(340f) Assessing the Response of Dynamic Catalytic Surfaces

The rate enhancement of catalytic reactions on metals, metal oxides, and less rigid structures, such as proteins, occurs due to the stabilization of adsorbed chemicals and the associated transition states between elementary reaction steps. Recent experimental and simulation evidence indicates that surface reactions can proceed even faster and more selectively when the surface and adsorbates change with time [1,2], even above the Sabatier maximum. However, the introduction of surface dynamics augments the number of parameters defining surface chemical reactions [3]; in addition, real chemical systems of relevance to energy, materials, and sustainability in general are comprised of ten or even more elementary steps. The difficulty associated with fruitfully exploring parameter space and optimizing selected performance criteria for complex dynamic surface kinetics, motivates advanced numerical methods of determining catalytic performance. In this work fixed point algorithms, both explicit and matrix-free, are developed to solve the system of dynamic equations defining oscillating energies, surface coverages, and rates of a multi-reaction system. Determination of the resulting entrained periodic solutions across a broad range of surface/operating parameters leads to an understanding of the relationships between the natural frequencies of adsorption, desorption,and surface reaction characteristic times with the applied frequencies and waveforms of binding energy.

[1] M. Alexander Ardagh, Omar A. Abdelrahman, Paul J. Dauenhauer, ”Principles of Dynamic HeterogeneousCatalysis: Surface Resonance and Turnover Frequency Response” ACS Catalysis, 2019, 9(8), 6929-6937.

[2] J. Gopeesingh, M.A. Ardagh, M. Shetty, S. Burke, P.J. Dauenhauer, O.A. Abdelrahman, ”Resonance-Promoted Formic Acid Oxidation via Dynamic Electrocatalytic Modulation,” ChemRxiv 2020. DOI: 10.26434/chem-rxiv.11972031.v1

[3] Alex M. Ardagh, Turan Birol, Qi Zhang, Omar Abdelrahman, Paul Dauenhauer, ”Catalytic Resonance Theory:SuperVolcanoes, Catalytic Molecular Pumps, and Oscillatory Steady State”Catalysis Science & Technology. 2019,9, 5058-5076. DOI: 10.1039/C9CY01543D