Journal of Catalysis 383 (2020) 322–330

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Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat

DFT and microkinetic comparison of Pt, Pd and Rh-catalyzed ammonia

oxidation
Hanyu Ma a, William F. Schneider a,b,⇑
a
Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, IN 46556, United States
b
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, United States

a r t i c l e i n f o a b s t r a c t

Article history: Ammonia oxidation is the heart of the Ostwald process and is important in emissions control. Catalytic
Received 26 November 2019 behaviors are a function of conditions and are observed to vary across the platinum group metals (PGMs)
Revised 7 January 2020 Pt, Pd, Rh. Here, we combine density functional theory computations and microkinetic modeling to
Accepted 29 January 2020
rationalize these dependencies. We compute reactions over model (2 1 1) and (1 1 1) surfaces of
Available online 20 February 2020
PGMs. Binding energies are similar on Pd and Pt and generally greater on Rh, while activation energies
vary across all metals. Rates on (2 1 1) surfaces are greater than (1 1 1) surfaces. The stepped Pt is most
Keywords:
active and stepped Rh most selective to N2 at ammonia slip conditions, while at Ostwald process condi-
Ammonia oxidation
Platinum group metals
tions, stepped Pd is most active and stepped Pt most selective to NO. Degree of rate and selectivity control
Density functional theory analysis provides insights into the reactions limiting performance of PGMs. Both activation barriers and
Microkinetic modeling surface coverages influence rates and selectivities.
Structure sensitivity Ó 2020 Elsevier Inc. All rights reserved.

1. Introduction
Ammonia oxidation is catalyzed by platinum-based materials to
effect both ammonia slip control and the Ostwald process [1]:
NH3 ðgÞ þ 0:75O2 ðgÞ ! 0:5N2 ðgÞ þ 1:5H2 OðgÞ
NH3 ðgÞ þ 1:25O2 ðgÞ ! NOðgÞ þ 1:5H2 OðgÞ
NH3 ðgÞ þ O2 ðgÞ ! 0:5N2 OðgÞ þ 1:5H2 OðgÞ
Selectivity to the thermodynamic N2 product over N2O and NO is a
key performance metric in ammonia slip applications for environ-
mental protection, in which the goal is to oxidize NH3 with O2 to
limit NH3 release from diesel vehicles or industrial point sources
to the environment. Pt nanoparticles are the most common cata-
lysts [2], and selectivities of current materials need to be improved
upon to meet increasingly stringent regulations to protect the envi-
ronment [3,4]. NO is the desired product of NH3 oxidation in the
Ostwald process, and a Pt-based gauze is the most common catalyst
[5]. While selectivity to NO is generally high, N2O, a greenhouse gas
and stratospheric ozone depleter, is a common secondary product.
Nitric acid plants are the largest source of N2O emissions in the
chemical industry [6].
⇑ Corresponding author at: Department of Chemical and Biomolecular Engineer-
ing, University of Notre Dame, Notre Dame, IN 46556, United State.
E-mail address: wschneider@nd.edu (W.F. Schneider).
Pt, Pd and Rh are the most studied platinum group metals
(PGMs) for ammonia oxidation [7,2,8–10]. In the low-
temperature regime, reaction rates are greatest for Pt while N2
selectivity is greatest over Rh [11,12]. In the high-temperature
regime, rates are greatest over Pd, while selectivity to NO is great-
ð1aÞ est for Pt [13,14]. The microscopic mechanisms that control the
rate and selectivity trends remain unclear.
ð1bÞ
Chmielarz et al. measured ammonia conversion and product
ð1cÞ selectivity over oxide-supported Pt, Pd and Rh particles in a plug
flow reactor (PFR) at temperatures relevant to ammonia slip con-
trol [11]. Independent of oxide support, NH3 conversion reached
100% at the lowest temperature over Pt, followed by Pd and Rh.
The N2 selectivity, however, followed the reverse order of
Rh > Pd > Pt, across temperatures from 373 to 773 K. Selectivities
over Pt and Pd were similar. Li and Armor reported similar exper-
iments over Al2O3-supported Pt, Pd and Rh catalysts [12]. Activities
were greatest and N2 selectivity least over the Pt catalyst. Activities
were lower and selectivities to N2 were greater over both Pd and
Rh. Pignet and Schmidt observed NH3 oxidation over Pt, Pd, and
Rh wires in a continuous stirred-tank reactor (CSTR) operated from
500 to 1673 K and total pressures of 0.1–1 Torr [14]. At tempera-
tures relevant to ammonia slip control, reaction rates followed
Pt > Pd > Rh and N2 selectivities tracked in the opposite order. At
higher temperatures relevant to the Ostwald process, rates fol-
lowed Pd > Pt > Rh and NO selectivities followed Pt > Pd > Rh.
Pérez-Ramírez et al. used Temporal Analysis of Products (TAP) to

