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org/JPCC Article

A DFT Study of the Ammonia Decomposition Mechanism on the

Electronically Modified Fe3N Surface by Doping Molybdenum
Diksha Praveen Pathak, Anwesh Kumar, Balathanigaimani Marriyappan Sivagnanam,* A. S. K. Sinha,*
and J. Karthikeyan*
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ABSTRACT: Ammonia is a potential carbon-free carrier for the on-site delivery of hydrogen and is
critical in the development of a hydrogen economy. Designing a noble metal-free catalyst for the low-
Downloaded via SICHUAN UNIV on November 14, 2023 at 04:28:38 (UTC).

temperature decomposition of NH3 is a challenging task in this route. We conducted first-principles

studies to have a comprehensive understanding of the ammonia decomposition mechanism on the
molybdenum-doped iron nitride (Fe3N) surface. The results indicate that when Mo is doped on the
surface of Fe3N(111) it donates electrons to the surface and alters the overall electronic structure of the
catalyst. The activation energy for the intermediate steps of ammonia decomposition is substantially
reduced on the Mo-doped Fe3N surface compared to undoped Fe3N. NH3 adsorbs preferably on Mo sites
over Mo-doped Fe3N(111). However, subsequent intermediate species NH2 and NH prefer Fe sites for
adsorption. The activation barrier for the recombination and desorption of nitrogen adatoms is highest
compared to the other elementary steps in the breakdown of NH3 on Mo-doped Fe3N(111) and therefore
limits the overall rate of the decomposition reaction of ammonia. The Bader charge, density of state
(DOS), and crystal orbital Hamiltonian population (COHP) calculations elucidate the electronic
properties of the catalyst.

1. INTRODUCTION mechanism of ammonia decomposition typically begins with

Hydrogen is a promising alternative to fossil fuels in a the adsorption of NH3 on the surface of a catalyst, followed by
sustainable, carbon-free economy. However, finding a safe and the sequential removal of hydrogen resulting in the formation of
economical technology for the storage and on-site generation of N and H adatoms, which later recombine and then desorb from
hydrogen is a major challenge. For this purpose, ammonia is the catalyst surface as N2 and H2.9−13
proposed as a viable hydrogen vector for on-site hydrogen The rate-governing step for ammonia breakdown is still
ambiguous. However, regardless of the catalyst material used,
production due to the large gravimetric hydrogen density (17.8
there are two possible rate-limiting steps for the decomposition
wt %), easy storage, and well-developed transmission technol-
process of ammonia: N−H bond cleavage and recombination−
ogy.1,2 In the process of producing hydrogen from ammonia, the
desorption of N2 from the catalyst surface.12 One of the earliest
N−H bonds in the ammonia molecule have to be broken,
studies of NH3 decomposition on iron by Brauner et al. reported
followed by N−N bond formation and desorption. However,
N2 desorption as the rate-deciding step.14 In 1966, Takezawa et
without a catalyst, this molecular decomposition reaction is
al. studied the temperature dependence of the NH3 decom-
sluggish and occurs at very high temperatures. It is believed that
position mechanism over the iron catalyst. They found that at
without a catalyst ammonia decomposition cannot be
lower temperatures N2 desorption controls the overall rate while
accomplished below 1100 °C. However, the degree of
the dehydrogenation of any of the adsorbed NHx (x = 1−3)
degradation is dependent on the type of catalyst with which
fragments determines the rate at higher temperatures.15 Wang et
ammonia interacts.3 Several noble- and non-noble-metal-based
al. also confirmed in their studies of ammonia decomposition
catalysts have been studied for these reactions; among them, Ru-
that strongly bonded N adatoms control the reaction rate at
metal-based catalysts were found to be the most efficient for
lower temperatures.16 A theoretical study on ammonia
ammonia decomposition to produce hydrogen. However, the
decomposition over Fe(111) reported the dehydrogenation of
high cost and scarcity of Ru limit its utilization on a large scale.
