Peripheral Coordination-Dependent Descriptor for Selective Interactions between Near-Frontier Molecular Orbitals and...

Area of Science:

• Catalysis
• Materials Science
• Computational Chemistry

Background:

• Selective adsorption of alpha,beta-unsaturated aldehydes (alpha,beta-UALs) is crucial for their hydrogenation into valuable unsaturated alcohols.
• A quantitative understanding of the interactions between the C=C/C=O bond of alpha,beta-UALs and catalysts is currently lacking.

Purpose of the Study:

• To develop a descriptor for quantitatively assessing the selectivity of single-atom catalysts (SACs) for the C=C/C=O bonds of alpha,beta-UALs.
• To enable efficient prediction of catalyst performance in hydrogenation reactions.

Main Methods:

• Comprehensive density functional theory (DFT) calculations were employed.
• A novel descriptor was developed by integrating near-frontier molecular orbitals of alpha,beta-UALs with physical properties of SACs.
• The descriptor accounts for the inner and outer coordination environment of the catalysts.

Main Results:

• The developed descriptor effectively combines electronic properties of adsorbates with catalyst characteristics.
• Parameters used in the descriptor are easily accessible and interpretable.
• The descriptor allows for efficient assessment of SAC selectivity for alpha,beta-UALs adsorption.

Conclusions:

• A new, interpretable descriptor has been established for predicting SAC selectivity in alpha,beta-UAL hydrogenation.
• This work provides a quantitative framework to guide the design of efficient catalysts for producing unsaturated alcohols.
• The findings facilitate advancements in selective catalytic hydrogenation processes.