Atomic Layer Deposition of Cu Catalysts on Gas Diffusion Electrodes for Electrochemical CO₂ Reduction

Abstract

Electrochemical CO 2 conversion is gaining attention as an important process for carbon fixation through the use of renewable electricity to address the climate change crisis. Copper is a unique single-element catalyst that can induce C-C coupling reactions to generate high-value-added compounds. The triple phase boundary has been successfully controlled at the catalyst interface using gas diffusion electrodes (GDEs) over the past few years, resulting in high C-C coupling performance. Therefore, methods to engineer the catalyst interface on the 3D structure of GDE are of significant importance. Generally, the catalyst on the GDE is introduced through physical vaper deposition (PVD) using sputtering or E-beam evaporation, or through solution methods such as spray coating and drop-casting of nano-particles. However, the porous and tortuous 3D structure of the GDE often result in limited conformality and difficulty in obtaining a uniform and controlled infiltration of the catalyst into the support structure. In this study, we synthesized Cu catalysts directly onto GDE surfaces using plasma-enhanced atomic layer deposition (PE-ALD), which allowed for precise tuning of the catalyst size and loading at the nanoscale [1]. The synthesized catalysts were confirmed to be polycrystalline Cu nanoparticles using grazing incidence X-ray diffraction. To demonstrate the advantages of the conformal and tunable control of PE-ALD deposition, we deposited the same areal mass loading of Cu catalyst onto the GDE substrates using PVD, and compared the CO 2 reduction activity in an H-cell environment. The PE-ALD Cu catalyst showed more than 3 times higher current density than the PVD catalyst at the same electrode potential, a low (~10%) Faradaic efficiency (FE) for the hydrogen evolution reaction (HER), and greater than 75% FE for C-C coupling to form C 2+ products including ethylene and ethanol, which is comparable to the highest performances reported to date for metallic Cu catalysts in a H-cell environment. Furthermore, stable operation was observed for a duration of 15 hours, with minimal changes in activity and selectivity. In conclusion, the introduction of catalysts using PE-ALD on GDE electrodes represents a powerful new synthesis method that can increase both C-C coupling performance and selectivity compared to PVD deposition, due to its adjustable Cu nanoparticle size and high conformality. Reference 1) J. D. Lenef, S.Y. Lee, K. M. Fuelling, K. E. Rivera Cruz, A. Prajapati, D. O. D. Cornejo, T. H. Cho, K. Sun, E. Alvarado, T. S. Arthur, C. A. Roberts, C. Hahn, C. C. L. McCrory, N. P. Dasgupta, Nano Lett . 23 , 10779-10787 (2023)