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The Fe-catalyzed F-T synthesis of Hydrocarbons: A DFT study
Fischer-Tropsch synthesis: An Introduction
(2n+1) H2 + n CO CnH2n+2 + n H2O
2n H2 + n CO CnH2n + n H2O
CO + H2O CO2 + H2
2 CO C + CO2
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2. Fischer-Tropsch Synthesis2. Fischer-Tropsch Synthesis
Absorption of CO + H2
Syngas moleculesCH HO
H2 +CO
CH H ODissociation of CO + H2
CH OHHCH2CH3 Hydrogenation of C and O
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2. Fischer-Tropsch Synthesis2. Fischer-Tropsch Synthesis
H OHHCHnCH4
CHm
H2OCH4
Initiation
CHp
C2Hp
HMonomer
H OHHCHnCH4
CHm
H2OCH4
Methanation
CH OHHCH2CH3 Hydrogenation of
C and O
Propagationchain
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2. Fischer-Tropsch Synthesis2. Fischer-Tropsch Synthesis
CHp
C3Hp+q
H
C3Hp+q+1
CHp
C2+nHnp+q
H
C2+nHnp+q+1
Initiation
CHp
C2Hp
HMonomer Propagation
chain
Propagation+ Termination
CHpC2+nHnp+q
C2+nHnp+q+1
Propagation+ Termination
Monomer
CHp
C3Hp+q
H
Propagationchain
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Franz Joseph Emil Fischer Hans Tropsch
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Methods of Computations
Fe system (less extensively studied than Co and Ru)
Surface energy: Fe(100) ≈ Fe(110) < Fe(111)
Spin-polarized periodic DFT with plane-wave basis sets (VASP) + Band with STO basis set
PW91 exchange-correlation functional at GGA level
PAW
Energy cutoff: 360 eV
k-point sampling of Brillouin zone
5-layer p(2 2) slabs mimicking Fe(100) surface separated by 10 Å vacuum layer
Model Experiment
Lattice constant
2.8553 Å 2.8665 Å
Bulk modulus 156 GPa 170 GPa
Magnetic moment
2.30 0 2.22 0
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Methanation on Fe(100) Surface
General reaction network for CH4 formation (including all byproducts such as CO2, H2O, H2CO and CH3OH)
A
B
CDE
F
GH
I
J
K L
Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Reactive intermediates on Fe(100) surface
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
Three adsorption sites available: on-top, bridge and hollow sites
Determine the most preferred adsorption sites
Calculate the binding energies at various surface coverage
Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
4-fold4-fold
2-fold2-fold
1-fold1-fold
C
CO
O
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Chemisorption of CO: KineticsLateral interaction: crucial factor affecting the adsorption kinetics
of CO
Activation barrier increases with
Desorption barrier decreases with
CO is less strongly bound at higher
Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
45
35
25
15
5
-5
-15
C
CO
O
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Dissociation of CO: Coverage dependence
Lateral interaction: affects the CO dissociation
CO dissociation is suppressed at = 0.75 ML
Eact generally increases
C + O becomes less stable w.r.t. CO
+0.06 kcal/mol
Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
C O C O
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Phenomenological kinetic simulation of CO addition and dissociation
Langmuir-Hinshelwood approach: all sites in (2x2) units are energetically homogeneous
Simulation parameters: CO:Ar (1:19) gas at 1 atm; ~28 hours; @ 150 and 473 K
Results: @ 150 K: 50% *CO; 50% vacancy; no *C and *O@ 473 K: 27% *CO; 27% vacancy; 23% *C; 23% *O
Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
150K150K
473K473K
C O C O
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Formation of carbon filaments on iron surface
Fe is active catalyst for the Boudouard reaction
Boudouard reaction assists the formation of coke on Fe(100) in the absence of H2
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Reactive intermediates on Fe(100) surface
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
Three adsorption sites available: on-top, bridge and hollow sites
Determine the most preferred adsorption sites
Calculate the binding energies at various surface coverage
Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
4-fold4-fold
2-fold2-fold
1-fold1-fold
H HH-H
H2
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Formation of CHx species on iron surface
Fe is active catalyst for the CHx formation
Reaction of C and H on Fe(100) in the absence of
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
€
Cn + H⇔ Cn+1
€
Cn + H⇔ Cn+1
CCH
CH2
CH3 CH3
CH4
CHCH2
H OHHCHnCH4
CHm
H2OCH4
Methanationand Hydrogenation
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Thermodynamic PES of CH4
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
Gokhale and Mavrikakis, Prep. Pap. - Am. Chem. Soc. Div. Fuel Chem. 50, U861 (2005)