https://doi.org/10.1016/j.jcat.2020.01.029
0021-9517/Ó 2020 Elsevier Inc. All rights reserved.
 H. Ma, W.F. Schneider / Journal of Catalysis 383 (2020) 322–330
measure ammonia oxidation rates over Pt, Pd and Rh wires at
1073 K [13]. The ammonia conversion rates follow Pd > Pt  Rh
and the NO selectivity followed Pt > Pd > Rh. Thus, relative rates
and selectivities differ across metals but are the same whether
the metal catalysts are supported or unsupported.
NH3 oxidation reaction pathways have been evaluated using
supercell density functional theory (DFT) models of Pt(2 1 1)
[15,16], Pt(1 1 1) [15,17], Pt(100) [18] and Rh(1 1 1) [19] surface
facets, and in the case of Pt, the results used to parametrize
microkinetic models [15,18,20]. A consistent set of DFT and
microkinetic results across metal and surface structure has not
been reported. DFT calculations report that barriers to oxidatively
activate ammonia are similar and barriers to form products are
lower at Pt(2 1 1) step models than on Pt(1 1 1) terraces [15].
NH3 activation and product desorption barriers are reported to
be lower still on Pt(100) than either Pt(1 1 1) or (2 1 1) [18]. These
results all suggest a strong structure sensitivity to catalytic activity.
However, microkinetic models parametrized from the Pt(1 1 1) and
Pt(2 1 1) DFT results report that selectivity shifts from N2 to NO
with increasing temperature, independent of facet, that these
selectivities are controlled by the relative coverages of adsorbed
N and O, and that while selectivities are structure-insensitive,
absolute rates on step sites exceed terraces at low temperatures,
where product desorption is rate-controlling, and converge at high
temperature, where ammonia activation becomes rate-controlling.
A similar DFT-computed reaction network has been reported over
Rh(1 1 1) [19]. In general, ammonia activation and product forma-
tion barriers are greater over Rh(1 1 1) than Pt(1 1 1). Correspond-
ing microkinetic results are not available.
Here, we report intrinsic reaction and activation energies of
reactions relevant to ammonia oxidation using supercell DFT and
(2 1 1) and (1 1 1) model surfaces of Pd and Rh and contrast against
Pt results. While Pt and Pd are similar, adsorption and activation
energies are systematically greater over Rh. We report microki-
netic models parametrized against these DFT results and compare
degrees of rate and selectivity control across all metals and two
surface structures. In general, predicted relative rates and selectiv-
ities are consistent with experimental observation: Pt is both most
active and least selective to N2 at NH3 slip conditions, and Rh is
selective to N2 at all conditions. While relative surface coverages
appear to control selectivity on Pt and Pd, selectivity on Rh arises
from the significantly lower barrier for N2 formation than NO.
These results highlight the interplay between NH3 activation and
product release kinetics that influence both rates and selectivities.
2. Computational details
Plane-wave, periodic supercell DFT calculations were per-
formed with the Vienna ab initio Simulation Package (VASP)
[21,22]. Ion core states were treated with the projector augmented
wave (PAW) method [23,24] and electron exchange and correlation
were treated within the generalized gradient approximation (PBE-
GGA) [25]. We included plane-waves to a cutoff energy of 400 eV
and converged the forces to 0.05 eV/Å. Transition states
were located by the Climbing-Image Nudged Elastic Band method
(CI-NEB) [26] and then refined using the dimer method [27]. We
further confirmed the transition states by performing vibrational
analysis, and identifying one imaginary mode along the reaction
coordinate.
The lattice constants of Pd and Rh are 3.941 and 3.825 Å, respec-
tively, within the model used here, as determined by fitting to the
Birch-Murnaghan equation of state [28,29]. These values agree
well with the experimental values of 3.950 and 3.820 Å [30]. We
modeled the (2 1 1) surfaces using five layers of close packed
(1 1 1) atoms in a 3  2 supercell, except for O2 dissociation
323
reactions, where a 3  3 supercell was used. The bottom two
(1 1 1) layers were fixed to bulk metal locations and the top three
(1 1 1) layers were allowed to relax in all optimizations. We sam-
pled the first Brillouin zone with a C-centered 5  5  1
Monkhorst-Pack k-point mesh [31,32]. We modeled the (1 1 1)
surface with five-layer-thick slab in a 2  2 supercell. The bottom
two layers were fixed and the top three metal layers were allowed
to relax. The first Brillouin zone was sampled with a C-centered
7  7  1 Monkhorst-Pack k-point mesh. Both the (2 1 1) and
(1 1 1) slabs were separated by a 14Å vacuum gap.
We calculated the rate constants of non-activated adsorption
steps using the Hertz-Knudsen equation. We then calculated the
adsorption equilibrium constants and estimated the desorption
rate constants [33]. In the Hertz-Knudsen equation (Eq. (2)), a is
a sticking coefficient, A is the area of one free site, m is the molec-
ular weight of a gas molecule, kB is the Boltzmann constant and T is
the absolute temperature [34]. Previous comparisons show that
that computed rate and selectivity trends are insensitive to details
of these sticking coefficients [15] for ammonia oxidation on Pt. We
take sticking coefficient here to be unity, as an upper limit on
adsorption rates [33].
aA
kads ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð2Þ
2pmkB T
We calculated the adsorption equilibrium constants with Eq. (3).
The enthalpies of adsorption are taken as the zero-point-energy-
corrected DFT energies. We used the entropies of gas molecules
from NIST-JANAF thermochemical tables [35] and estimated the
entropies of adsorbates using harmonic oscillator (HO) model. For
NH3 and H2O, we exclude the molecular rotational modes parallel
to surfaces from the HO model. These modes have frequencies near
50 cm1 and their contributions to the overall entropies are esti-
mated to be small with the hindered rotor model. However, these
rotational entropies are severely overestimated by the HO model
[36].
 
