(Invited) Electrochemistry Happens at the Interface
Authors: Baeumer Christoph 
Published: February 2024

Earth-abundant, active, selective and stable electrocatalysts are the cornerstone in our transition to defossilisation of the chemical industry, sector coupling, and sustainable energy. The catalyst surface is known to transform at the interface to the electrolyte, especially under operation conditions. Only the properties of the transformed interface coupled to the underlying layer gives rise to observed metrics like activity and stability. This complicates predictive electrocatalyst materials design – a challenge which can only be tackled by collaborative and interdisciplinary efforts, at the Interface between Chemistry, Physics, Materials Science, and Engineering. I believe this presents one of the main tasks for the young electrochemistry researchers in Europe and around the world, especially since the same challenges also arise in related technologies like Li-ion batteries.
In my talk I will discuss how the old wisdom from semiconductor research “the Interface is the device” can be translated into the current challenge “Electrochemistry happens at the Interface”. We need new approaches in designing and studying these electrochemical interfaces for fundamental insights that may in a next step yield better performance in future applications. The talk will be split in two parts.
Firstly, I will introduce how single crystalline surfaces can be obtained using epitaxial thin films, and discuss how these can be used to derive atomic-level structure-property relations by synergetic experimental and theoretical investigation. Such films can be fabricated with unit-cell or even atomic-layer precision and enable direct comparison to single facets typically investigated in density functional theory.
Secondly, I will discuss opportunities and challenges in surface-sensitive operando characterization in a liquid medium.1 Information from the outermost surface of a catalyst can be obtained through a standing-wave approach2,3 or extraction of a surface-only signal from careful thickness-dependent studies.4 In my ERC project “Interfaces at work”, we are also developing interface-sensitive, laboratory-based operando X-ray photoelectron spectroscopy approaches based on the new XPS user facility at the University of Twente.
Throughout the talk, I will refer to examples from LaNiO3 thin films, which are atomically flat both before and after application as electrocatalysts for the OER during water electrolysis. We selectively tuned the surface cationic composition in epitaxial growth. The Ni-termination is approximately twice as active for the OER as the La-termination.2 Our ex situ and operando characterization confirmed that the surface transformation pathways – and therefore the electrochemical functionality – depend on a single atomic layer at the surface. A second example will be the introduction of multi-cation compositions in so-called high entropy perovskite oxides (HEO), which can maximize the catalytic activity. The HEO LaCr0.2Mn0.2Fe0.2Co0.2Ni0.2O3-δ
outperforms all of its parent compounds (single TM-site element in the LaTMO3 perovskite) by orders of magnitude.5 X-ray photoemission studies reveal a synergistic effect of simultaneous oxidation and reduction of different transition metal cations during adsorption of reaction intermediates.

Rao, R. R., van den Bosch, I. C. G. & Baeumer, C. Operando X-ray characterization of interfacial charge transfer and structural rearrangements. in Reference Module in Chemistry, Molecular Sciences and Chemical Engineering 1–24 (Elsevier, 2023). doi:10.1016/B978-0-323-85669-0.00068-4.

Baeumer, C. et al. Tuning electrochemically driven surface transformation in atomically flat LaNiO3 thin films for enhanced water electrolysis. Nat Mater
20, 674–682 (2021).

Martins, H. P. et al. Near total reflection x-ray photoelectron spectroscopy: quantifying chemistry at solid/liquid and solid/solid interfaces. J Phys D Appl Phys
54, 464002 (2021).

Baeumer, C. Operando characterization of interfacial charge transfer processes. J Appl Phys
129, 170901 (2021).

Kante, M. V et al. A High-Entropy Oxide as High-Activity Electrocatalyst for Water Oxidation. ACS Nano (2023) doi:10.1021/acsnano.2c08096.

Figure 1