Hence, it is important to find a nonprecious-metal-based catalyst
that can decompose the ammonia at low temperatures to make Received: June 22, 2023
the process of hydrogen production economically viable.4−8 It is Revised: July 30, 2023
critical to have detailed insight into the ammonia decomposition Published: August 9, 2023
mechanism for developing a less expensive catalyst that can
break down ammonia at low temperatures and understand why
ruthenium has better activity than other elements. The

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The Journal of Physical Chemistry C
NH to N as the rate-determining step.17 NH3 breakdown over
Co(111), Fe(110), and Ni(111) surfaces has shown the
recombination reaction of N adatoms to be more energy costly
than any of the dehydrogenation steps.18
It has been proposed that transition-metal nitrides with
properties like those of noble metals may efficiently operate as
catalysts in the processes of hydrodenitrogenation, Fischer−
Tropsch synthesis, hydrodesulfurization, and the synthesis and
breakdown of ammonia.19−22 Transition-metal nitrides have
high mechanical, thermal, and chemical stability, and they can
transfer electrons from the nitrogen atom.23 The nitrogen in
metal nitrides, in general, is present in the interstitial spaces
between the large metal atoms, altering the surface’s electronic
characteristics. This lowers the energy of activation for ammonia
decomposition on nitride surfaces.24 Also, the surface (lattice)
nitrogen in nitrides participates in the rate-determining N2
desorption step.25 The studies conducted on the decomposition
mechanism of ammonia on Mo2N and MoN surfaces have
reported that the recombinative desorption process limits
overall ammonia decomposition.26,27 The rate of the catalytic
breakdown of ammonia into iron nitrides increases with an
increase in the concentration of ammonia. As compared to clean
iron, the activation energy for ammonia decomposition is
approximately 2 times lower on iron nitrides.28 The lattice
nitrogen atoms in transition-metal nitrides assist the catalytic
formation and breakdown of NH3 by following a Mars−van
Krevelen mechanism.29−32 Iron nitride (Fe3N) has been
reported to be a promising catalyst in ammonia breakdown
and a potential alternative for scarce and costly noble-metal-
based catalysts. Schnepp and co-workers reported hydrogen
generation via the ammonia breakdown reaction on the surface
of the Fe3N catalyst at a gas hourly space velocity of 15 000 cm3
gcat−1 h−1. These results demonstrate that ammonia decom-
position begins at 500 °C and reaches 100% decomposition at
800 °C. The catalyst’s stability at 600 °C improves gradually
over the observation time.33 Further investigations on the
surface reactions as well as the recombination and desorption of
adsorbed N atoms are required to have a full understanding of
the decomposition process of ammonia over Fe3N catalysts.
In this study, we have conducted a comprehensive theoretical
investigation of the NH3 decomposition mechanism on the Mo-
doped Fe3N(111) catalyst surface using plane wave-based
density functional theory calculations. The decomposition of
NH3 over Fe3N occurs at very high temperatures, which limits its
utilization for decomposing ammonia. To overcome this
limitation, we suggest that molybdenum doping in Fe3N as
among transition-metal nitrides Mo2N is considered to be best
and equivalent to platinum in terms of its catalytic activity for
ammonia decomposition.34 The presence of electron-donating
species improves the catalytic activity by balancing the charge of
the intermediate steps of ammonia breakdown.12,35 Our study
shows that Mo transfers the electron to the surface and acts as
the most stable site for NH3 adsorption. We utilized DFT
calculations to determine the adsorption sites and configurations
of all of the reactive intermediates that are involved in the
process of decomposing ammonia over Mo-doped Fe3N(111).
The role of the lattice nitrogen atom in the ammonia
decomposition is included. We also calculated the adsorption
energies, reaction energies, and activation barriers for the
sequential dehydrogenation steps of NH3 and associative N
desorption. The electronic effect of doping Mo on Fe3N has
been demonstrated by the density of states and the COHP
analysis. The objectives of the current work are to understand
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the fundamentals of the catalytic decomposition of ammonia on
Mo-doped Fe3N(111), explain how doping improves the
catalytic activity, and provide insight into the development of
an efficient noble-metal-free catalyst for low-temperature
ammonia decomposition.
2. COMPUTATIONAL METHODS
The atomic structure and electronic structure of catalyst surfaces
and various intermediate products of NH3 decomposition
reactions are studied using plane wave-assisted density func-
tional theory calculations (DFT) as implemented in the Vienna
Ab Initio Simulation Package.36−38 A plane-wave energy cutoff
of 500 eV is fixed in all of the calculations. The electron−ion
potentials are defined using PAW pseudopotentials, and the
electron−electron exchange and correlation energy are
corrected using the Perdew, Burke, and Ernzerhof (PBE)
functional39 described within generalized gradient approxima-
tions. The VASP computed data was further analyzed using
VASPKIT, and the crystal structures were illustrated using
VESTA.40,41 All of the atoms in the bulk Fe3N structure are
relaxed without any constraints, while for the surface models, the
lattice parameters of bulk structures are fixed and the atoms of
adsorbed molecules are relaxed completely. For the electronic
and ionic relaxations, tight convergence criteria of 10−6 and 0.01
eV/Å, respectively, are fixed in all of the calculations. The
Brillouin zone was sampled using 8 × 8 × 1 Monkhrost-Pact k-
mesh.42 A 15 Å vacuum space in the z direction was used. The
surface energy per Fe3N unit per unit area (Es) of various surface
slabs is defined as
[E(surface) m × E(bulk Fe3N)]
Es =
[2A] (1)
where E(surface) is the total energy of the surface slab, E(bulk‑Fe3N) is d
the total energy per Fe3N formula unit of bulk Fe3N, A is the
surface area of the slab, and m is the number of Fe3N units
present in this slab. The adsorption energy Eads values were
obtained by utilizing the given equation
Eads = E(ads *+surface) E(ads*) E(surface) (2)
where E(ads*) and E(surface) are the total energies of the gaseous
adsorbate and the pristine surface, respectively, and the
combined adsorbate/surface system is represented as
E(ads*+surface). The reaction energy (Erxn) is equivalent to the
energy of the product minus the energy of the reactant. The
formation energy of Mo-doped Fe3N(111) by the substitution
of Mo on pristine Fe3N(111) is calculated using the given
formula
formation energy = {E(Mo Fe3N) + E(Fe)} {E(Fe3N) + E(Mo)}
(3)
where E(Mo‑Fe3N) and E(Fe3N) are the total energies of Mo-doped
d d
Fe3N(111) and pristine Fe3N(111), respectively, E(Fe) is the
energy of a single Fe which will be substituted by Mo on pristine
Fe3N(111), and E(Mo) is the energy of a single Mo obtained from
either the Mo dimer (Mo-poor limit) or Mo bulk (Mo-rich
limit).
