatives for use in acidic environments presents a material stability challenge, especially for long-term device operation. Platinum (Pt)-based materials are used in typical commercial PEMFC cathode formulations due to their simultaneous high performance and long-term stability despite the prohibitively high material cost. Developing lower-cost, longer-life catalyst materials based on earth abundant transition metals can accelerate the adoption of PEMFC technology. The impact of potential, current density, and local microenvironment has been shown to cause degradation of non-Pt materials but standard ex situ measurements can only probe surface restructuring and cumulative dissolution after operation. Material-specific degradation mechanisms that are strong functions of the operating conditions cannot be ascertained without in situ quantification of material degradation under PEMFC-relevant conditions. Information about the degradation pathways of these non-precious catalysts can assist with material design for devices; however, most efforts towards developing an in-situ understanding of PEMFC cathode catalyst degradation under operating conditions are generally limited to Pt-based materials. Extensive in situ characterization has revealed Pt-specific mechanistic information about corrosion pathways as well as conditions that exacerbate Pt alloy leaching. It has been hypothesized that the Pt degradation processes are related to oxide formation under potential cycling. With this critical in-situ information, Pt conditioning protocols have been developed to enhance material lifetime; however, investigations on non-precious materials are less common. Insights into non-precious catalyst degradation in PEMFC operating conditions are not as well-established but could be essential in enabling low-cost materials for commercial use. There is a need for more insights into a vast array of materials which necessitates the development of faster, preferably benchtop techniques for degradation analysis.

In this work, we use an in situ electrochemical flow cell assembly and coupled it with an inductively coupled plasma-mass spectrometer (ICP-MS) to quantify the loss of material in real time for several non-Pt materials under reaction conditions. The flow cell is fed by a peristaltic pump at 2.5 mL/min of gas-saturated acidic electrolyte for optimal mass transport. The cell has a three-electrode configuration with a compression-mounted metal foil working electrode, silver/silver chloride reference electrode, and Pt counter electrode downstream of other components. We evaluate a variety of transition metals across the spectrum of ORR activity: palladium, silver, nickel, copper, manganese, and cobalt. Each metal is tested under oxygen and nitrogen saturation in five electrolytes of identical pH: perchloric acid, sulfuric acid, nitric acid, hydrochloric acid, and hydrobromic acid. This setup allows for nearly real time measurement of ORR kinetics and in situ element-specific dissolution rates as a function of time. With careful design of experimental conditions and controlled variables, we are able to suggest mechanisms of degradation with specific reference to conditions under which material loss occurred such as high/low potential, oxygen-saturated/nitrogen-saturated electrolyte, or faradaic/non-faradaic current. We find some metals are stable under nitrogen-saturated electrolyte but corrode more under oxygen-saturated electrolyte only while ORR active. Furthermore, other metals are stable in nitrogen saturated electrolyte at all tested electrochemical conditions but unstable under oxygen saturated electrolyte but only outside the ORR range, implying that cathodic faradaic processes might be stabilizing the surface at low potentials. This stabilization where a thermodynamically unstable material (based on its Pourbaix diagram) exhibits greater immunity while performing ORR in certain electrolytes could inform the development stability mechanisms that direct the design of next generation, non-precious PEMFC cathode catalyst materials. With combined in situ catalyst stability analysis in five pH 1 electrolytes, we can recommend specific conditions for optimizing activity and stability based on the potential range of operation and the electrolyte composition/saturation. We can also distill mechanistic insights from these experiments by creating models that validate causes of catalyst degradation. These models are built using “graphical causal modeling”, which is a mathematical field that goes beyond correlative predictions by venturing into causal inference. We hope to expand this framework into other electrocatalytic reactions of interest. The in-situ ICP-MS electrochemical flow cell setup exhibits promise for accelerating materials stability analysis for enabling next generation Pt-free ORR electrocatalysts through practical experiments and direct comparability to established electrochemical techniques.