TY - JOUR
T1 - Phenol deoxygenation mechanisms on Fe(110) and Pd(111)
AU - Hensley, Alyssa J.R.
AU - Wang, Yong
AU - McEwen, Jean Sabin
N1 - Publisher Copyright:
© 2014 American Chemical Society.
PY - 2015/2/6
Y1 - 2015/2/6
N2 - The catalytic deoxygenation of phenolic compounds has become a major area of interest in recent years because they are produced during the pyrolysis of lignin and are present in biofuels. Our previous work showed that a PdFe bimetallic catalyst was catalytically active for the deoxygenation of phenolics. To better understand and control the catalytic deoxygenation reaction of phenolics, the detailed surface reaction mechanisms are needed for phenol, a key intermediate in phenolic deoxygeantion. Here, we have examined five distinct reaction mechanisms for the deoxygenation of phenol on the Fe(110) and Pd(111) surfaces so as to identify the most likely deoxygenation mechanism on these surfaces. Our results show that the elementary phenol deoxygenation reaction step for each mechanism was highly endothermic on Pd(111), whereas the same mechanisms are exothermic on Fe(110). On the basis of the reaction energy studies, detailed mechanistic studies were performed on the Fe(110) surface, and it was found that the most energetically and kinetically favorable reaction mechanism occurs via the direct cleavage of the C-O bond.
AB - The catalytic deoxygenation of phenolic compounds has become a major area of interest in recent years because they are produced during the pyrolysis of lignin and are present in biofuels. Our previous work showed that a PdFe bimetallic catalyst was catalytically active for the deoxygenation of phenolics. To better understand and control the catalytic deoxygenation reaction of phenolics, the detailed surface reaction mechanisms are needed for phenol, a key intermediate in phenolic deoxygeantion. Here, we have examined five distinct reaction mechanisms for the deoxygenation of phenol on the Fe(110) and Pd(111) surfaces so as to identify the most likely deoxygenation mechanism on these surfaces. Our results show that the elementary phenol deoxygenation reaction step for each mechanism was highly endothermic on Pd(111), whereas the same mechanisms are exothermic on Fe(110). On the basis of the reaction energy studies, detailed mechanistic studies were performed on the Fe(110) surface, and it was found that the most energetically and kinetically favorable reaction mechanism occurs via the direct cleavage of the C-O bond.
KW - BEP Relations
KW - Benzene Production
KW - Density Functional Theory
KW - Fe(110)
KW - Minimum Energy Pathways
KW - Pd(111)
KW - Phenol Deoxygenation
KW - Transition State Theory
UR - http://www.scopus.com/inward/record.url?scp=84923091763&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84923091763&partnerID=8YFLogxK
U2 - 10.1021/cs501403w
DO - 10.1021/cs501403w
M3 - Article
AN - SCOPUS:84923091763
SN - 2155-5435
VL - 5
SP - 523
EP - 536
JO - ACS Catalysis
JF - ACS Catalysis
IS - 2
ER -