DEDFT þ DEZPE  T DS ðTÞ
KðTÞ ¼ exp  ð3Þ
kB T
We calculated the rate constants of desorption processes with Eq.
(4) to enforce thermodynamic consistency, where P is the standard
pressure of 1 bar:
kads P
kdes ¼ ð4Þ
K
Reaction rate constants (k) involving activated chemisorption
and surface reactions were calculated using harmonic transition
state theory (hTST):
 
kB T qTS Ea
k¼ exp  ð5Þ
h qIS kB T
Here h is the Planck constant and Ea is the zero-point-corrected
energy difference between the transition state and the adsorbed
reactants at infinite separation. We assume qqTSIS ¼ 1 for surface reac-
tions; we show that this simplification has negligible influence on
computed microkinetic rates and selectivities when compare
against models parametrized within a harmonic oscillator model
[15]. The steady-state surface coverages, rates and selectivities were
solved assuming fixed pressures of gaseous species with a mean-
field microkinetic model [37]. The results are equivalent to kinetics
of catalysts in a continuous stirred-tank reactor with infinite small
residence time. The differential equations for the coverage of sur-
face species i are written as:
@hi X
¼ cij rj ð6Þ
@t
j
324 H. Ma, W.F. Schneider / Journal of Catalysis 383 (2020) 322–330
and
Y c
Y c
Y c Y c
r j ¼ kþj hþj ij Pþj ij  kj hjij Pjij
þj þj j j
where cij is the coefficient for the stoichiometry of species i in reac-
tion j and r j is the net rate of surface reaction j. The forward and
backward reactions are represented as þj and j, respectively. kj
is the rate constant and hj and P j are the coverages and pressures
of different species involved in reaction j, respectively. The coverage
is conserved for a surface:
X ence of fcc or hcp sites across different metals and surfaces. Bind-
h þ hi ¼ 1
i
where h is the coverage of free sites. We solved the ordinary differ-
ential equations (ODE) at steady state, where @h@t
i
¼ 0, using a method
that automatically switches between nonstiff (Adams) and stiff
(BDF) solvers, as implemented in scipy.integrate.odeint in Python.
The steady-state coverages can also be solved from a system of alge-
P
braic equations ( j cij rj ¼ 0). We further solved the system of alge-
braic equations using the coverages solved from ODE as initial
guesses to confirm the steady state coverages. We used Newton’s
method, as implemented in mpmath.findroot in Python.
3. Results and discussion
We included ammonia oxidation pathways suggested by both
prior experimental and theoretical work, including NHx
(x ¼ 0; 1; 2; 3) activation over metal, O*, and OH* sites, where *
indicates a surface-bound species. N2, NO, and N2O are assumed
to be formed from N* combination with N*, O* and NO*. Possible
routes from NH3 adsorption to product generation are shown in
Scheme 8. Experimentally, surface-bound NHx (x ¼ 0; 1; 2; 3) and
OHy (y ¼ 0; 1) have been observed on Pt(1 1 1) under ultrahigh vac-
uum conditions after dosing O and NH3 [38]. Surface-bound NHx
(x ¼ 0; 1; 2; 3) and O have been identified on Ir(1 1 1) with X-ray
photoelectron spectroscopy (XPS) following dosing of O and NH3
[39]. Similarly, NHx and O were observed on stepped Pt(533) with
in situ XPS at low pressures [40]. Recently, Dann et al. observed N
and O insertion into supported metallic Pd at low and high T
respectively with operando X-ray absorption fine structure spec-
troscopy, suggesting high surface coverage of N at low T and O at
high T [10]. Theoretically, the reaction pathways were evaluated
with DFT computation on Pt(2 1 1) [15,16], Pt(1 1 1) [15,17], Pt
(1 0 0) [18], Rh(1 1 1) [19], Au(1 1 1) [41] and Cu(1 1 1) [42].
Microkinetic models on Pt(2 1 1), Pt(1 1 1), and Pt(1 0 0) including
the aforementioned pathways capture the essential rate and selec-
tivity trends of experimental observations [15,18,20]. We therefore
