Insight into CH(4) formation in iron-catalyzed Fischer-Tropsch synthesis.
Spin-polarized density functional theory calculations have been performed to investigate the carbon pathways and hydrogenation mechanism for CH(4) formation on Fe(2)C(011), Fe(5)C(2)(010), Fe(3)C(001), and Fe(4)C(100). We find that the surface C atom occupied sites are more active toward CH(4) formation. In Fischer-Tropsch synthesis (FTS), CO direct dissociation is very difficult on perfect Fe(x)C(y) surfaces, while surface C atom hydrogenation could occur easily. With the formation of vacancy sites by C atoms escaping from the Fe(x)C(y) surface, the CO dissociation barrier decreases largely. As a consequence, the active carburized surface is maintained. Based on the calculated reaction energies and effective barriers, CH(4) formation is more favorable on Fe(5)C(2)(010) and Fe(2)C(011), while Fe(4)C(100) and Fe(3)C(001) are inactive toward CH(4) formation. More importantly, it is revealed that the reaction energy and effective barrier of CH(4) formation have a linear relationship with the charge of the surface C atom and the d-band center of the surface, respectively. On the basis of these correlations, one can predict the reactivity of all active surfaces by analyzing their surface properties and further give guides for catalyst design in FTS.
Huo
Chun-Fang
CF
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, People's Republic of China.
Li
Yong-Wang
YW
Wang
Jianguo
J
Jiao
Haijun
H
D002244:Carbon / Q000737:chemistry; D017554:Carbon Compounds, Inorganic / Q000737:chemistry; D002384:Catalysis; D006865:Hydrogenation; D007501:Iron / Q000737:chemistry*; D058085:Iron Compounds / Q000737:chemistry; D008697:Methane / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory; D013499:Surface Properties
D017554:Carbon Compounds, Inorganic; D058085:Iron Compounds; C541825:iron carbide; D002244:Carbon; D007501:Iron; D008697:Methane