Propiolic Acid on Cu(100) and Oxygen-Precovered Cu(100): Multiple Adsorption States and Diversified Reaction Routes

Multiple adsorption geometries and diversified reaction pathways of the bifunctional propiolic acid (HCC–COOH) on Cu(100) and oxygen-covered Cu(100) (O/Cu(100)) have been investigated, using the surface analytical techniques of X-ray photoelectron spectroscopy, reflection–absorption infrared spectroscopy, and temperature-programmed reaction/desorption, with the assistance of density functional theory calculations. Upon adsorption on O/Cu(100) at 105 K, the deprotonation occurs promptly to form perpendicular HCC–COO (propiolate) with the COO attaching to the surface. Decomposition of this intermediate results in the loss of CO and CO2 at ∼230 K and formation of the plausible surface intermediates of CCCOOH, tilted HCCCOO, and CCH. The first two are derived from rearrangement or geometric transformation of the perpendicular HCC–COO. CCH is the precursor for the C2H2 desorption at ∼335 K. C2 (acetylide) and >CCO (ketenylidene) exist on the surface at higher temperatures and are responsible for the desorption of CO and CO2 at 580 K. On Cu(100), adsorption of propiolic acid at 105 K generates tilted HCCCOOH and HCCCOO, via the HCC group bonding to the surface. Perpendicular HCC–COO is an additional species found at a higher coverage. Hydrogenation of the HCCCOO occurs, possibly involving the surface species of CHCHCOO and CH2CCOO. H2, H2O, CO, and CO2 evolve from decomposition of these carboxylates at ∼315 K, also forming perpendicular CH2CHCOO and >CCO. Adsorbed CH3CH2COO can be produced at a higher coverage. In addition, C2H2 and C2H4 desorb at ∼360 K. Decomposition of the perpendicular CH2CHCOO, >CCO, and CH3CH2COO is responsible for the products of H2, CO, CO2, and C6H6 found at ∼550 K.