Theoretical study of adsorption of organic phosphines on transition metal surfaces

ABSTRACT

The adsorption properties of organic phosphines on transition metal (TM) surfaces (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) have been studied to explore the possibility of building novel heterogeneous chiral catalytic systems based on organic phosphines. Preferred adsorption sites, adsorption energies and surface electronic structures of a selected set of typical organic phosphines adsorbed on TM surfaces are calculated with density-functional theory to obtain a systematic understanding on the nature of adsorption interactions. All organic phosphines considered are found to chemically adsorb on these TM surfaces with the atop site as the most preferred one, and the TM–P bond is formed via the lone-pair electrons of the P atom and the directly contacted TM atom. These findings imply that it is indeed possible to build heterogeneous chiral catalytic systems based on organic phosphines adsorbed on TM surfaces, which, however, requires a careful design of molecular structure of organic phosphines.

KEYWORDS:

• Adsorption
• transition metal surfaces
• first-principles calculations
• organic phosphines
• heterogeneous chiral catalysis

Acknowledgments

This project was partly supported by National Basic Research Program (No. 2011CB201402) of the Ministry of Science and Technology of China and the National Key Research and Development Program of China (No. 2016YFB0701100).

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

National Key Research and Development Program of China [number 2016YFB0701100]; Ministry of Science and Technology of the People's Republic of China [number 2011CB201402].