We used the climbing image nudged elastic band model (CI-
NEB) to calculate the activation barriers and transition states for
the ammonia breakdown process on the Mo-doped Fe3N-
(111).43 The density of states analysis was performed to examine
the electronic structure of the catalyst surface. We evaluated
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Figure 1. Optimized structures of (a) Fe3N; (b) cleaved Fe3N(111), where Fe1 and Fe2 represent iron coordinated with one and two nitrogens,
respectively, B and H represent bridging and hollow sites, respectively, on Fe3N(111); and (c) Mo-doped Fe3N(111), where B1, B2, and B3 are the
bridging sites and H1, H2, and H3 are the hollow sites on Mo-doped Fe3N(111). (d) Formation energy plot of Mo-doped Fe3N(111) (orange = Fe,
blue = N, and cyan = Mo).
crystal orbital Hamiltonian population (COHP) observations
using LOBSTER.44,45
3. RESULTS AND DISCUSSION
3.1. Optimized Structure and Charge-Transfer Study
of the Catalyst Surface. The optimized structure of pristine
Fe3N is shown in Figure 1(a), and nitrogen atoms are present in
one-third of the octahedral voids formed by Fe atoms with an
ABAB...-type stacking, leaving 2/3 of the voids empty. To check
the catalytic activity on different crystalline surfaces, the Fe3N
bulk structure was cleaved along primary crystal planes such as
(100), (001), (110), and (111). The surface energies of these
planes are calculated using the formula given in the Computa-
tional Methods section, and the values are reported in Table 1.
Among these planes, the (111) surface is the most stable, which
is in accordance with a previous experimental investigation on
the Fe3N catalyst, where the (111) plane has the most intense
Table 1. Surface Energy of the Different Planes of Fe3N
Plane Surface Energy/Unit Area (eV/Å2/Fe3N)
111 0.21
100 0.23
001 0.25
110 0.26
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XRD peak.33 Hence, we selected the (111) surface for further
studies of the ammonia decomposition reaction. The optimized
structure of the (111) slab is shown in Figure 1(b), and there are
two types of iron present on the surface, that is, Fe1 (iron
attached with one nitrogen atom) and Fe2 (iron attached with
two nitrogen atoms). B is the bridging site between two Fe1
atoms, and H is the hollow site formed by one Fe2 and two Fe1
atoms. Furthermore, the Fe3N(111) surface is doped with Mo,
and Mo prefers to substitute the Fe2 atom on the Fe3N(111).
The optimized structure of Mo-doped Fe3N(111) is shown in
Figure 1(c). There are mainly two kinds of adsorption sites
available on this doped surface, namely, bridging sites B1, B2,
and B3 and hollow sites H1 and H2. The bridging site B1 is
present between Fe1 and Fe2, B2 is located above Fe1 and Mo,
and B3 is between Fe2 and Mo. The hollow site H1 is
coordinated with three Fe1 atoms, H2 is formed between two
Fe1 atoms and one Mo atom, and H3 is formed between Fe1,
Fe2, and Mo atoms.
We calculated the formation energy for Mo-doped Fe3N(111)
to confirm its stability. Figure 1(d) shows the plot between the
formation energy of Mo-doped Fe3N(111) and the Mo chemical
potential. The formation energy is negative in the region with a
Mo-poor limit and becomes almost zero in the region of a Mo-
rich limit. This explains that during the formation of Mo-doped
Fe3N(111) by the reaction of Mo and pristine Fe3N(111), when
there is a small amount of Mo present in the atmosphere (i.e., if
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Figure 2. Differential density plots of Mo-doped Fe3N(111). Isosurface levels (a) ±0.004 e−/Å3 and (b) ±0.00008 e−/Å3. Pink represents the charge
buildup region, and green represents the charge depletion region remaining Color code: similar to that in Figure 1.

Figure 3. Optimized adsorption configurations for NHx (x = 0−3) and a hydrogen atom on the Fe3N(111) surface. Here, “v” represents the vertical
adsorption geometry of N2, and “p” represents the parallel adsorption geometry of N2. All bond lengths are in Å (white = H; remaining color code is
similar to that in Figure 1).

the Mo comes from a Mo dimer), it can easily substitute the Fe
from pristine Fe3N(111) and form a stable Mo-doped Fe3N.
