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The reaction pathways and the energetics for the direct methane-methanol and benzene-phenol conversions
that occur on the surface of Fe-ZSM-5 zeolite are analyzed from B3LYP DFT computations. We propose
a reasonable model for “R-oxygen”, a surface oxygen species responsible for the catalytic reactivities of
Fe-ZSM-5 zeolite. Our model involves an iron-oxo species on the AlO4 surface site of the zeolite as a
catalytic active center and as a source of oxygen. The essential features of the reaction pathways for the
methane-methanol and benzene-phenol conversions are identical, especially in bonding characters. In the
initial stages of each reaction, methane or benzene comes into contact with the active iron site of the “R-
oxygen” model, leading to the reactant (methane or benzene) complex. After the initial complex is formed,
each reaction takes place in a two-step concerted manner, via neither radical species nor ionic intermediates.
The concerted reaction pathway for the methane (benzene) hydroxylation involves an H atom abstraction and
a methyl (phenyl) migration at the iron active center. From computed energetics for the reaction pathways,
we predict that the benzene hydroxylation should be energetically more favorable than the methane
hydroxylation.
TABLE 1: Computed Atomic Charges and Spin Densities manner via a three-centered transition state (TS2) in which an
on a Model of “r-oxygen” of Fe-ZSM-5 Zeolite Fe-C bond breaking and a C-O bond formation occur
quartet sextet simultaneously, as indicated in Figure 1. This transition state
atom atomic charge spin density atomic charge spin density correctly connects the hydroxy intermediate and the product
complex, being responsible for an intramolecular [1,2] methyl
Fe +1.30 +3.15 +1.38 +3.97
O(oxo) -0.63 -0.22 -0.67 +0.93
migration. Optimized Fe-C and O-C distances are 2.543 and
O -0.85 +0.03 -0.86 +0.05 1.852 Å, respectively. The three-centered structure of TS2 is
Si +0.40 +0.01 +0.39 +0.01 thus appropriate for the transition state of the concerted methyl
Al +0.91 -0.01 +0.91 -0.01 migration from the Fe ion to the OH group.
Let us finally look at the product complex that involves
Methane Hydroxylation on Fe-ZSM-5 Zeolite methanol as a ligand. The basic structure of the methanol moiety
Structures of the Reaction Species. Having set up our model in the product complex is not significantly changed from that
of “R-oxygen”, let us next consider the methane hydroxylation of free methanol. The Fe-O distance of 1.989 Å is much longer
on it. In this section we look at computed geometries of the than 1.608 Å in the reactant complex and 1.765 Å in the hydroxy
reaction species in the quartet spin state for the conversion of intermediate. The Fe-O bond of the product complex is thus
methane to methanol on the model complex. The reaction viewed as a typical coordinate bond in contrast to those of the
pathway that we address here is essentially identical to that of reactant complex and the hydroxy intermediate. The product
the gas-phase methane-methanol conversion by FeO+.9 Since complex and the final complex from which methanol is released
the low-spin quartet potential energy surface provides a low- involve Fe(I) that needs to be reoxidized back to Fe(III) upon
cost energy pathway, as described later, we take a look at the decomposition of N2O. In a previous paper,11 we studied from
reaction species on the quartet reaction pathway. Optimized DFT computations the energetics for the conversion of [Fe]+
structures of the reaction species in the sextet state are similar f [FeO]+ by N2O that regenerates the active center for further
to those in the quartet state. The first step of this reaction is reaction. Fe(I) is in general a rather unstable oxidation state for
C-H bond activation of methane. As shown in Figure 1, a iron, but according to a textbook,27 the existence of Fe(I) cannot
methane (or reactant) complex is formed in the initial stages of be ruled out. Panov et al.4b proposed a diiron model that
the reaction. The methane molecule is weakly bound to the reasonably allows two-electron oxidation-reduction between
three-coordinate iron of the model complex; computed binding Fe(III)/Fe(III) and Fe(II)/Fe(II). Our mechanism is, of course,
energies of 1.6 and 3.9 kcal/mol in the quartet and sextet states, extended to diiron complexes, as can be seen in our previous
respectively, are small, but we think that the formation of this papers on the mechanism of methane monooxygenase.28
