Theoretical evidence of the CO reduction by a Mo-based complex: a DFT study based on the reaction force decomposed...

Area of Science:

• Catalysis
• Computational Chemistry
• Green Chemistry

Background:

• Direct hydrogenation of carbon dioxide (CO2) to methanoic acid with H2 faces high activation energy, rendering it kinetically unviable.
• This high energy barrier stems from unfavorable reaction force components hindering the process.

Purpose of the Study:

• To investigate the mechanism of CO2 hydrogenation to methanoic acid.
• To explore the catalytic effect of a Molybdenum-based complex in reducing the activation energy.
• To analyze reaction forces and works to understand the mechanistic differences.

Main Methods:

• Density Functional Theory (DFT) calculations using BP86 functional and appropriate basis sets.
• Reaction force analysis to probe reaction mechanisms.
• Utilized Gaussian 16 and AOMix software for calculations and bond order determination.

Main Results:

• The Molybdenum complex [(PYMe)Mo(III)(H)(OH)] significantly reduced the activation energy by 98.5%.
• Reaction force analysis revealed that the Molybdenum complex balances retarding and driving force components, lowering the overall energy barrier.
• Direct hydrogenation is dominated by retarding forces, while the catalyzed reaction shows a balance of forces.

Conclusions:

• The Molybdenum complex is highly effective in catalyzing the hydrogenation of CO2 to methanoic acid.
• Understanding reaction force dynamics provides insight into catalytic mechanisms.
• This catalytic approach offers a more kinetically feasible pathway for CO2 conversion.