Escolar Documentos
Profissional Documentos
Cultura Documentos
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, PR China
Leibniz-Institut fr Katalyse e.V. an der Universitt Rostock, Albert-Einstein Strasse 29a, 18059 Rostock, Germany
a r t i c l e
i n f o
Article history:
Received 25 January 2010
Received in revised form 11 March 2010
Accepted 12 March 2010
Available online 17 March 2010
Keywords:
DFT calculation
Molecular dynamics
Goethite
Dehydration
a b s t r a c t
In FischerTropsch synthesis (FTS), the prepared catalyst hematite (a-Fe2O3) originates from goethite (aFeOOH) dehydration in calcinations process. The structure of a-FeOOH and its topotactic transformation
into a-Fe2O3 under 300900 K have been modeled within the framework of density functional theory.
Molecular dynamics simulations show that the transformation begins preferentially on the surface and
the dehydration is associated with the formation of voids. The loss of H2O in a-FeOOH does not modify
the morphology extremely with respect to that of the original a-FeOOH. The transformation process
involves hydrogen migration with the formation of adsorbed water, followed by desorption of the water
molecule. The calculated barriers for hydrogen migration (118 kJ/mol) and water desorption (82 kJ/mol)
suggest a direct reaction path without the formation of intermediates.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Iron oxides have attracted enormous attention owing to their
interesting electronic, magnetic, catalytic properties, chemical stability and relatively low production costs [14]. They have a wide
range of potential applications as electro-optic materials, sorbents,
pigments, ion exchangers, magnetic resonance imaging and particularly catalysts [510]. Hematite (a-Fe2O3) is thermodynamically
the most stable form of iron oxides under atmospheric conditions
and often the end form of oxidative transformation of other iron
oxides [11].
In FischerTropsch synthesis (FTS), iron oxide-based catalysts
are widely used due to their high watergas shift (CO + H2O = CO2 + H2) activity when coal-derived syngas is used as feeding
[12]. The prepared catalyst is a mixture mainly containing aFe2O3 and magnetite (Fe3O4).
It is known that a-Fe2O3 phase in iron catalysts originates from
goethite (a-FeOOH) dehydration in calcinations process [13,14],
and it is of scientic and technological importance for its detailed
dehydration process, which has been the subject of many studies
[1521]. XRD and Mssbauer studies revealed that the iron
oxide-based catalysts samples consist of a-FeOOH, Fe3O4 and aFe2O3 after precipitation, and there is no signicant phase transformation during the drying process at about 523 K [22]. Then with
temperature rising, a-FeOOH can transform to a-Fe2O3, which
has been proved to contribute signicantly to the catalyst surface
W.-J. Zhang et al. / Journal of Molecular Structure: THEOCHEM 950 (2010) 2026
2. Computational methods
All calculations were performed in the framework density functional theory (DFT) in the standard KohnSham formalism [35], as
implemented in Vienna ab Initio Simulation Package (VASP)
[36,37]. Atomic cores are described with the projected augmented
wave method (PAW) [38,39], used in combination with the Perdew, Burke and Ernzerhof exchangecorrelation functional (PBE)
[40]. The wave functions are developed on a basis set of plane
waves. Periodic boundary conditions are set. All these methods
were tested and validated [4144].
Fe-bearing minerals present a signicant challenge for calculations because of their magnetic properties [45]. In our study, we
must set the spin states of individual Fe atoms carefully because
a-FeOOH is anti-ferromagnetic [45]. The total energies of periodic
blocks of atoms are calculated within the generalized gradient
approximation (GGA) along with special treatment of on-site Coulomb interactions for d electrons on Fe, using the so-called GGA+U
approximation [4648]. In our study, the effective on-site Coulomb
and exchange interaction parameters for each Fe atom were set to
4 and 1 eV [45], respectively, and this was used for all Fe throughout the calculations. The magnetizations for the Fe atoms were set
to ve, with alternating in positive and negative spin directions to
make sure that the total magnetization of a-FeOOH is zero [49].
The cutoff energy is 700 and 500 eV for optimization and molecular
dynamics (MD) simulations, respectively, which ensures a good
convergence of the total energies.
The Monkhorst Pack scheme was used to generate the k-point
sampling grids within the Brillouin zone. The accurate precision level was used in the optimization of a-FeOOH bulk structure, while
for MD simulations low precision level is denitely sufcient. MD
simulations were performed in a canonical ensemble, using scaled
velocities to the temperature at each time step. The convergence
criteria for geometry optimization were set to: (a) SCF tolerance
of 1 10 4 eV, (b) atomic force tolerance of 0.02 eV/.
