(Invited) Electrocatalysis at Modified Electrochemical Interfaces
Authors: Strmcnik Dusan , Kozlica Dzevad K , Martins Milena , Farinazzo Bergamo Dias Martins Pedro , Logar Anja , Vodeb Ozbej , Mathew Maris M , Finsgar Matjaz , Genorio Bostjan , Gaberscek Miran 
Published: December 2024

Electrochemical energy storage and conversion technologies, which include fuel cells, electrolyzers, batteries, photoelectrochemical devices are at the forefront of the transition to a sustainable future. Although they have all been in use for more than half a century, they are far from reaching their full potential as defined by the laws of thermodynamics. Their performance rests almost entirely on the electrochemical interface - the boundary between the electronic conductor (electrode) and the ionic conductor (electrolyte). The desire of both phases to reduce the surface energy as well as the appearance of electrochemical potential across the interface can manifest itself as the formation of unique (near)surface atom arrangements (e.g. surface relaxation or reconstruction), as significant differences in electrode composition close to the surface (e.g. segregation profile), via substrate-adsorbate covalent and non-covalent interactions, via formation of a passive film as well as ordering of solvent and/or electrolyte molecules several nm away from the surface. This extremely complex and sensitive "interfacial bridge", is a consequence of inherent incompatibility of two materials, brought into contact, and is very hard to control. However, to control it means to control the energy efficiency, power density, durability and safety – the most important metrics of any energy conversion and storage device.

In this presentation we will discuss, how the chemical nature of non-covalently and covalently [1,2] adsorbed species as well as thicker passive films and their morphology at the electrochemical interface affect the individual terms of the common rate equation [1], including the free energy of adsorbed intermediates and adsorbed spectators, mass transport, availability of active sites and electronic and ionic resistivity for common electrocatalytic reactions in acid and alkaline aqueous as well as in non-aqueous media on a plethora of metal electrodes (Pt, Ir, Au, Ni, Cu) as well as carbon. We will draw parallels between HER, OER, HOR and ORR in electrolyzers [1], fuel cells [2] and Li-ion batteries [3,4]. The interphase properties will be discussed through the lens of deviations of modified electrode properties from its intrinsic properties. Examples of artificially modified interfaces [5,6] will be given to demonstrate our ability to tailor their activity, stability and selectivity to our liking.

[1] Strmcnik, D. Lopes, P.P., Genorio, B., et al. Design principles for hydrogen evolution reaction catalyst materials, Nano Energy, 29, 29-36 (2016)

[2] Strmcnik, D., Uchimura, M., Wang, C. et al. Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption. Nature Chem 5, 300–306 (2013)

[3] Strmcnik, D., Castelli, I.E., Connell, J.G. et al. Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries. Nat Catal 1, 255–262 (2018)

[4] Martins, M., Haering, D., Connell, J.G., et al. Role of Catalytic Conversions of Ethylene Carbonate, Water, and HF in Forming the Solid-Electrolyte Interphase of Li-Ion BatteriesACS Catalysis 13, 9289-9301 (2023)

[5] Zorko, M. Martins, P.F.B.D., Connell, J.G. et al. Improved Rate for the Oxygen Reduction Reaction in a Sulfuric Acid Electrolyte using a Pt(111) Surface Modified with Melamine, ACS Applied Materials & Interfaces 13, 3369-3376 (2021)

[6] Strmcnik, D., Escudero-Escribano, M., Kodama, K. et al. Enhanced electrocatalysis of the oxygen reduction reaction based on patterning of platinum surfaces with cyanide. Nature Chem
2, 880–885 (2010)