complex is very much indicative of methane activation. We We have described the essential electronic processes for the
predict from DFT computations that the Fe ion is closer to one methane hydroxylation on a model of “R-oxygen”. The most
pair of H atoms of the bound methane; this initially formed important point of our proposal for the reaction pathway is that
species is an η2-CH4 complex. Since methane is bound to the methane is activated on a coordinatively unsaturated iron-oxo
neutral complex, the driving force for this binding is unlikely species leading to a methane complex and that two-step
to be direct electrostatic interactions between the methane concerted migrations of hydrogen and methyl successfully
molecule and the complex. Methane complexes with an η2- or convert methane to methanol on the complex. Finally, we should
η3-CH4 binding mode have been proposed to be involved in its indicate that the structure of the four-sided figure of FeO2Al
C-H bond activation; extensive indirect data have been obtained remains almost unchanged throughout the reaction and that the
to support the intermediary of small-alkane complexes.26 One catalytically active center can be reproduced by the introduction
such example was obtained by Billups et al.26i The neutral Co- of N2O gas.
(CH4) complex is formed during photolysis of the CH3CoH Energetics for the Hydroxylation of Methane. We present
complex in an argon matrix, which was confirmed from the in Figure 2 computed energy diagrams in the sextet and quartet
observation that the triply degenerate T2 vibrational mode of spin states for the methane hydroxylation on the possible model
methane at 1305 cm-1 was observed from FTIR measurements of “R-oxygen” of Fe-ZSM-5 zeolite. The overall reaction is
to split into two peaks in the Co(CH4) complex. 23.9 kcal/mol endothermic on the quartet surface and 26.0 kcal/
After this methane complex is formed, one of the H atoms mol endothermic on the sextet surface. The essential features
of the methane molecule is abstracted in a concerted fashion of the energy diagrams are similar to those of the gas-phase
via a four-centered transition state (TS1), leading to a reaction process by FeO+.9 We see crossing between the two potential
intermediate that involves the resultant OH and CH3 groups as energy diagrams to occur twice in the vicinity of the reactant
ligands. We call this species a hydroxy intermediate, which plays and the product complexes. Spin inversion can take place in
a central role in the methane-methanol conversion. This process the vicinity of these crossing points. From an inspection of the
can be viewed as a [1,3] migration of the H atom; the two energy diagrams, we expect that the quartet potential surface
dissociating C-H bond and the forming O-H bond were should afford an energetically low-cost reaction pathway
predicted to be 1.309 and 1.357 Å, respectively, the values being whereas the sextet state is the ground state in the entrance and
appropriate for this concerted electronic process. This four- the exit channels. Although the crossing occurs twice near the
centered structure is quite similar to the corresponding transition- reactant and the product complexes, the spin inversion has little
state structure in the gas-phase process by the bare FeO+ effect on the energetics of the reaction pathway because the
complex. This mechanism for the C-H dissociation of hydro- sextet and the quartet states in the entrance and the exit channels
carbon substrates is strikingly different from the conventional are close-lying in energy. We therefore conclude that the quartet
radical mechanism that is considered to take place through a potential energy surface should play a dominant role in this
transition state with a linear C-H-O array. reaction, which is somewhat different from that of the reaction
The second half of the reaction starts from the hydroxy pathway for the gas-phase methane-methanol conversion by
intermediate. The hydroxy intermediate thus formed is then FeO+,9 where such spin inversions play a very important role
converted into a methanol (or product) complex in a concerted in determining the energetics of the reaction pathway.8a
Methane-Methanol and Benzene-Phenol Conversions J. Phys. Chem. B, Vol. 104, No. 4, 2000 737
Figure 1. Ball-and-stick structures of the reaction intermediates and the transition states for the direct methane hydroxylation on a model of
“R-oxygen” of Fe-ZSM-5 zeolite in the quartet state. Bond lengths are in angstroms.
