TY - JOUR
T1 - Propiolic Acid on Cu(100) and Oxygen-Precovered Cu(100)
T2 - Multiple Adsorption States and Diversified Reaction Routes
AU - Lin, Jong Liang
AU - Lin, Hong Ping
AU - Lin, Ming Wei
AU - Tseng, Kuan Wen
AU - You, Zheng Jie
AU - Lin, Han Sheng
AU - Ho, Yi Wen
AU - Wang, Chia Hsin
AU - Yang, Yaw Wen
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/4/6
Y1 - 2023/4/6
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.jpcc.2c08856
DO - 10.1021/acs.jpcc.2c08856
M3 - Article
AN - SCOPUS:85151307817
SN - 1932-7447
VL - 127
SP - 6294
EP - 6310
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 13
ER -