Selectivity in Catalysis
Bukas Group
Welcome to the Catalysis group of the FHI Theory department!
We are working on fundamental understanding of heterogeneous thermal and electro-catalytic processes, with a special focus on product selectivity.
Our research integrates electronic structure calculations with thermodynamic and kinetic modeling, thus aiming to provide predictive-quality simulations of atomic-scale resolution. Among the many challenges that we want to tackle are questions about e.g. the evolving catalyst surface under realistic operating conditions, microscopic mechanisms of (de)activation/poisoning, and the main factors or descriptors that govern catalytic performance. Our models are continuously challenged and tested against well-defined experiments through active collaborations within the new Catalysis Laboratory or 'CatLab' platform (click here for more information on CatLab’s scientific mission and goals).
One of the group’s key objectives is to elucidate catalyst selectivity, the origin of which often remains poorly understood especially in the field of electrocatalysis. A characteristic example is the oxygen reduction reaction (ORR) which is known from experiments to proceed either via a four-electron reduction process toward H2O and/or two-electron reduction toward H2O2, depending upon the specific reaction conditions and catalyst in question. The ORR product distribution is not captured by simplified thermodynamic models - despite their many other successes - as these always favor the four-electron over the two-electron route. To answer the question of electrocatalytic selectivity, we work towards a better understanding of interfacial charge transfer reactions: the mechanisms of electron/proton transfer and theoretical modeling of electrochemical barriers.
Selected Publications
Selected recent publications are listed below (a full list can be found under Publications):
Origin of Electrocatalytic Selectivity during the Oxygen Reduction Reaction on Au(111), E. Diesen, A. M. Dudzinski, K. Reuter, and V. J. Bukas, ACS Catalysis (2025)
Exploring mesoscopic mass transport effects on electrocatalytic selectivity, H. H. Heenen, H. S. Pillai, K. Reuter, and V. J. Bukas, Nature Catalysis (2024)
First Step of the Oxygen Reduction Reaction on Au(111): A Computational Study of O2 Adsorption at the Electrified Metal/Water Interface, A. M. Dudzinski*, E. Diesen*, H. H. Heenen, V. J. Bukas, and K. Reuter, ACS Catalysis (2023)
A spin promotion effect in catalytic ammonia synthesis
A. Cao*, V. J. Bukas*, V. Shadravan*, Z. Wang*, H. Li, J. Kibsgaard, I. Chorkendorff and J. K. Nørskov, Nature Communications (2022)
Enhancement of lithium-mediated ammonia synthesis by addition of oxygen, K. Li*, S. Z. Andersen*, M. J. Statt*, M. Saccoccio, V. J. Bukas, K. Krempl, R. Sazinas, J. B. Pedersen, V. Shadravan, Y. Zhou, D. Chakraborty, J. Kibsgaard, P. C. K. Vesborg, J. K. Nørskov and I. Chorkendorff, Science (2021)
Increasing stability, efficiency, and fundamental understanding of lithium-mediated electrochemical nitrogen reduction, S. Z. Andersen*, M. J. Statt*, V. J. Bukas*, S. G. Shapel, J. B. Pedersen, K. Krempl, M. Saccoccio, D. Chakraborty, J. Kibsgaard, P. C. K. Vesborg, J. K. Nørskov and I. Chorkendorff, Energy & Environmental Science (2020)
Combining experiment and theory to unravel the mechanism of two-electron oxygen reduction at a selective and active co-catalyst, V. J. Bukas, H. W. Kim, R. Sengpiel, K. Knudsen, J. Voss, B. D. McCloskey and A. C. Luntz, ACS Catalysis (2018)
Hot adatom diffusion following oxygen dissociation on Pd (100) and Pd (111): A first-principles study of the equilibration dynamics of exothermic surface reactions, V. J. Bukas and K. Reuter, Physical Review Letters (2016)