TY - JOUR
T1 - The mechanism of CO2 chemisorption on zigzag carbon active sites
T2 - A computational chemistry study
AU - Radovic, Ljubisa R.
N1 - Funding Information:
The initial stages of this research were supported in part by an appointment to the US Department of Energy Fossil Energy Faculty Research Participation Program at the Federal Energy Technology Center administered by the Oak Ridge Institute for Science and Education (ORISE); the hospitality and collaboration of Bradley Bockrath and Anthony Cugini (NETL, Pittsburgh, PA) is gratefully acknowledged. Access to the Lion-XL Computational Cluster at Penn State’s Materials Simulation Center (Jorge Sofo, director) is much appreciated.
PY - 2005
Y1 - 2005
N2 - A computational chemistry study was carried out to evaluate the various options for CO2 adsorption on one or two adjacent zigzag sites in a graphene layer. Density functional theory was used with the 6-31G(d) basis set, as implemented in the Gaussian software package in conjunction with GaussView and Chem3D. Various electronic environments of a four-ring model, with and without surface oxygen and with special emphasis on carbene-like structures, were analyzed. The resulting optimized geometries were quite sensitive to such electronic configurations. In agreement with long-standing experimental evidence, dissociative CO2 adsorption was found to be particularly favorable; furthermore, dissociation was found to be favored on isolated carbene-like zigzag sites. It is recommended that such a pathway, rather than dual-site adsorption and C-CO2 complex formation, deserves the dominant attention in further theoretical studies of adsorption, reaction and desorption processes during CO2 gasification of carbons.
AB - A computational chemistry study was carried out to evaluate the various options for CO2 adsorption on one or two adjacent zigzag sites in a graphene layer. Density functional theory was used with the 6-31G(d) basis set, as implemented in the Gaussian software package in conjunction with GaussView and Chem3D. Various electronic environments of a four-ring model, with and without surface oxygen and with special emphasis on carbene-like structures, were analyzed. The resulting optimized geometries were quite sensitive to such electronic configurations. In agreement with long-standing experimental evidence, dissociative CO2 adsorption was found to be particularly favorable; furthermore, dissociation was found to be favored on isolated carbene-like zigzag sites. It is recommended that such a pathway, rather than dual-site adsorption and C-CO2 complex formation, deserves the dominant attention in further theoretical studies of adsorption, reaction and desorption processes during CO2 gasification of carbons.
UR - http://www.scopus.com/inward/record.url?scp=13944266436&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=13944266436&partnerID=8YFLogxK
U2 - 10.1016/j.carbon.2004.11.011
DO - 10.1016/j.carbon.2004.11.011
M3 - Article
AN - SCOPUS:13944266436
SN - 0008-6223
VL - 43
SP - 907
EP - 915
JO - Carbon
JF - Carbon
IS - 5
ER -