The nudged elastic band (NEB) method [5052] with eight
equally spaced images along the pathway is used to locate the minimum energy path and the transition state for the hydrogen migration from one hydroxyl group to the adjacent one without
considering quantum mechanical tunneling for the H-atom transfer. The vibrational frequency of H migration is determined by
diagonalizing a nite difference construction of the Hessian matrix
with displacements of 0.015 (only allowing relevant H and O
atoms to move). Energy difference of 1 10 6 eV was used as convergence criteria in the frequency calculation. Only one imaginary
frequency for the transition state structure was found, based on
which we can make sure that the transition state structure and
the activation energy calculated for the transition states is correct
and reliable. The computed activation barriers agree reasonably
with the available experimental data [5355].
Recently, Krokidis et al. studied the dehydration process of
boehmite (c-AlOOH) to c-alumina (c-Al2O3) by MD simulations
[56]. The elementary steps of c-AlOOH dehydration process have
been proposed and the proposed c-Al2O3 structure terminated
21
22
W.-J. Zhang et al. / Journal of Molecular Structure: THEOCHEM 950 (2010) 2026
Fig. 1. Top (a and b) and side (c and d) views of a-FeOOH and a-Fe2O3 (blue ball for Fe atom; red ball for O atom; and small white ball for H atom), respectively. (For
interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)
Fig. 2. Schematic representation of the a-FeOOH periodic supercell used in MD simulation: (a) side view (b) top views. The arrows show the hydrogen transfers discussed in
the text and depicted in Fig. 3.
495 K. As temperature rises, Fe1 and Fe3 just vibrate near the equilibrium positions indicating the formation of a stable bond.
Fig. 3c shows that the Fe1O2 distance does not change so
much (about 2.0 ) at the initial temperature, indicating that they
just vibrate around themselves, but it gradually grows longer and
the bond cleaves as the temperature hoisted to about 600 K.
Fig. 3d shows that the Fe2O2 distance does not change (2.1 )
so much at initial temperature, indicating that they just vibrate
around themselves, but grows gradually longer as the temperature
W.-J. Zhang et al. / Journal of Molecular Structure: THEOCHEM 950 (2010) 2026
23
Fig. 3. MD results about the distance between atoms performed on a slab representing the (0 1 0) surface of a-FeOOH in the interval of 300900 K (red line represent the
distance between relevant two atoms in a-FeOOH). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)
bining the changes of Fe1O2, Fe2O2, H2O2 and Fe2O2 distances, we can draw a conclusion that O2 transfers to Fe4 as a
hydroxyl group.
From the above analysis, we can get the following conclusions:
(a) a-FeOOH will dehydrate in the interval of 560655 K which is
Fig. 4. The formation and cleavage of bonds along the dehydration process.
24
W.-J. Zhang et al. / Journal of Molecular Structure: THEOCHEM 950 (2010) 2026
Fig. 5. The structure comparison of (a) a-FeOOH, (b) a-FeOOH obtained after dehydration between 300 and 600 K and (c) a-FeOOH obtained after dehydration between 600
and 900 K.
W.-J. Zhang et al. / Journal of Molecular Structure: THEOCHEM 950 (2010) 2026
the inner two layers do not have major breakdown of the atomic
patterns. The morphology of the particles does not change signicantly with respect to that of the original a-FeOOH after losing
water molecules at lower temperatures, which has also been
observed [64].
When heated at low temperatures, the removal of OH from
surface will form instantaneous vacancy. With the temperature
rising, other ions will move to the vacancy, which will lead to pore
in inner space, as a result of which the dehydration will proceed
from the outer surface to the inner centre. This is in agreement
with previous experimental results [18,65].
At 300900 K, Fe3+ has less rearrangement than O2 (Fig. 5) and
O2 can rearrange more quickly than Fe3+ which is in accordance
with previous experimental investigations [66]. This is mainly
due to that oxygen ions are smaller and lighter, and move faster
than iron ions and the positions of oxygen ions are of small shifts
during the dehydration. But the main modication from a-FeOOH
to a-Fe2O3 is due to the migration of iron ions in the interlayer
space to ll in tunnels at higher temperatures [19]. In other words,
the structure of the crystal is full of lattice distortion; even it is not
a real crystal of a-Fe2O3 after heating in the temperature range of
300900 K.
On the other hand, if the a-FeOOH did not dehydrate
completely, a certain number of H atoms and OH groups may
remain within the structure [67,68] which is due to the local defect
of hydrogen transfer process generated by a break of symmetry in
Fig. 2 appears as follows suggested [56]: H1 leaves with O2H2,
while H2 leaves with another O atom bonded to Fe4, then a
hydroxyl group remains in the crystal which may be responsible
for local crystalline defects.
