PDOS

The reaction mechanism in heterogeneous catalysis which is involving O2 or atomic oxygen has been dicussed
intensely because the spin change of O2 molecule and atomic O during the reaction. To understand the mechanism
of CO oxidation is key for design of advanced materials. Here we demonstrate spin conversion occurs in
the path of CO oxiation on Fe-doped graphene (Fe-Gr) with or without electric field according to our DFT
investigations. Moreover, the reations proceed via the similar favourable spin state along the pathways both
without and with the considered electric field. Additionally, the negative eletric field applied is revealed to
promote CO oxidation due to its improving activation of O-O bond in O2, but also induce a competition between
the atomic O removal via CO+O*→CO2 for the catalyst regeneration and the carbonate-like species formation
via CO2+O* →CO3* when the negative electric field stronger than −0.25 V/Å. Therefore, a more appropriate
for CO oxidation on Fe-Gr is proposed as evidenced under −0.10 V/Å with a lower determined reaction barrier
of 0.62 eV at 298.15 K and expelling the carbonate-like species formation. These findings offer a new view of CO
oxidation on the doped graphene.

The reaction mechanism in heterogeneous catalysis which is involving O2The reaction

mechanism in heterogeneous catalysis which is involving O2The reaction mechanism in
heterogeneous catalysis which is involving O2The reaction mechanism in heterogeneous
catalysis which is involving O2The reaction mechanism in heterogeneous catalysis which is
involving O2The reaction mechanism in heterogeneous catalysis which is involving O2The
reaction mechanism in heterogeneous catalysis which is involving O2The reaction mechanism
in heterogeneous catalysis which is involving O2The reaction mechanism in heterogeneous
catalysis which is involving O2The reaction mechanism in heterogeneous catalysis which is
involving O2The reaction mechanism in heterogeneous catalysis which is involving O2The
reaction mechanism in heterogeneous catalysis which is involving O2The reaction mechanism
in heterogeneous catalysis which is involving O2The reaction mechanism in heterogeneous
catalysis which is involving O2The reaction mechanism in heterogeneous catalysis which is
involving O2The reaction mechanism in heterogeneous catalysis which is involving O2The
reaction mechanism in heterogeneous catalysis which is involving O2The reaction mechanism
in heterogeneous catalysis which is involving O2The reaction mechanism in heterogeneous
catalysis which is involving O2The reaction mechanism in heterogeneous catalysis which is
involving O2The reaction mechanism in heterogeneous catalysis which is involving O2The
reaction mechanism in heterogeneous catalysis which is involving O2The reaction mechanism
in heterogeneous catalysis which is involving O2The reaction mechanism in heterogeneous
catalysis which is involving O2

In the past several decades, carbon monoxide (CO) oxidation has

received significant attentions in heterogeneous catalysis due to its high
academic value in evaluating catalyst activity, selectivity and durability.
It is also widely used in environmental protection and industries
related to CO removal. As we can know, numerous catalysts for CO
oxidation have been developed and the mechanisms have been wellestablished.
The catalytic mechanisms are summarized into the
Langmuir-Hinshelwood (LH) mechanism, and Eley-Rideal (ER) mechanism
[1–9]. In the LH mechanism, precoadsorption of CO and O2 are
required to form a peroxide-type like intermediate. While in the ER
mechanism, the free standing CO molecule directly reacts with a surface
activated O2 or the remaining atomic oxygen. In the past several decades, carbon monoxide (CO) oxidation has
received significant attentions in heterogeneous catalysis due to its high
academic value in evaluating catalyst activity, selectivity and durability.
It is also widely used in environmental protection and industries
related to CO removal. As we can know, numerous catalysts for CO
oxidation have been developed and the mechanisms have been wellestablished.
The catalytic mechanisms are summarized into the
Langmuir-Hinshelwood (LH) mechanism, and Eley-Rideal (ER) mechanism
[1–9]. In the LH mechanism, precoadsorption of CO and O2 are
required to form a peroxide-type like intermediate. While in the ER
mechanism, the free standing CO molecule directly reacts with a surface
activated O2 or the remaining atomic oxygen. In the past several decades, carbon monoxide (CO) oxidation has
received significant attentions in heterogeneous catalysis due to its high
academic value in evaluating catalyst activity, selectivity and durability.
It is also widely used in environmental protection and industries
related to CO removal. As we can know, numerous catalysts for CO
oxidation have been developed and the mechanisms have been wellestablished.
The catalytic mechanisms are summarized into the
Langmuir-Hinshelwood (LH) mechanism, and Eley-Rideal (ER) mechanism
[1–9]. In the LH mechanism, precoadsorption of CO and O2 are
required to form a peroxide-type like intermediate. While in the ER
mechanism, the free standing CO molecule directly reacts with a surface
activated O2 or the remaining atomic oxygen. In the past several decades, carbon monoxide (CO) oxidation has
received significant attentions in heterogeneous catalysis due to its high
academic value in evaluating catalyst activity, selectivity and durability.
It is also widely used in environmental protection and industries
related to CO removal. As we can know, numerous catalysts for CO
oxidation have been developed and the mechanisms have been wellestablished.
The catalytic mechanisms are summarized into the
Langmuir-Hinshelwood (LH) mechanism, and Eley-Rideal (ER) mechanism
[1–9]. In the LH mechanism, precoadsorption of CO and O2 are
required to form a peroxide-type like intermediate. While in the ER
mechanism, the free standing CO molecule directly reacts with a surface
activated O2 or the remaining atomic oxygen.

It is noted that either the activated O2 molecule or the remaining

atomic oxygen is the oxidant agent in CO oxidation process, of which
the ground states are both triplet (3Σg
− for O2 molecule, 3P for O atom).
However, when one of these species reacts with the catalyst in CO
oxidation, spin coupling of the valence electrons would take place,
which results in spin conversion and might obtain differentIt is noted that either the activated O2 molecule or the remaining
atomic oxygen is the oxidant agent in CO oxidation process, of which
the ground states are both triplet (3Σg
− for O2 molecule, 3P for O atom).
However, when one of these species reacts with the catalyst in CO
oxidation, spin coupling of the valence electrons would take place,
which results in spin conversion and might obtain differentIt is noted that either the activated O2 molecule or the remaining
atomic oxygen is the oxidant agent in CO oxidation process, of which
the ground states are both triplet (3Σg
− for O2 molecule, 3P for O atom).
However, when one of these species reacts with the catalyst in CO
oxidation, spin coupling of the valence electrons would take place,
which results in spin conversion and might obtain differentIt is noted that either the activated O2 molecule or the remaining
atomic oxygen is the oxidant agent in CO oxidation process, of which
the ground states are both triplet (3Σg
− for
O2 molecule, 3P for O atom).
However, when one of these species reacts with the catalyst in CO
oxidation, spin coupling of the valence electrons would take place,
which results in spin conversion and might obtain different