However, if the atmosphere is Mo-rich or Mo comes from Mo-
bulk, then the formation energy becomes almost zero, indicating
16445
that formation of Mo-doped Fe3N is less favorable in a Mo-rich
environment.
In order to elucidate the effect of Mo doping on the electronic
structure of the (111) surface, we have performed the worse
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Figure 4. Optimized adsorption configurations for NHx (x = 0−3) and a hydrogen atom on the Mo-doped Fe3N(111) surface. Here, “v” represents the
vertical adsorption geometry of N2, and “p” represents the parallel adsorption geometry of N2. All bond lengths are in Å (white = h; remaining color
code is similar to that in Figure 3).

charge calculations. The calculated Bader charge revealed that Table 2. Adsorption Characteristics of the Optimized
the doped molybdenum atom on the catalyst surface transfers Reaction Intermediates in Ammonia Decomposition on
electrons to the surface, which is clearly evident from the before Fe3N(111)
and after doping Bader charge values of Mo which are 6e− and
Adsorbate Adsorption Sites Ead (eV) dN−M (Å) dN−H (Å)
4.7e−, respectively. Furthermore, to confirm the same, the
NH3 Top(Fe2) −0.56 2.13 1.02
differential charge density plots are demonstrated in Figure 2. In
NH2 B(Fe1, Fe1) −3.18 1.95, 2.00 1.02
the surface plot, the electron-rich region is covered with a pink
NH H(1 Fe2 and 2 Fe1) −5.00 1.83−1.9 1.02
isosurface, and the electron-deficient region is covered with a
N H(1 Fe2 and 2 Fe1) −6.13 1.76−1.82
green isosurface. It is clear from the isosurface plot that Mo is
N2(v) Top(Fe2) −0.39 1.81
transferring electron density to the nearby Fe atoms while it itself N2(p) Top(Fe2) 0.34 2.07, 2.08
is becoming electron-deficient. Similar to the earlier studies of H H(1 Fe2 and 2 Fe1) −0.69
charge transfer between Ru and CNT in the Ru/CNT system,
this charge transfer may aid in better adsorption and in lowering Table 3. Adsorption Characteristics of the Optimized
activation barriers on the surface of the catalyst, hence Reaction Intermediates in Ammonia Decomposition on Mo-
enhancing the overall catalytic activity.46−48 Doped Fe3N(111)
3.2. Preferred Adsorption Site of Reaction Intermedi-
ates. Adsorption energy calculations are performed to obtain Ead dN−H
Adsorbate Adsorption Sites (eV) dN−M (Å) (Å)
the most preferred adsorption configurations of the reactive
intermediates in the ammonia decomposition process. NHx (x = NH3 Top(Mo) −1.11 2.26 1.02
0−3) species and the hydrogen atom are adsorbed at various NH2 B1(Fe1, Fe2) −3.22 1.93, 1.99 1.02
NH H1(3 Fe1) −4.96 1.83−1.9 1.02
positions over Fe3N(111) and Mo-doped Fe3N(111). The
N H2(2 Fe1 and 1 Mo) −6.3 1.82−1.9
optimized geometries of preferred configurations on Fe3N(111)
N2(v) Top(Mo) −0.85 2.06
and Mo-doped Fe3N(111) are represented in Figures 3 and 4,
N2(p) Top(Mo) + B2(Fe1, Mo) −0.86 1.83−2.22
respectively, and their corresponding adsorption energies and
H Hollow(H2) −0.77
bond distances are summarized in Tables 2 and 3.
On an optimized Fe3N(111) surface, the NH3 adsorbs
preferably on the Fe2 site with an adsorption energy of −0.56 eV (Figure 3 ii(a) and ii(b)) with Eads = −3.18 eV and Erxn = 0.01
(Figure 3 i(a) and i(b)). However, the other reactive eV. The subsequent dehydrogenated species NH prefers the
intermediates NH2, NH, and N prefer the Fe1 site. NH2 is hollow site H formed by one Fe2 and two Fe1 atoms (Figure 3
adsorbed at a bridging position B between two iron atoms iii(a) and iii(b)), where Eads = −5 eV and Erxn = 0.37 eV. After
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Figure 5. Optimized adsorption geometries of Nlat−NHx (x = 0−2) on the Mo-doped Fe3N(111) surface. The upper and lower panels show top and
side views, respectively. (The color code is similar to that in Figure 4.)
the removal of H from NH, the nitrogen atoms remain adsorbed
at the hollow site H (Figure 3 iv(a) and iv(b)) with Eads = −6.13
eV and Erxn = 0.70 eV. N2 adsorbs in a perpendicular
configuration with an adsorption energy value of 0.34 eV,
suggesting that N2 does not favor the perpendicular config-
uration (Figure 3 v(a) and v(b)). The N2 species is preferably
adsorbed in a vertical configuration on top of Fe2 with an
adsorption energy of −0.39 eV (Figure 3 vi(a) and vi(b)). The
H atom is also adsorbed at hollow site H with Eads = −0.69 eV
(Figure 3 vii(a) and vii(b)).
