(Invited) Understanding the Effects of Metal Nanoparticle Exsolution from La_0.3Ca_0.7Fe_0.7Cr_0.3O_3-δ Perovskites on CO₂-CO Electrocatalysis

Solid Oxide Fuel Cells (SOFCs) and Solid Oxide Electrolysis Cells (SOECs) are highly useful devices, capable of generating and storing large amounts of energy, respectively.1 They can do this by catalyzing CO oxidation at a SOFC anode and CO2 reduction (CO2RR) at a SOEC cathode, while the other electrode catalyzes oxygen reduction or evolution. The conduction of oxide ions through the electrolyte completes the circuit, making Solid Oxide Cells (SOCs) an excellent choice for clean energy production and use since there are no undesired byproducts.1 While traditional SOC electrodes are composed of oxide-conducting ceramics mixed with electronically conducting metals,1 a newer category of catalysts are Mixed Ionic Electronic Conductors (MIECs), with one example being the perovskite La0.3M0.7Fe0.7Cr0.3O3-δ (M = Sr, Ca) (LMFCr), investigated heavily by our group.2,3,4 As an MIEC, the full surface of LMFCr is electrochemically active, giving excellent activity at both the cathode and anode, including for CO2RR and CO oxidation.2,3 However, efforts are being made to further improve the CO2RR-CO oxidation kinetics and durability, with the Ca analogue having a better chemical match with standard electrolytes.4 One approach used recently to improve MIEC oxide performance is B-site doping with transition metals (TMs) while also creating an A-site deficiency, resulting in nanoparticle (NP) formation (exsolution) when the perovskite is subjected to reducing conditions.2 For instance, Fe-Ni NPs of a ~20 nm average size can be exsolved from (La0.3Ca0.7)0.95Fe0.7Cr0.25Ni0.05O3-δ(LCFCrNi), even at 600 °C in 70CO2:30CO (pO2 ~10-18 atm). Furthermore, NP features can easily be tailored by changing the reducing conditions or dopant used.2 In general, higher temperatures and lower pO2 lead to larger NPs over time, and more easily reducible metals tend to exsolve first under less harshly reducing conditions.2 Recent studies have suggested that NP formation enhances electrocatalytic activity by creating additional sites of reactivity, suggesting that strong NP-substrate interactions are important to catalysis.5 However, there is no clear understanding of the role played by exsolved NPs in catalyzing SOC reactions. To gain further insights, detailed electrochemical studies of LCFCrNi electrodes were done on 1-inch diameter cells constructed using Samarium-Doped Ceria buffered Scandia-Stabilized Zirconia electrolyte substrates. LCFCrNi was made into an ink and tape-cast on 0.5 cm2 on one side (working electrode, WE) and 1 cm2 on the other (counter electrode, CE) on each substrate. The cells were sintered at 1100 °C for 2 h, coated with Au ink, and sintered at 850 °C for 1 h. Electrochemical Impedance Spectroscopy (EIS) was performed at 600 °C with 70CO2:30CO at the WE and air at the CE, followed by exsolution in 5H2:95N2 at a higher temperature, and then EIS was repeated multiple times under the same conditions at 600 °C. Cells were imaged via Scanning Electron Microscopy (SEM) after ramping down to room temperature in N2 to determine the size and distribution of the NPs for each set of exsolution conditions. Under all conditions employed, the polarization resistance (Rp) was found to be stable before exsolution occurred, but started decreasing once the NPs formed, especially via a shrinking of the low frequency resistance. The low frequency resistance has been associated with CO oxidation,2 so the fact that it improves with exsolution is an indication that the increased electrode area serves to improve CO oxidation more than CO2RR. When exsolution was carried out at 800 °C for 25 h, Rp decreased more rapidly than after exsolution at 800 °C for 14 h. Exsolution at 800 °C for 25 h also showed a more rapid decrease in Rp compared to 700 °C exsolution for 25 h. These results argue that the initial formation of larger NPs (formed after longer time or at a higher temperature) results in a faster increase in the active surface area of the electrode at the lower 600 °C temperature. Further experiments are being carried out to better understand whether it is the growth of NPs or new NP formation after higher temperature exsolution that is the reason behind this observation. The results of operando synchrotron studies in CO2/CO environments before and after exsolving, as well as the use of different transition metal dopants, are also being investigated for this purpose. References [1] Mogensen, Current Opinion in Electrochemistry, 2020, 21, 265-273. [2] Ansari et al., Journal of Materials Chemistry A,2022, 10, 2280–2294. [3] Addo et al., Fuel Cells, 2015, 15, 689-696. [4] Molero-Sánchez et al., International Journal of Hydrogen Energy, 2015, 40, 1902-1910. [5] Xiong, X. et al., Journal of Materials Science & Technology, 2022, 125, 51-58.

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