On-surface dehydrogenative lateral homo-coupling and aromatization of n-octane on Pt(111)

TL;DR

This study investigates how linear n-octane molecules undergo dehydrogenation, aromatization, and homocoupling on Pt(111) surfaces at high temperatures, revealing detailed molecular mechanisms of aromatic product formation.

Contribution

It provides new molecular-level insights into the catalytic processes of aromatization and homocoupling of alkanes on platinum surfaces, combining microscopy and ab initio calculations.

Findings

Formation of benzene rings from n-octane via bending and dehydrogenation.

Pt(111) catalyzes homocoupling through a zipper-like C-C bond formation.

Revealed mechanisms of aromatic product generation on catalytic surfaces.

Abstract

Aliphatic hydrocarbons, such as normal alkanes, constitute a naturally abundant source of carbon atoms. Of special interest is the formation of cyclic and aromatic products from aliphatic reactants. Combining scanning tunneling microscopy and ab initio calculations, we investigate the thermal induced aromatization of linear n octane molecules on the catalytic Pt(111) surface and the reactions of intermolecular homocoupling between them at temperatures above 600 K. The cycloaromatization of individual n octane molecules requires bending the linear adsorbates prior to their dehydrogenation and the formation of an intramolecular C-C bond, yielding adsorbed benzene rings. In addition, the Pt(111) surface catalyzes a homocoupling reaction by initiating the formation of a C-C bond between the dehydrogenated methyl ends of the chemisorbed n octane molecules and then propagating along the carbon backbone in a zipper like fashion. Our findings provide molecular level insight into the heterogeneous catalytic processes underlying the generation of aromatic products and stable on surface polycyclic species.