performed plane-wave, supercell DFT computation within the gen-
eralized gradient approximation on the reactions shown in
Scheme 8 for Pd(2 1 1), Pd(1 1 1), Rh(2 1 1) and Rh(1 1 1). We
include previously reported results using the same methods for
Pt(2 1 1) and Pt(1 1 1) for comparison [15].
Scheme 8. Schematic representation of possible reaction pathways from NH3 adsorption to oxidation product generation. Each segment represents an elementary step, and
widths are arbitrary. Light pink, light blue, and light gray segments denote successive N–H cleavage steps across metal, O*, and OH* sites, respectively. Orange, pink, and blue
segments represent pathways leading to NO, N2O, and N2, respectively.
3.1. Adsorption
ð7Þ
The most favorable binding sites of surface intermediates and
their corresponding geometries are comparable on the three met-
als (Table S1, Fig. S1 and Fig. S2). In general, NH3 and H2O prefer
atop sites, NH2 and OH prefer bridge sites, and NH, N and O prefer
hollow sites for both (2 1 1) and (1 1 1) surfaces. The site prefer-
ences of NO and N2O are different on (2 1 1) and (1 1 1) surfaces,
but the preference across PGMs are unvaried. For intermediates
that bind on hollow sites, there is no obvious trend on the prefer-
ð8Þ ing energies are summarized in Table S1 and results on all surfaces
are plotted against results on Pt [15] in Fig. 1. Binding energies are
greatest in magnitude on Rh and similar on Pd and Pt, independent
of facet. The exceptions are NH3 and H2O, which bind similarly on
all surfaces, and NO, which binds more strongly on Pd than Pt.
Binding site preferences and binding energies are consistent with
previous reports [43–45].
3.2. Ammonia activation and product formation
The similar adsorption site preferences suggest similar reaction
pathways on the three metals, and as shown in Fig. S3-S14, com-
puted transition state structures are similar on all metals. In sum-
mary, the minimum energy path (MEP) is a convolution of H2N-H
bond scission followed by NH2 migration from an atop to bridge
site, and the highest point along this MEP corresponds with the lat-
ter migration process. H-transfer corresponds to the highest barrier
for NH2 and NH activation, similar to observations on Pt(2 1 1) [16],
Pt(1 1 1) [17], Rh(1 1 1) [19], Au(1 1 1) [41] and Cu(1 1 1) [42]. On
the (2 1 1) surfaces of the three metals, oxidative NH3 and NH acti-
vation is preferred at the (2 1 1) step while NH2 activation occurs
on the terrace. N2 and NO formation occur on the step of (2 1 1) and
N2O formation occurs on the terrace, consistent with a previous
report [46]. Fig. 2 compares reaction profiles on the (2 1 1) facets
of the three metals. NHx activations on O* sites have smaller reac-
tion and activation energies than on OH* sites, except for the NH2
activation barriers. Activation barriers for the reactions occurring
on the terrace—NH2 activation and N2O formation—are greater
than those occurring at the (2 1 1) step.
Fig. 3 reports corresponding results on the (1 1 1) facet. Unlike
the (2 1 1) surfaces, ammonia activations on OH* site of (1 1 1) sur-
faces have smaller reaction and activation energies than on O sites.
These reaction energies are related to reaction (9) in Table S2,
OH* + OH* M O* + H2O*. As a result, the energy difference between
NH3* + OH* M NH2* + H2O* and NH3* + O* M NH2* + OH* is positive
on (2 1 1) surfaces and negative on (1 1 1) surfaces, for instance.
N2* and NO* formation barriers on (1 1 1) surfaces are much
greater than those on (2 1 1) surfaces, suggesting lower N2 and
NO production rates on the former than the latter.
Activation barriers are plotted against Pt results in Fig. 4 to
illustrate variations with metal. Ammonia activation barriers are
 H. Ma, W.F. Schneider / Journal of Catalysis 383 (2020) 322–330 325

