(389f) Activity, Selectivity, and Stability: Tracing New Routes for Electrocatalysts Design By Using First-Principles Methods

Electronic-structure methods are powerful tools for the rationalization of reaction mechanisms and for guiding the synthesis of electrocatalysts with tailored properties. In this contribution, I will present selected case studies in which computational approaches were used to elucidate the principles that govern the activity, selectivity, and stability of electrocatalytic materials under realistic reaction conditions. These works were carried out during my postdoctoral experiences at the University of Wisconsin-Madison (Mavrikakis Group) and at the Technical University of Denmark (Nørskov Group).

We derived fundamental understanding on state-of-the-art and newly-discovered catalytic materials for technologically-relevant processes, ranging from CO₂ reduction reaction [1], to hydrogen oxidation reaction [2] and the ammonia oxidation reaction. I will show how electronic-structure calculations, combined with experimental high-precision electrochemistry methods, were used to define a new class of highly active and stable catalytic architectures: Non-stoichiometric Overlayers [3]. Finally, I will put these works in the context of the EU-funded MSCA project “CAMELLIA” (ComputAtional Mapping of ELectrocataLytic InterfAces) which is aimed at i. elucidating the in-situ nature of electrocatalyst active sites, ii. bridging the gap between experimental and computational methods in addressing key processes hindering the development of active and stable electrocatalytic; iii. going beyond state-of-the-art computational models based on well-defined extended surfaces, towards the simulation of nanoparticles with realistic sizes in a complex electrochemical environment.

[1] F. Yang, A. Elnabawy, R. Schimmenti, S. Yao, R. Deng, S. Song, Y. Lin, W. Xu, M. Mavrikakis “Bismuthene for Highly Efficient Carbon Dioxide Electroreduction Reaction” Nature Communications, 2020, 11, 1088

[2] Y. Gao, Y. Yang, R. Schimmenti, E. Murray, H. Peng, Y. Wang, C. Ge, W. Jiang, G. Wang, F.J. DiSalvo, D. A. Muller, M. Mavrikakis, L. Xiao, H. D. Abruña, L. Zhuang “A completely precious metal–free alkaline fuel cell with enhanced performance using a carbon-coated nickel anode” Proceedings of the National Academy of Sciences of the United States of America, 2022, e2119883119

[3] P.P. Lopes, D. Li, H. Lv, C. Wang, D. Tripkovic, Y. Zhu, R. Schimmenti, H. Daimon,Y. Kang, J. Snyder, N. Becknell, K.L. More, D. Strmcnik, N.M. Markovic, M. Mavrikakis, V.R. Stamenkovic “Eliminating Dissolution of Pt-based Electrocatalysts at the Atomic Scale” Nature Materials, 2020, 19,1207-1214