Abstract
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 CO2 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.
Highlights
(‘Catalysis’ in Figure 2); and an alternative metal-ligand cooperative (MLC) path, which may proceed to a thermodynamicallystable CO2 adduct 7 that cannot further promote the catalytic reaction (‘deactivation’)
DFT calculations on stable intermediates within the catalytic reaction network provides a thermodynamic description of the complex multicomponent liquid-phase catalytic system, and allows operando modeling of the behavior of the overall system under variable conditions
The validity of the approach has been demonstrated on an example of CO2 hydrogenation to formates with homogeneous Ru PNP and CNC pincer catalysts, which exhibit drastically different behavior in the catalytic process
Summary
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