TY - JOUR
T1 - Comparative study on the reaction pathways of 2-chloropropanoic acid on Cu(100) and O/Cu(100)
AU - Yang, Zi Xian
AU - Chen, Shang Wei
AU - Lee, Szu Han
AU - Chen, Tai You
AU - Lin, Jong Liang
N1 - Funding Information:
This research was financially supported by the Ministry of Science and Technology of the Republic of China (MOST 105- 2113-M-006-002). We thank Dr. Chia-Hsin Wang and Dr. Yaw-Wen Yang for their assistance in obtaining the photoelectron spectra in the National Synchrotron Radiation Research Center, the Republic of China.
Funding Information:
This research was financially supported by the Ministry of Science and Technology of the Republic of China (MOST 105-2113-M-006-002). We thank Dr. Chia-Hsin Wang and Dr. Yaw-Wen Yang for their assistance in obtaining the photo- electron spectra in the National Synchrotron Radiation Research Center, the Republic of China.
PY - 2017/1/12
Y1 - 2017/1/12
N2 - CH3CHCOOH and CH3CHCOO have been theoretically predicted to be important in the decarboxylation or decarbonylation of propanoic acid on Pd(111). In the present study, we explore the possibility to prepare these two intermediates on Cu(100) and oxygen-predosed Cu(100) (O/Cu(100)), with CH3CHClCOOH as the precursor, and to investigate their adsorption geometries and reactions on the surfaces using X-ray photoelectron spectroscopy, reflection- absorption infrared spectroscopy, temperature-programmed reaction/desorption, and calculations of density functional theory. CH3CHClCOO and CH3CHCOO are suggested to be formed on Cu(100) at 250 K by heating the CH3CHClCOOH adsorption layers. However, CH3CHCOO can promptly recombine with the H from the deprotonation of CH3CHClCOOH to generate CH3CH2COO. The adsorbed propanoate decomposes mainly into H2, CO, and CO2 at a temperature higher than ~380 K. On O/Cu(100), CH3CHClCOO is the predominant species found in the dissociation of CH3CHClCOOH at 250 K. The preadsorbed O disables the CH3CHCOO hydrogenation to form CH3CH2COO due to the lack of adsorbed H. This intermediate is not stable above ~400 K and decomposes into H2, H2O, CO, and CO2, probably with a small amount of acrolein or methylketene. The CH3CHCOO is shown theoretically to be bonded on Cu(100) via the unsaturated carbon and one of the oxygen atoms.
AB - CH3CHCOOH and CH3CHCOO have been theoretically predicted to be important in the decarboxylation or decarbonylation of propanoic acid on Pd(111). In the present study, we explore the possibility to prepare these two intermediates on Cu(100) and oxygen-predosed Cu(100) (O/Cu(100)), with CH3CHClCOOH as the precursor, and to investigate their adsorption geometries and reactions on the surfaces using X-ray photoelectron spectroscopy, reflection- absorption infrared spectroscopy, temperature-programmed reaction/desorption, and calculations of density functional theory. CH3CHClCOO and CH3CHCOO are suggested to be formed on Cu(100) at 250 K by heating the CH3CHClCOOH adsorption layers. However, CH3CHCOO can promptly recombine with the H from the deprotonation of CH3CHClCOOH to generate CH3CH2COO. The adsorbed propanoate decomposes mainly into H2, CO, and CO2 at a temperature higher than ~380 K. On O/Cu(100), CH3CHClCOO is the predominant species found in the dissociation of CH3CHClCOOH at 250 K. The preadsorbed O disables the CH3CHCOO hydrogenation to form CH3CH2COO due to the lack of adsorbed H. This intermediate is not stable above ~400 K and decomposes into H2, H2O, CO, and CO2, probably with a small amount of acrolein or methylketene. The CH3CHCOO is shown theoretically to be bonded on Cu(100) via the unsaturated carbon and one of the oxygen atoms.
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U2 - 10.1021/acs.jpcc.6b09624
DO - 10.1021/acs.jpcc.6b09624
M3 - Article
AN - SCOPUS:85035137327
SN - 1932-7447
VL - 121
SP - 315
EP - 323
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 1
ER -