Gong, Raval and Hu, J. Chem. Phys. 122, 024711 (2005)
Ciobica et al., J. Phys. Chem. B 104, 3364 (2000)
Stability of CHn assuming the infinite separation approximation
For Fe(100), Co(0001) and Ru(0001), CH is the most thermodynamically stable intermediate
For Fe(110), surface carbide is the most preferred species
CH is likely the most abundant active C1 species on Fe(100) while CH, CH2 and CH3 have significant coverage on Co under the F-T conditions
A possible F-T mechanism: proceeding via CH coupling reaction
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Temperature effects on the rate of CH4 formation
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
Lox and Froment, Ind. Eng. Chem. Res. 32, 61 (1993); 32, 71 (1993)
Simulations including both CO and H2 at industrial reaction conditions
P(CO)/P(H2)=1/3
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Pressure effects on the rate of CH4 formation
The rate of CH4 formation exhibits a strong dependence on the partial pressures of CO and H2
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
Lox and Froment, Ind. Eng. Chem. Res. 32, 61 (1993); 32, 71 (1993)
Fixed pressures of CO and H2: p(CO) = 0.2 MPa,
p(CO) = 0.2 MpaT=525 K
(b)
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Initiation C-C bond coupling reactions on Fe(100) surface
(a) (b)
(c)
(c)
(d)
(d)
(e)
(e)
(f)
12
3
4
5
6
7
8
9
10
11
12
13
14
15
Lo and Ziegler, J. Phys. Chem. C 111, 13149 (2007)
CHp
C2Hp
H
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19
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Mechanisms of F-T synthesis
Most widely accepted carbene mechanism (Fischer & Tropsch (1926))
How is methane formed?
How do the C1 units couple?
How does the chain grow?
Maitlis et al. JACS 124, 10456 (2002)
AB
C
DE
F
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Kinetics of the C-C coupling reactions on Fe(100)
C-C bond coupling reactions are usually kinetically demanding processes
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 13149 (2007)
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21
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Kinetics of the C-C coupling reactions on Fe(100)
C-C bond coupling reactions are usually kinetically demanding processes
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 13149 (2007)
C with CH/CH2 bond coupling reactions kinetically and thermodynamically favorable
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22
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Kinetics of the C-C coupling reactions on Fe(100)
C-C bond coupling reactions are usually kinetically demanding processes
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 13149 (2007)
CH to CH/CH2 bond coupling reactions kinetically favorable but thermodynamically
unfavorable
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Kinetics of the C-C coupling reactions on Fe(100)
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 13149 (2007)
Hydrogenation reactions occur rather rapidly at room temperatures
Many hydrogenation reactions are indeed endothermic and require energy
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Kinetics of the C-C coupling reactions on Fe(100)
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 13149 (2007)
With this information we may construct the kinetic profile for the formation of ethane ethylene
Isomerization processes are not kinetically favorable
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Kinetic profile of ethane formation
The formation of CH3CH3 is kinetically feasibleThe rate-determining step is the C + CH2 coupling reactionThe C + CH step has to overcome a much higher barrier (> 29 kcal/mol), and is thus less likely
Lo and Ziegler, J. Phys. Chem. C 111, 13149 (2007)
Propagating chainMonomer
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26
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
General chain propagation reactions on Fe(100) surface
Very complicated processes because of a large number of active surface species
Information obtained from previous sections:
*C and *CH are the most abundant surface species (monomers)
*CCH, *CCH2 and *CCH3 are stable C2 fragments on Fe(100)(growing chains)
For Co and Ru, the following mechanisms have been proposed:
Unsaturated carbon)Unsaturated carbon)
one hydrgenone hydrgen
two hydrgenstwo hydrgens
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27
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
General chain propagation reactions on Fe(100) surface
Very complicated processes because of a large number of active surface species
Information obtained from previous sections:
*C and *CH are the most abundant surface species (monomers)
*CCH, *CCH2 and *CCH3 are stable C2 fragments on Fe(100)(growing chains)
For Co and Ru, the following mechanisms have been proposed:
Unsaturated carbon)Unsaturated carbon)
one hydrgenone hydrgen
two hydrgenstwo hydrgens
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
C-C bond coupling reactions
Coupling reactions with C-CHn fragments are generally endothermic important only at high reaction temperatures
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
C-C bond coupling reactions
Reactions between *C and CHCH2/CH-CH3 and CH2CH3 possess lower activation barriers on Fe
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
C-C bond coupling reactions
Therefore, the carbide route should be the dominant mechanism in the Fe-catalyzed F-T synthesis (thermodynamically favorable but kinetically demanding)
Reactions between *CH/*CH2 and CHCH2/CH-CH3 or CH2CH3 possess higher activation barriers on Fe
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
C-C bond coupling reactions
Therefore, the carbide route should be the dominant mechanism in the Fe-catalyzed F-T synthesis (thermodynamically favorable but kinetically demanding)
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Thermodynamic stability of C2 species
Direct formation of C2 from *C is not favorable
Lateral interaction is an important factor determining the relative stability
Ethane is more preferred to ethylene thermodynamically in the F-T synthesis
Highly unsaturated -C species are more stable because of their high coordination to Fe surface Lo and Ziegler, J. Phys. Chem. C 111, 13149 (2007)
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Plausible reaction scheme of chain propagation
According to the computed C-C bond coupling reaction barriers, the following possible reaction scheme leading to the formation of propane and propylene can be deduced:
The kinetic profiles for the production of propane and propylene can be obtained if the activation energies for all these hydrogenation reactions are known
Reference: Liu and Hu, J. Am. Chem. Soc. 124, 11568 (2002).
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Thermodynamic stability of reactive C3 fragments
Reference: Lo and Ziegler, J. Phys. Chem. C (to be submitted)
Kca
l/mol
Propylene
Lo and Ziegler, J. Phys. Chem. C 111(2008),submitted
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Kinetic potential energy surface for propane formation
Lo and Ziegler, J. Phys. Chem. C 111, 2008,submitted
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Kinetic potential energy surface for propane formation
Lo and Ziegler, J. Phys. Chem. C 111, 2008,submitted
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The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
CO dissociation channel: Fe(100) v.s. Fe(310)
Two stable configurations are located on Fe(310): 4f and 4f2
Barrier for CO activation on Fe(310) edge is lowered compared to that on flat Fe(100) at 0.250 ML surface coverage
At higher coverage, the Fe(310) 4f2 becomes the most feasible path, having the barrier of only 22.7 kcal/mol, and a large exothermicity of 12.1 kcal/mol
It is estimated that for an Fe catalyst with 10% Fe(310) steps by surface area, the resulting percentage of adsorbed CO undergoing decomposition becomes:
(compared to 50% for Fe(100) surface)
Lo and Ziegler J. Phys. Chem. C. 2008; 112; 3692-3700
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38
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Use of AlloysUse of Alloys
Lo and ZieglerJ. Phys. Chem. C 2008, 112, 3667-3678Lo and ZieglerJ. Phys. Chem. C 2008, 112, 3667-3678
1. H2 activation1. H2 activation
2. CO activation2. CO activation
J. Phys. Chem. C.; (Article); 2008; 112(10); 3679-3691. J. Phys. Chem. C.; (Article); 2008; 112(10); 3679-3691.
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39
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Conclusions
The process of Co hydrogenation on Fe catalyst has been investigated computationally, and the associated kinetics has been explored.
CO addition on Fe(100) has been controlled by the entropy lost during the process, and in maximum 50% of the surface active sites can be occupied.
The most abundant C1 species on Fe(100) is *CH, but the chain initiation takes place making use of *CH2 instead.
The carbide mechanism, in which *C inserts into surface *CnHm units, is found to be more thermodynamically feasible than the well-known alkenyl or alkylidene mechanisms.
The activity of Fe catalyst in the F-T synthesis can be improved by introducing surface defects, such as steps, or doping of other metals.