On the surface of Mo-doped Fe3N(111), NH3 adsorbs very
weakly on top of Fe1 (Eads = −0.10 eV) and does not adsorb over
Fe2. Ammonia preferentially adsorbs over Mo with an
adsorption energy value of −1.11 eV which is in accordance
with one previously reported DFT study on the Mo2N(111)
surface having approximately similar NH3 adsorption energy.26
As evident from the adsorption energy values, the binding
affinity of NH3 on the catalyst surface is almost doubled by
doping Mo on the surface of undoped Fe3N. The adsorbed NH3
has a Mo−N bond length of 2.26 Å, and the N−H bond distance
is 1.02−1.03 Å, similar to that of free ammonia (Figure 4 i(a)
and i(b)).49 Here, Mo helps in the activation of the N−H bond
of NH3 to initiate the decomposition reaction. The N−H bond
activation of ammonia has been further analyzed with the help of
a crystal orbital Hamiltonian population (COHP) analysis in
section 3.4. In the next step of the decomposition process, first
the deprotonation of NH3 takes place, leaving NH2 on the
surface. NH2 adsorbs on a bridging site (B1) between two iron
atoms with an adsorption energy of −3.22 eV and Erxn = 0.22 eV.
Here, the bridged NH2 has N−Fe bond distances of 1.93 and
1.99 Å, and the N−H bond distance is 1.02 Å (Figure 4 ii(a) and
ii(b)). In the subsequent step, after the second deprotonation,
the NH will be generated on the surface. NH prefers a hollow
site (H1) for adsorption which is formed by three irons with an
adsorption energy value of −4.96 eV, and the Fe−N bond
lengths are 1.83, 1.85, and 1.9 Å. The N−H bond distance is 1.02
Å, as shown in Figure 4 iii(a) and iii(b). In the last step of NH3
breakdown, NH is deprotonated, and an N atom is formed on
the catalyst surface. This N atom is preferentially adsorbed over
the hollow space H3 coordinated with two Fe atoms and one Mo
atom with an adsorption energy value of −6.30 eV, which is
lower than those of both Fe(100) (Eads = −7.35 eV) and
Mo2N(111) (Eads = −7.17 eV) and equivalent to that of
Mo2N(100) (Eads = −6.29 eV).26,50 Here the Fe−N bond
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distances are 1.82 and 1.90 Å, and the Mo−N bond length is
1.91 Å (Figure 4 iv(a) and iv(b)). Clearly, the adsorption energy
increases as the number of H atoms decreases from NHx (x = 0−
3) species since the total number of metal−nitrogen
coordinations increases and the metal−nitrogen bond distance
gets shorter.51 The adsorbed N atoms then combine to form N2.
Molecular N2 may adsorb in either a vertical or a perpendicular
configuration on the catalyst surface. N2 adsorbs in vertical
configurations with an adsorption energy of −0.85 eV on the Mo
top with a Mo−N bond length of 2.06 Å and a N−N bond length
of 1.13 Å, which is almost equivalent to that of N2(g) (Figure 4
v(a) and v(b)). However, N 2 favors a perpendicular
configuration with the adsorption energy equivalent to −0.86
eV (Figure 4 vi(a) and vi(b)). Here the N2 molecule adsorbs in
such a way that both N atoms are adsorbed on top of Mo but one
N is in a bridging position between Mo and Fe atoms with an
M−N bond length in the range of 1.83−2.22 Å and a N−N bond
length of 1.2 Å, which is marginally longer than that of N2 in its
gaseous form. Some other possible adsorption configurations of
the intermediates in the NH3 decomposition reaction have been
represented in Figure S2, and their corresponding adsorption
energy values are summarized in Table S1. The H atoms that are
generated during the dehydrogenation steps in the NH3
decomposition process prefer to get adsorbed over a hollow
site constituting two Fe atoms and one Mo atom with an
adsorption energy of −0.77 eV (Figure 4 vii(a) and vii(b)).
Another stable site for H adsorption is on the bridge between
two iron atoms, having an adsorption energy of −0.59 eV
(Figure 4 viii(a) and viii(b)).
Reactive intermediates generated during the catalytic break-
down of ammonia can also adsorb at the lattice nitrogen (Nlat)
sites. After the dehydrogenation of ammonia at the Mo site, the
resultant NH2 may move to the nearby lattice nitrogen atom and
form Nlat−NH2 (Figure 5 ia and ib). The adsorption energy for
this attachment of NH2 at Nlat is −0.82 eV, which is much lower
than that at its other three adsorption sites (B1, B2, and B3) on
the catalyst surface (Table S1). Later, the dehydrogenation of
Nlat−NH2 will generate Nlat−NH over the surface of the catalyst.
