Molybdenum phosphide as an o-propylaniline hydrodenitrogenation catalyst: a first principles study

Area of Science:

• Catalysis
• Surface Science
• Computational Chemistry

Background:

• Molybdenum phosphide (MoP) is an experimentally verified catalyst for hydrodenitrogenation (HDN).
• Understanding the interaction of organic molecules with MoP surfaces is key to optimizing catalytic performance.
• o-Propylaniline serves as a model compound for nitrogen-containing heterocyclic molecules in HDN reactions.

Purpose of the Study:

• To investigate the adsorption structure and energetics of o-propylaniline on the Mo-terminated MoP(001) surface.
• To elucidate the reaction mechanism and energy barriers for the hydrodenitrogenation of o-propylaniline on MoP.
• To provide fundamental insights into the catalytic activity of MoP for C-N bond activation.

Main Methods:

• Density Functional Theory (DFT) calculations were employed to model the MoP(001) surface.
• The adsorption of o-propylaniline on the Mo-terminated surface was studied to determine structural and energetic properties.
• Transition states, reaction pathways, and energy barriers for specific HDN reaction branches were calculated.

Main Results:

• Detailed structures of the free MoP(001) surface and adsorbed o-propylaniline were obtained.
• Adsorption energies of o-propylaniline on MoP(001) were quantified.
• The transition state, reaction path, and energy barrier for the hydrogenolysis of the C-N bond, leading to propylbenzene formation, were reported.

Conclusions:

• MoP exhibits specific adsorption characteristics for o-propylaniline, influencing its catalytic behavior.
• DFT calculations successfully mapped key reaction pathways and energy barriers in the HDN of o-propylaniline.
• The findings contribute to a deeper understanding of MoP-based catalysis for C-N bond activation in hydrodenitrogenation.