Online Stability Investigations of Platinum Electrodes in Nonaqueous Media

In the process of developing novel electrocatalysts, the focus mainly lies on finding highly active and selective materials. The stability of electrodes is often underestimated, even though a poor stability is inextricably related to economic losses. Fundamental understanding of electrode dissolution processes in nonaqueous media is not only crucial for applications like nonaqueous battery systems, sensors, capacitors but also for organic electrosynthesis. The reasons for electrode degradation are among others anodic dissolution, cathodic dissolution or cathodic corrosion. Enhanced knowledge of dissolution mechanisms, especially understanding the influence of factors like composition or structure of electrodes, electrolytes and temperature, is important to optimize the operation conditions of reactors, and with that limit electrode degradation and increase the lifetime of devices and improve processes. Coupling electrochemical measurements with an inductively coupled plasma mass spectrometer (ICP-MS), allows online stability studies and gives valuable insights into degradation mechanisms of different electrodes and catalyst materials, which are relevant in various applications. We have developed an electroanalytical flow cell (EFC) coupled to an ICP-MS, which is suitable for the use in aggressive nonaqueous electrolytes. Furthermore, the EFC is operated in an argon filled glovebox, which allows otherwise unattainably strict control of experimental conditions, like the water content of electrolytes [1,2]. In order to demonstrate the capabilities of this novel method, dissolution of platinum as an ideal model system will be depicted first: this metal has excellent electrocatalytic activity and somewhat falsely supposed inertness. It is widely used in various fields of applications and its behavior in aqueous media is fairly well known. New aspects of its stability in different nonaqueous electrolytes are unveiled together with dependences on the chemical properties of the solvents and the conducting salts. While the dissolution behavior of completely water-free protic and aprotic electrolytes is very similar, the dissolution behavior changes markedly upon temperature variation or in presence of trace amounts of water. Different platinum dissolution profiles in several nonaqueous electrolytes will be discussed and dissolution mechanisms will be proposed, based on studies with changing water content. The dissolution of this electrode material has been followed during a running electrosynthesis. The correlation of possible reaction intermediates with the stability will be illustrated for a Kolbe electrolysis. Literature: [1] J. Ranninger, et al., Electrochem. Comm., 2020, 114 (106702), [2] J. Ranninger, et al., J. Electrochem. Soc., 2020, 167 (121507)