3.3. Transition state simulation
We have calculated the energy barrier of hydrogen migration
from one hydroxyl group to adjacent one with the formation of
adsorbed water as shown in Fig. 7. In the transition state structure,
the distance of H1 O1 is 1.27 , H1 O2 is 1.30 , O2 Fe1 is 1.98
25
4. Conclusions
Fig. 6. The size of the tunnel of a-FeOOH and size of H2O molecule.
26
W.-J. Zhang et al. / Journal of Molecular Structure: THEOCHEM 950 (2010) 2026
Acknowledgments
The authors thank Prof. James D. Kubicki for helpful discussions
on the parameters setting for the optimization of a-FeOOH structure, as well as the National Natural Science Foundation of China
(Grant No. 20873173) and the National Outstanding Young Scientists Foundation of China (Grant No. 20625620) for supports. we
also thank Dr. Jianwen Liu (HU Berlin).
Appendix A. Supplementary data
The results of the benchmark calculations of bulk a-FeOOH are
included. Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.theochem.2010.
03.013.
References
[1] L. Pauling, S.B. Hendricks, J. Am. Chem. Soc. 47 (1925) 781.
[2] M.F. Haque, S. Arajs, J. Heat Mass Transfer 42 (1999) 1617.
[3] Y. Einaga, M. Taguchi, G.-M. Li, T. Akitsu, Z.-Z. Gu, T. Sugai, O. Stato, Chem.
Mater. 15 (2003) 8.
[4] J. Chen, L.-N. Xu, W.-Y. Li, X.-L. Gou, Adv. Mater. 17 (2005) 582.
[5] D.N. Strivastava, N. Perkas, A. Gedanken, I. Felner, J. Phys. Chem. B 106 (2002)
1878.
[6] S. Miteva, M. Stoimenova, J. Colloid Interface Sci. 273 (2004) 490.
[7] D.S. Toledano, V.E. Henrich, J. Phys. Chem. B 105 (2001) 3872.
[8] U. Shwertmann, R.M. Cornell, Iron Oxides in the Laboratory: Preparation and
Characterization, Wiley InterScience, Weinheim, New York, 1991.
[9] A.W. Apblett, S.I. Kuriyavar, B.P. Kiran, J. Mater. Chem. 13 (2003) 983.
[10] L. Babes, B. Denizot, G. Tanguy, J.J. Le Jeune, P.J. Jallet, J. Colloid Interface Sci.
212 (1999) 414.
[11] S.-X. Yin, D.E. Ellis, Surf. Sci. 602 (2008) 2047.
[12] R.B. Anderson, The FischerTropsch Reaction, Academic Press, London, 1984.
[13] T.R. Motjope, H.T. Dlamini, G.R. Hearne, N.J. Coville, Catal. Today 71 (2002) 335.
[14] D.B. Bukur, L. Nowichi, R.K. Manne, X. Lang, J. Catal. 155 (1995) 366.
[15] C.J. Goss, Mineral. Mag. 51 (1987) 437.
[16] F. Watari, V. Van Landuyt, P. Delavignette, S. Amelinckx, J. Solid State Chem. 29
(1979) 137.
[17] F. Watari, P. Delavignette, V. Van Landuyt, S. Amelinckx, J. Solid State Chem. 48
(1983) 49.
[18] D. Walter, G. Buxbaum, W. Laqua, J. Therm. Anal. Calorim. 63 (2001) 733.
[19] Y. Cudennec, A. Lecerf, Solid State Sci. 7 (2005) 520.
[20] . zdemir, D.J. Dunlop, Earth Planet Sci. Lett. 177 (2000) 59.
[21] E. Wolska, U. Schwertmann, Z. Kristallogr. 189 (1989) 233.
[22] T.-Z. Li, Y. Yang, C.-H. Zhang, Z.-C. Tao, H.-J. Wan, X. An, H.-W. Xiang, Y.-W. Li,
Colloids Surf. A 302 (2007) 498.
[23] L. Senzi, S. Krishnamoorthy, A.W. Li, G.D. Meitzner, E. Iglesia, J. Catal. 206
(2002) 202.
[24] W. Hoppe, Z. Kristallogr. 103 (1940) 73.
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
[54]
[55]
[56]
[57]
[58]
[59]
[60]
[61]
[62]
[63]
[64]
[65]
[66]
[67]
[68]