Fig. 1. Binding energies of (a) NHx and (b) oxygen-containing species on Pt(2 1 1), Pd(2 1 1) and Rh(2 1 1) plotted against those on Pt(2 1 1). Binding energies of (c) NHx and
(d) oxygen-containing species on Pt(1 1 1), Pd(1 1 1) and Rh(1 1 1) plotted against those on Pt(1 1 1).

Fig. 2. Energy diagrams for O*- and OH*-assisted ammonia activation on (a) Pt(2 1 1), (b) Pd(2 1 1) and (c) Rh(2 1 1). Energy diagrams for N2, NO and N2O formation on (d) Pt
(2 1 1), (e) Pd(2 1 1) and (f) Rh(2 1 1).

generally greater on Rh than Pd and Pt. Activation barriers are sim-
ilar on (1 1 1) facets of Pt and Pd and lower on Pd(2 1 1) than Pt
(2 1 1). Barriers to form products are greater on Rh than on Pt
and Pd. These differences suggest differences in performance in
ammonia oxidation that we explore next.
3.3. Rate and selectivity
To explore the kinetic consequences of these differences, we
parametrized a mean-field microkinetic model with the computed
DFT reaction and activation energies to predict the steady-state
reaction rates and selectivities at temperatures relevant to both
ammonia slip control and the Ostwald process [37]. We assume
adsorbate diffusion is much faster than surface reactions, consis-
tent with convention [47]. We first computed rates at zero ammo-
nia conversion to capture the intrinsic activities of the surfaces. We
then parametrized a continuous stirred-tank reactor (CSTR) to
determine reaction rates and selectivities as a function of conver-
sion. Rate parameters are in Table S2-S5. The evolution of most
abundant surface intermediate (MASI) with T at the same reaction
326 H. Ma, W.F. Schneider / Journal of Catalysis 383 (2020) 322–330

Fig. 3. Energy diagrams for O*- and OH*-assisted ammonia activation on (a) Pt(1 1 1), (b) Pd(1 1 1) and (c) Rh(1 1 1). Energy diagrams for N2, NO and N2O formation on (d) Pt
(1 1 1), (e) Pd(1 1 1) and (f) Rh(1 1 1).