Transit of the NH molecule adsorbed at the hollow site H1
(Figure 4 iiia and iiib) toward the neighboring Nlat may also
generate Nlat−NH. Afterward, the NH migrates and gets
adsorbed in the hollow site formed by Fe, Mo, and Nlat (Figure
5 iia and iib) with an adsorption energy value equivalent to
−3.16 eV and Erxn = 1.91 eV. Further dehydrogenation will result
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in the formation of Nlat−N. The nitrogen atom formed after the
dehydrogenation of adsorbed NH is settled at a hollow site
coordinated with Nlat, Fe, and Mo (Figure 5 iiia and iiib). The
adsorption energy for this step is −4.47 eV, and the reaction
energy is endothermic by 2.01 eV. This elucidates that the
formation of Nlat−N on the catalyst surface is challenging and
energy-intensive.
3.3. Decomposition Reactions of Ammonia. We
investigated the reaction pathway of ammonia decomposition
on Fe3N(111) and Mo-doped Fe3N(111) and calculated the
activation barriers for each step involved in the decomposition
process. Figure 6 illustrates the potential energy profile for the
Figure 6. Schematic representation of the reaction pathway for
ammonia decomposition on Fe3N(111) and Mo-doped Fe3N(111) via
Mo and Fe atoms. Here, TS = transition state and N* = adsorbed
nitrogen. The energies are calculated using the pristine surface and two
NH3 molecules as reference. The color code is similar to that in Figure
4.
sequential dehydrogenation processes of ammonia on Fe3N-
(111) and Mo-doped Fe3N(111) including the optimized
configurations of the transition states. On Fe3N(111), the
decomposition process begins with the adsorption of NH3 on
top of Fe2. Afterward, the adsorbed ammonia is dissociated into
NH2, which remains adsorbed at Fe2, and the H is adsorbed on
nearby surface nitrogen. The adsorbed NH2 then moves from
the Fe2 to the Fe1 site, and H moves to the nearby hollow site
formed by three iron atoms. The activation barrier for this
dissociation is 1.82 eV, which is significantly high, suggesting
that the first dehydrogenation on Fe3N(111) is energy-extensive
and unfavorable. The transition state corresponding to this first
dehydrogenation step TS1 is represented in Figure 6(a) where
NH2 is adsorbed between two irons with an N−H bond distance
of 1.04 Å, and hydrogen is adsorbed at the nearby nitrogen. For
the Mo-doped Fe3N case, NH3 is preferentially adsorbed on the
Mo site, which is consistent with the earlier theoretical
investigations of the preferential adsorption of ammonia at the
atop site on transition metals.5,18,26,51−54 Furthermore, the
adsorbed NH3 is dehydrogenated and the dissociated H atom
migrates to a bridging position between two iron atoms, while
NH2 remains intact at the Mo site. For this pathway, the
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activation barrier is 0.14 eV, which is significantly lower than in
the Fe3N case, and it is exothermic by −0.3 eV. As represented in
Figure 6(b), in the first transition state (TS1) NH2 is adsorbed
over the Mo top and H settles between Mo and the nearby Fe
atom. Here the bond distance between N and H is 1.86 Å. After
the first dehydrogenation, NH2 adsorbed at Fe1 on Fe3N(111)
is further dehydrogenated into NH and H, and the
corresponding transition state for the same is shown in Figure
6(c). Here, both the NH and H are present at the bridging
position between two irons, and the N−H bond length is 1.02 Å.
The activation barrier for this second dehydrogenation step on
Fe3N(111) is 0.50 eV and is minutely exothermic by −0.01 eV.
The NH2 adsorbed at Mo on Mo-doped Fe3N(111) moves to its
most stable adsorption site, which is the bridging site B1 with a
diffusion barrier of 0.60 eV, and H migrates toward hollow site
H2. The second dehydrogenation starts with NH2 being
stabilized at the bridging position between two iron atoms and
is then dissociated into NH which settles over the hollow site
(H1) and hydrogen at the hollow site (H2) interacting with two
irons and one molybdenum. This disintegration reaction has an
activation barrier of 0.33 eV and is exothermic by −0.62 eV. In
the second transition state, NH adsorbs among three iron atoms;
meanwhile, H settles over one of the nearby iron atoms, forming
the hollow site (H1) with an N−H bond length of 1.34 Å
(Figure 6(d)). During the last step of dehydrogenation, NH is
present at the hollow site (H) on Fe3N(111) and decomposes to
N, which remains intact at the hollow site, and H migrates to the
bridging position. Figure 6(e) represents the third transition
state corresponding to the last dehydrogenation step on
Fe3N(111) here; the N is present at the void among three
iron atoms, and H is transitioning to the bridging position. The
activation barrier for this step is 0.58 eV and endothermic by 0.3
eV. On Mo-doped Fe3N, the NH adsorbed at the hollow site is
further dissociated into N and H. The N stays at the hollow site,
and H moves to the bridging position between two iron atoms.
The energy barrier for this pathway is 0.77 eV, which is the
highest among all of the dehydrogenation steps and is slightly
endothermic by 0.02 eV. For the third transition state, N is
adsorbed in the hollow space among three iron atoms, and H
attaches to the nearby iron atom (Figure 6(f)). Then the N
moves to its most stable adsorption configuration at the hollow
site (H2), and H is stabilized on the hollow site (H3)
coordinated with the molybdenum atom and two iron atoms.