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40
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Use of AlloysUse of Alloys
Lo and ZieglerJ. Phys. Chem. C 2008, 112, 3667-3678Lo and ZieglerJ. Phys. Chem. C 2008, 112, 3667-3678
1. H2 activation1. H2 activation
2. CO activation2. CO activation
J. Phys. Chem. C.; (Article); 2008; 112(10); 3679-3691. J. Phys. Chem. C.; (Article); 2008; 112(10); 3679-3691.
![Page 41: 1 The Fe-catalyzed F-T synthesis of Hydrocarbons: A DFT study Fischer-Tropsch synthesis: An Introduction (2 n+1) H 2 + n CO C n H 2n+2 + n H 2 O 2n H](https://reader033.vdocuments.site/reader033/viewer/2022061416/56649e425503460f94b344c2/html5/thumbnails/41.jpg)
41
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Conclusions
The process of Co hydrogenation on Fe catalyst has been investigated computationally, and the associated kinetics has been explored.
CO addition on Fe(100) has been controlled by the entropy lost during the process, and in maximum 50% of the surface active sites can be occupied.
The most abundant C1 species on Fe(100) is *CH, but the chain initiation takes place making use of *CH2 instead.
The carbide mechanism, in which *C inserts into surface *CnHm units, is found to be more thermodynamically feasible than the well-known alkenyl or alkylidene mechanisms.
The activity of Fe catalyst in the F-T synthesis can be improved by introducing surface defects, such as steps, or doping of other metals.
![Page 42: 1 The Fe-catalyzed F-T synthesis of Hydrocarbons: A DFT study Fischer-Tropsch synthesis: An Introduction (2 n+1) H 2 + n CO C n H 2n+2 + n H 2 O 2n H](https://reader033.vdocuments.site/reader033/viewer/2022061416/56649e425503460f94b344c2/html5/thumbnails/42.jpg)
42
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Fischer-Tropsch synthesis: An Introduction
First discovered by Sabatier and Sanderens in 1902:
CO +H2 CH4Ni,Fe,Co
Fischer and Tropsch reported in 1923 the synthesis of liquid hydrocarbons with high oxygen contents from syngas on alkalized Fe catalyst (Synthol synthesis)
(2n+1) H2 + n CO CnH2n+2 + n H2O
2n H2 + n CO CnH2n + n H2O
CO + H2O CO2 + H2
2 CO C + CO2
Commercialized by Shell (Malaysia), Sasol (S. Africa) and Syntroleum (USA)
Øyvind Vessia, Project Report, NTNU, 2005.
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43
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Mechanisms of F-T synthesis
CO insertion mechanism(Pichler and Schultz (1970s))
insertion
A
B
C
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44
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Chemisorption of CO: Kinetics
Lateral interaction: crucial factor affecting the adsorption kinetics of CO
Activation barrier increases with
Desorption barrier decreases with
CO is less strongly bound at higher
Calculations predict full coverage by CO? Something is missing … ENTROPY !
Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
IncreaseIn free energyWith 4 kcalFor each 100K
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45
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Chemisorption of CO: Entropic contribution
Different components of entropy for a gaseous molecule can be computed using statistical thermodynamics
Generally speaking, one can write the total entropy as a sum (reference: Surf. Sci. 600, 2051 (2006))
This term will be completely lost because of the assumption that the adsorbed species is immobile
This term is small compared to the rotational entropy, and is thus neglected
This term mostly vanishes during adsorption for immobile species; but it is not possible to compute such quantity for adsorbed molecules, and is thus assumed zero after adsorption (crude approximation)
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46
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Reactive intermediates on Fe(100) surface
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
Three adsorption sites available: on-top, bridge and hollow sites
Determine the most preferred adsorption sites
Calculate the binding energies at various surface coverage
Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
4-fold4-fold
2-fold2-fold
1-fold1-fold
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47
The Fe-catalyzed F-T synthesis of hydrocarbons: A DFT study
Reactive intermediates on Fe(100) surface
Reference: Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
Three adsorption sites available: on-top, bridge and hollow sites
Determine the most preferred adsorption sites
Calculate the binding energies at various surface coverage
Lo and Ziegler, J. Phys. Chem. C 111, 11012 (2007)
4-fold4-fold
2-fold2-fold
1-fold1-fold