Achieving Theory-Experiment Parity for Activity and Selectivity in Heterogeneous Catalysis Using Microkinetic...

Area of Science:

• Heterogeneous catalysis
• Computational chemistry
• Surface science

Background:

• Microkinetic modeling, based on density functional theory (DFT) energies, is crucial for understanding heterogeneous catalysis.
• Traditional models often lack quantitative reliability due to limitations in energy input estimation and surface coverage effects.
• Lack of robust microkinetic software hinders the analysis of complex catalytic systems.

Purpose of the Study:

• To refine microkinetic modeling predictions for enhanced accuracy in heterogeneous catalysis.
• To achieve parity between theoretical predictions and experimental observations for catalytic activity and selectivity.
• To address limitations in current microkinetic modeling approaches.

Main Methods:

• Introduction of CATKINAS, a novel microkinetic software designed to overcome limitations of traditional software.
• Development and application of a molecular dynamics method for accurate free-energy calculations of adsorption/desorption processes.
• Rigorous consideration of surface coverage effects in microkinetic models.

Main Results:

• CATKINAS enables kinetic analysis of more sophisticated reaction systems.
• Molecular dynamics provides crucial missing energy inputs for adsorption/desorption.
• Incorporating surface coverage effects leads to more realistic models and accurate kinetic results.

Conclusions:

• The refined microkinetic modeling approach significantly improves quantitative understanding of catalytic mechanisms.
• Studies on acetylene hydrogenation on Pd catalysts demonstrate enhanced insights into active sites and structural sensitivity.
• This work paves the way for more reliable theoretical guidance in catalyst design and optimization.