The Role of Metal Adatoms in a Surface-Assisted Cyclodehydrogenation Reaction on a Gold Surface

Dehydrogenation reactions are key steps in many metal-catalyzed chemical processes and in the on-surface synthesis of atomically precise nanomaterials. The principal role of the metal substrate in these reactions is undisputed, but the role of metal adatoms remains, to a large extent, unanswered, particularly on gold substrates. Here, we discuss their importance by studying the surface-assisted cyclodehydrogenation on Au(111) as an ideal model case. We choose a polymer theoretically predicted to give one of two cyclization products depending on the presence or absence of gold adatoms. Scanning probe microscopy experiments observe only the product associated with adatoms. We challenge the prevalent understanding of surface-assisted cyclodehydrogenation, unveiling the catalytic role of adatoms and their effect on regioselectivity. The study adds new perspectives to the understanding of metal catalysis and the design of on-surface synthesis protocols for novel carbon nanomaterials.Funding Agencies|Alexander von Humboldt foundation; Swedish Research Council; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [200900971]; MCIN/AEI [PID2020-113142RB-C21, IJCI-2014-19291]; ERDF A way of making Europe [MAT2017-85089-C2-1-R]; ESF Investing in your future [RYC2018-024364-I]; Swiss National Science Foundation [200020_182015, 51NF40-205602]; Knut and Alice Wallenberg (KAW) Foundation; Max Planck Society