Figure 7 depicts the reaction paths of N2* production on Mo-
doped Fe3N(111), along with the transition states. For the
activation barrier calculation, we placed two nitrogen atoms
adjacent to each other and then optimized the configuration.
The activation energy for this pathway is 2.23 eV, which is
approximately 0.7 eV higher as compared to that of Ru13@
CNT.46 However, when compared to the N2 formation barrier
on Mo2N(100) [Ebarrier = 3.59 eV (2N*-Diff + Diff-TS1)] it is
1.36 eV less and on Mo2N(111) [Ebarrier = 2.76 ev (2N*-Diff +
Diff-TS1)] it is lower by 0.53 eV.26 The activation barrier for the
N2* formation is much higher as compared to that of other
dehydrogenation steps involved in the ammonia breakdown
over Mo-doped Fe3N(111) and limits the overall reaction.
3.4. Density of States and COHP Analysis. The effect of
Mo doping on the electronic structure of the catalyst and its role
during the NH3 decomposition reaction are clearly explained by
the density of states and d-band center analysis. We investigated
the d-band center energies of the d orbitals for the two
adsorption sites of ammonia on the catalyst surface, Mo and Fe1,
to examine their electronic structure. The d-band method by
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Figure 7. Potential energy diagram of N2 formation on Mo-doped
Fe3N(111) including the transition state. The color code is similar to
that in Figure 2.
Hammer and Norskov is used to determine the projected
density of states.55 NH3 has a lone pair of electrons having both
up and down spins. Figure 8 shows the PDOS plots of both
molybdenum and iron sites before and after ammonia
adsorption. Before the Mo−NH3 binding, Mo shows d bands
in the range of −8 to 3 eV, whereas after coupling with the
Figure 8. d-orbital projected density of states for Fe1, Mo (before NH3
adsorption) and Fe1*, Mo* (after NH3 adsorption). Up and down
arrows represent up and down spin states, and the Fermi level is
represented by a dotted line.
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ammonia, the d bands are stretched from −10 to 3.5 eV, which
means that the d bands are moving away from the Fermi level
after the donation of a lone pair of electrons from ammonia to
the empty d orbitals of molybdenum, indicating a strong Mo−
NH3 interaction. However, for the Fe1 site, the d bands are a bit
shifted toward the Fermi level after NH3 adsorption from −8 to
6 eV, resulting in weak Fe−NH3 interaction and low adsorption
energy as perceived in our calculations. For Mo, both the up and
down spin states are present near the Fermi level, so ammonia
can easily donate its lone pair of electrons to the available up and
down d orbitals of Mo and will be strongly adsorbed. However,
for Fe1 only down spin states are available near the Fermi level,
which will make it difficult for ammonia to donate its lone pair,
resulting in a weaker Fe1−NH3 interaction (Figure 8). From
Table S1, we can observe that the adsorption energies are on the
order of Eads,Mo > Eads,Fe1, which is consistent with the availability
of up-spin states of molybdenum and iron near the Fermi level.
The COHP plots for NH3 adsorbed at Mo and Fe1 sites are
represented in Figure 9(a) and (b), respectively. It is clear that in
Figure 9. Crystal orbital Hamiltonian population (COHP) plots of (a)
N*-Mo and (b) N*-Fe1 (N* is the N of adsorbed NH3, UP = up spin,
DW = down spin, and εf = Fermi level).
the case of N*−Fe1, antibonding states are slightly more
occupied near the Fermi level while bonding states are more
occupied in the case of N*−Mo. Here, N* is the N of NH3
adsorbed on the surface. More occupied antibonding states
make the molecule unstable, while more occupied bonding
states favor the stability of the molecule. Thus, the adsorption of
NH3 on the Mo site will be more stable and stronger as
compared to that on the Fe1 site. The DOS and COHP analyses
elucidate the strong adsorption of NH3 at Mo as compared to
the iron sites.
The arrangement of Fe d and N p states on the Fe3N(111)
surface (Figure 10(a)) was significantly skewed by the overlap of
the Fe d and N p states after Mo doping (Figure 10(b)). The
substantial transfer of the charge from Mo to the surface Fe and
N, which was shown in the Bader charge calculation, is also
reasonably supported by this observation. The iron d states and
nitrogen p states show a small overlap in Fe3N(111), although
after Mo doping, a significant overlap between the Fe d and N p
states is clearly visible as most of the N p states which were
earlier present between −2 and −4 eV (Figure 10(a)) are now
shifted to between −6 and −8 eV (Figure 10 (b)). The Mo d and
N p states also show a notable interaction with each other. This
may be a sign of hybridization and bonding between Mo and the
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The Journal of Physical Chemistry C
Figure 10. DOS of all of the Mo(d), Fe(d), and N(p) orbitals of (a)
Fe3N(111) and (b) Mo-doped Fe3N(111). Here the curly bracket from
−6 eV to −8 eV represents the regions of small overlap between Fe(d)
and N(p), before Mo doping shown in (a) and a significant overlap after
Mo doping shown in (b). Up and down arrows represent up and down
spin states, and the Fermi level is represented by a dotted line.