Figure 3. Ball-and-stick structures of the reaction intermediates and the transition states for the direct benzene hydroxylation on a model of
“R-oxygen” of Fe-ZSM-5 zeolite. Bond lengths are in angstroms.
surface, 26.6 kcal/mol is required for the release of the product reaction system should move preferentially on the quartet
methanol. Even if we consider the spin inversion to take place potential energy surface judging from the previous study on
in the exit channel, this value would not change because the the corresponding gas-phase process.10 The initially formed
sextet and the quartet states of the product complex, indicated complex exhibits an η2-C6H6 mode in which the Fe ion is closer
at right in Figure 2, are close-lying in energy. Thus, the quartet to one pair of carbon atoms of the benzene ring. The benzene
potential energy surface plays a dominant role in this reaction. ring remains nearly planar, so the complex is a kind of π
complex. The binding energy for the reactant complex was
Benzene Hydroxylation on Fe-ZSM-5 Zeolite predicted to be 10.2 kcal/mol. After this complex is formed, an
Structures of the Reaction Species. Economical, direct H atom abstraction occurs via TS1 that connects the reactant
conversion of benzene to phenol over Fe-ZSM-5 zeolite has complex and the hydroxy intermediate. The C-H bond and the
attracted the attention of researchers in applied chemistry,2 but O-H bond in the four-centered structure were computed to be
little is known of the reaction mechanism by which benzene is 1.298 and 1.364 Å, respectively. These values are reasonable
oxidized to phenol. We believe that our theoretical study on for a transition-state structure responsible for C-H bond
the benzene hydroxylation on Fe-ZSM-5 zeolite will be of breaking and O-H bond forming. The C-H bond is signifi-
significant use in the interpretation of the catalytic processes cantly deviated from the benzene plane, and the four-centered
and in the rational design of high-performance zeolite catalysts. structure is nearly orthogonal to the benzene plane. Thus, the
In a previous paper,10 we addressed the reaction pathway and first half of the reaction ends with the formation of the
the energetics for the gas-phase benzene-phenol conversion intermediate complex that involves the resultant OH and C6H5
by the bare FeO+ complex. We can apply our previous results groups as ligands.
to the catalytic processes on Fe-ZSM-5 zeolite. We next take a look at the hydroxy intermediate. This
Figure 3 presents ball-and-stick structures for the reaction intermediate is likely to play a central role in the reaction
intermediates and the transition states along the reaction pathway pathway for the benzene-phenol conversion, by analogy with
for the benzene hydroxylation on the “R-oxygen” model. The the reaction pathway for the methane-methanol conversion. The
reaction mechanism is identical to that for the methane FeOH moiety is nearly coplanar with the benzene ring. TS2 is
hydroxylation discussed earlier in essential bonding characters. a transition state in which Fe-C bond breaking and C-O bond
Our discussions can be reasonably restricted to the reaction formation occur in a concerted manner to connect the hydroxy
pathway in the quartet state because the quartet potential energy intermediate and the product complex that involves phenol as
surface is low-lying compared to the sextet state and thus the a ligand. This three-centered transition state is responsible for
Methane-Methanol and Benzene-Phenol Conversions J. Phys. Chem. B, Vol. 104, No. 4, 2000 739
Conclusions
The reaction pathways and the energetics for the direct
hydroxylation of methane and of benzene that occur on the
surface of Fe-ZSM-5 zeolite have been computed and analyzed
Figure 4. Potential energy diagram for the direct benzene hydroxy- using the B3LYP DFT method. We proposed a reasonable
lation on a model of “R-oxygen” of Fe-ZSM-5 zeolite in the quartet model for “R-oxygen”, a surface oxygen species that is
state. Relative energies are in kcal/mol. responsible for the catalytic reactivities of Fe-ZSM-5 zeolite;
our model involves an iron-oxo species on the AlO4 surface
the process for a phenyl migration from the iron active center site as an active center. The salient features of the two reaction
to the oxygen atom. The breaking Fe-C bond and the forming pathways proposed are identical in essential bonding characters.
