Catalytic Resonance Theory: Negative Dynamic Surfaces for Programmable Catalysts

17 August 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Catalysts that change with time via programmed variation of their electronic occupation to accelerate surface reactions were evaluated in the case of negative adsorption energy scaling relations. Defined as the relative change in adsorption enthalpy, the gamma linear scaling parameter is negative when two adsorbates alternatively weaken and strengthen as catalysts are electronically perturbed. Simulations were conducted of a single transition state connecting two generic adsorbates representative of multiple reaction classes to understand the resulting negative gamma catalytic ratchet mechanism and its ability to accelerate catalytic reactions above the Sabatier peak and away from equilibrium. Relative to conventional positive gamma catalytic ratchets, the Sabatier volcanoes of negative gamma catalysis are narrower with greater enhancement of dynamic turnover frequency when catalysts are electronically oscillated. Promotion of the catalytic surface reaction forwards or backwards was predictable by a descriptor accounting for the relative rates of forward and reverse kinetics under oscillatory conditions.

Keywords

Energy
Catalysis
Storage
Dynamics

Supplementary materials

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Title
Supporting Information - Catalytic Resonance Theory: Negative Dynamic Surfaces for Programmable Catalysts
Description
Supporting information including model description and data interpretation methodology
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