Fe3N(111) surface. The significant interaction among Mo, Fe,
and N may further enhance the strong Mo−NH3 interaction as
well as increase the adsorption energy.56 The presence of a more
positive charge on Mo observed in the charge-transfer
calculation (Figure 2) also suggests the strong adsorption of
NH3 at the Mo site compared to iron. Thus, charge-transfer
Figure 11. Crystal orbital Hamiltonian population (COHP) plots of (a) N−H of NH3(g) and (b) N−H of NH3* at Mo (NH3* is the adsorbed NH3,
UP = up spin, DW = down spin, and εf = Fermi level).
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analysis, density of states, and COHP calculations clearly explain
the preferable adsorption of NH3 at the Mo site as observed in
this study.
In Figure 11, the COHP plots for the N−H bond of (a)
isolated gaseous NH3 and (b) NH3 adsorbed on the Mo top
have been plotted. For the N−H bond of isolated NH3(g),
antibonding peaks do not occur near the Fermi level, suggesting
a strong N−H interaction. However, for N−H bond of NH3
adsorbed on the Mo site, the occurrence of some of the
antibonding peaks near the Fermi level suggests the destabiliza-
tion and activation of the N−H bond.57
4. CONCLUSIONS
We theoretically investigated the Mo-doped Fe3N(111) surface
for NH3 decomposition. Our results showed that doping
molybdenum in the iron nitride increases its catalytic efficiency.
The presence of Mo on the catalyst surface offers two main
benefits: (i) NH3 has a strong binding tendency for Mo (Eads =
−1.11 eV on Mo-doped Fe3N) as compared to Fe (Eads = −0.56
eV on Fe3N), which is crucial for the reaction to begin, and (ii)
Mo donates electrons to the catalyst surface that helps in the
rate-controlling step of N2 recombination and desorption. The
activation barrier is highest for the nitrogen recombination step,
and it limits the overall ammonia decomposition reaction.
However, the comparatively lower activation barrier (Ebarrier =
2.23 eV for nitrogen recombination) and adsorption energy
(Eads = −6.30 eV for nitrogen) values observed in this study
indicate the enhanced potential of the Mo-doped Fe3N catalyst
compared to those of other well-known catalysts such as
Fe(100) and Mo2N for NH3 breakdown.26,50 This may be due to
the presence of two different active metal sites: Mo, which
strongly adsorbs NH3 while NH2 and NH intermediate species
are adsorbed at iron sites, and N, which prefers combined Fe−
Mo sites. Similar to our observations, an experimental study also
demonstrated that the combined iron−molybdenum catalyst
Fe3Mo3N has better activity than Mo2N for the ammonia
decomposition reaction due to the presence of a binary Fe−Mo
site.25 The preferable adsorption of ammonia at the Mo site is
clearly explained by the DOS and COHP calculations. Bader
charge calculations and charge-transfer analysis offer insight into
the electronic modification of the catalyst surface due to Mo
doping. Hence, it is proposed that Mo-doped Fe3N(111) may
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The Journal of Physical Chemistry C
act as a sustainable and efficient catalyst for carbon-free H2
generation through ammonia decomposition.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.3c04207.
Optimized structure of different planes of the catalyst
surface; adsorption sites of reaction intermediates other
than the most stable sites; PDOS plot of Mo-doped
Fe3N(111); and zero point energy-corrected adsorption
energy values of the reactive intermediates (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Balathanigaimani Marriyappan Sivagnanam − Department of
Chemical and Biochemical Engineering, Rajiv Gandhi Institute
of Petroleum Technology, Amethi 229304 Uttar Pradesh,
India; orcid.org/0000-0001-5862-6215;
Email: msbala@rgipt.ac.in
A. S. K. Sinha − Department of Chemical and Biochemical
Engineering, Rajiv Gandhi Institute of Petroleum Technology,
Amethi 229304 Uttar Pradesh, India; Email: asksinha@
rgipt.ac.in
J. Karthikeyan − Department of Sciences & Humanities, Rajiv
Gandhi Institute of Petroleum Technology, Amethi 229304
Uttar Pradesh, India; Department of Physics, National
Institute of Technology, Durgapur 713209 West Bengal,
India; orcid.org/0000-0002-1781-8357;
Email: karthikeyan.jeyakumar@phy.nitdgp.ac.in
Authors
Diksha Praveen Pathak − Department of Chemical and
Biochemical Engineering, Rajiv Gandhi Institute of Petroleum
Technology, Amethi 229304 Uttar Pradesh, India;
orcid.org/0000-0002-1321-0926
Anwesh Kumar − Department of Chemical and Biochemical
Engineering, Rajiv Gandhi Institute of Petroleum Technology,
Amethi 229304 Uttar Pradesh, India
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.3c04207
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This research is supported by the Department of Science and
Technology, India, through a DST Inspire Faculty Award Grant
(grant no. DST/INSPIRE/04/2019/000283), and all authors
are grateful to the Center for Computing and Information
Sciences RGIPT-Jais for high-performance computing.
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