C-O bond were computed reasonably well to be 1.999 and In the initial stages of each reaction, methane or benzene comes
1.730 Å, respectively. The three-centered (Fe,O,C) structure into contact with the active iron site of the “R-oxygen” model
responsible for the phenyl migration is again nearly orthogonal leading to the reactant complex. H atom abstraction from
with the benzene ring. Let us finally look at the product methane or benzene occurs via a four-centered transition state
complex. Note that the basic structure of the phenol moiety in (TS1), resulting in the formation of the hydroxy intermediate.
the product complex is not significantly changed from that of The hydroxy intermediate is next transformed into the product
free phenol. complex via a three-centered transition state (TS2). These
We thus conclude that the direct conversion of benzene to electronic processes take place in a two-step concerted manner
phenol should proceed in a concerted manner, via neither radical with a stable reaction intermediate. Our proposals for the zeolite-
species nor ionic intermediates. Our computational results are, catalyzed reactions are essentially identical to those for the gas-
generally, in good agreement with the proposals of Panov et phase methane-methanol and benzene-phenol conversions by
al.1 Burch and Howitt29 proposed that the mechanism for the the bare iron-oxo complex.9,10 The overall reaction for the
selective oxidation of benzene involves a radical cation as an methane hydroxylation is 23.9 kcal/mol endothermic on the
intermediate, but our proposal is different from theirs. quartet surface and 26.0 kcal/mol endothermic on the sextet
Energetics for the Hydroxylation of Benzene. We show in surface, and that for the benzene hydroxylation is 8.6 kcal/mol
Figure 4 a computed energy diagram for the benzene hydroxy- endothermic on the quartet surface. Thus, we predict that the
lation on the model of “R-oxygen”. Because the overall reaction benzene-phenol conversion should be energetically more
is 8.6 kcal/mol endothermic on the quartet surface, we predict favorable than the methane-methanol conversion.
that the benzene-phenol conversion should be energetically We think that the “two-step concerted mechanism” should
more favorable than the methane-methanol conversion (23.9 be widely applicable in interpreting how hydrocarbon hydroxy-
kcal/mol endothermic). This is likely in good agreement with lations are catalyzed by transition-metal oxides. The reaction
the experimental results of Panov et al.1,4 In the initial stages pathways proposed in this article may have relevance to certain
of the reaction, benzene comes into contact with the iron active enzymatic processes concerning hydrocarbon hydroxylations,
site of the “R-oxygen” model to form the reactant complex. in which various iron-oxo complexes play a central role.30,31
The binding energy for the reactant complex was predicted to Our mechanistic proposals are completely consistent in the gas-
be 10.2 kcal/mol, which is clearly larger than the value in the phase,9,10 enzymatic,28 and zeolite-catalyzed reactions.
methane case (1.6 kcal/mol), due to the higher reactivity of the
frontier π orbitals of benzene. After the reactant complex is Acknowledgment. We are grateful to the “Research for the
formed, one of the H atoms of the benzene molecule is Future” Program of the Japan Society for the Promotion of
abstracted in a concerted manner via TS1. The barrier height Science (JSPS-RFTF96P00206) and to a Grant-in-Aid for
for this electronic process was computed to be 15.4 kcal/mol Scientific Research on the Priority Area “Molecular Biometal-
from the reactant complex and 5.2 kcal/mol from the dissociation lics” from the Ministry of Education, Science, Sports, and
limit on the quartet surface. We think that this transition state Culture of Japan for their support of this work. Y.S. is grateful
should be thermally accessible. to the JSPS for a graduate fellowship. Computations were partly
The hydroxy intermediate thus formed is also stable in energy. carried out at the Supercomputer Laboratory of Kyoto University
Therefore, the barrier height for TS2 was predicted to be very and at the Computer Center of the Institute for Molecular
large (31.1 kcal/mol) if measured from the hydroxy intermediate. Science.
However, from a close inspection of the energy diagram, the
height of TS2 is found to be comparable to the dissociation References and Notes
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