Operando Modeling of Multicomponent Reactive Solutions in Homogeneous Catalysis: from Non-standard Free Energies to Reaction Network Control.

Optimization and execution of chemical reactions are to a large extend based on experience and chemical intuition of a chemist. The chemical intuition is rooted in the phenomenological Le Chatelier's principle that teaches us how to shift equilibrium by manipulating the reaction conditions. To access the underlying thermodynamic parameters and their condition-dependencies from the first principles is a challenge. Here, we present a theoretical approach to model non-standard free energies for a complex catalytic CO hydrogenation system under operando conditions and identify the condition spaces where catalyst deactivation can potentially be suppressed. Investigation of the non-standard reaction free energy dependencies allows rationalizing the experimentally observed activity patterns and provides a practical approach to optimization of the reaction paths in complex multicomponent reactive catalytic systems.