Fig. 4. Activation barriers of (a) ammonia oxidation and (b) product formation on Pt(2 1 1), Pd(2 1 1) and Rh(2 1 1) plotted against those on Pt(2 1 1). Activation barriers of (c)
ammonia oxidation and (d) product formation on Pt(1 1 1), Pd(1 1 1) and Rh(1 1 1) plotted against those on Pt(1 1 1). The activation barriers for product formation are
calculated as A* + B* ? AB(g) + 2*.

conditions of Fig. 5 is shown in Fig. S15. The MASIs on Pt(2 1 1) and
Pd(2 1 1) are comparable, evolving from N* to NO* to O* with
increasing T. Unlike Pt(2 1 1) and Pd(2 1 1), NO* is not observed
on Rh(2 1 1) and the MASI changes from N* to O* with increasing
T. The absence of NO* is consistent with its low decomposition
energy and barrier to decompose to N* and O*. The MASI profile
on terrace surfaces are similar across the three metals: N* domi-
nates at low T, transitioning to O* at high T.
Fig. 5(a) and (b) report computed rates as Arrhenius plots at
zero conversion. TOFs are greater on stepped than terraced facets
at low and intermediate temperatures across all on the metals. Ter-
raced surfaces have a more pronounced temperature dependence,
 H. Ma, W.F. Schneider / Journal of Catalysis 383 (2020) 322–330
Fig. 5. (a) Reaction rate against reciprocal temperature on Pt(2 1 1), Pd(2 1 1) and Rh(2 1 1). (b) Reaction rate against reciprocal temperature on Pt(1 1 1), Pd(1 1 1) and Rh
(1 1 1). (c) Selectivities to reaction products on Pt(2 1 1), Pd(2 1 1) and Rh(2 1 1). (d) Selectivities to reaction products on Pt(1 1 1), Pd(1 1 1) and Rh(1 1 1). Pressures of NH3, O2
and H2O are 0.001, 0.02 and 0.05 bar, respectively.
and thus rates begin to converge at the highest temperature limits.
Relative activity trends across metal are both facet and
temperature-dependent. Stepped Pt rates are greatest at the lower
temperatures characteristic of ammonia slip catalysis, and stepped
Pd rates exceed Pt at Ostwald conditions. Fig. 5(c) and (d) compare
corresponding product selectivities, defined as the relative product
formation rates, si :
ri
si ¼ P
j rj
where i represents a product and j indexes over the three products.
The N2 selectivity decreases and NO selectivity increases with
increasing T across all models, consistent with experimental obser-
vations. The temperatures at which products change from N2 to NO,
and the propensity to generate N2O in the transition region, vary
with both metal and facet. The step surfaces evolve from N2 to
NO selectivity in the order T Pt < T Pd  T Rh , with only Pt predicted
to produce N2O. While Pt results are relatively insensitive to facet,
transition temperatures are substantially decreased on Rh(1 1 1)
and Pd(1 1 1), and the latter in particular is predicted to produce
a substantial fraction of N2O at intermediate temperatures.
To understand the sensitivity of these predictions to NH3 con-
version, we applied the (2 1 1) parameters to a continuous
stirred-tank reactor (SI, Page 19) with the inlet conditions the same
as those in the zero conversion model (Fig. 5), varying the reactor
residence time at fixed number of active sites per volume. Results
are reported in Fig. S16 and Fig. S17. The conversion of NH3
increases from 0 to 100% by increasing the residence time. The
light-off residence time, s, follows sPt < sPd < sRh at 500 K and
sPd < sPt < sRh at 1000 K. Both trends are consistent with the pre-
dicted rate trends at zero conversion. At 500 K, all three surfaces
are selective to N2 across different conversions, except that Pt
(2 1 1) shows decrease of N2 and increase of N2O selectivities when
conversion approaches unity. At 1000 K, NO selectivities on Pt
and Pd drop with NH3 conversion. Pt shows much higher NO
327
selectivities than Pd at high conversions of NH3. Significant N2O
selectivity is observed at high conversion on Pt. Rh shows high
N2 selectivities at different conversions. Selectivity trends are also
consistent with the predicted orders at zero conversion.
The predicted rate and selectivity trends compare well with a
number of experimental observations. In plug-flow reactor exper-
iments at conditions representative of NH3 slip control, NH3
conversions are greatest and N2 selectivities least on oxide-
ð9Þ supported Pt nanoparticle catalysts [11]. Conversions are dimin-
ished and N2 selectivities greater on Pd and Rh. These results are
consistent with TOF and selectivity in Fig. 5(a) and (c). The rate
and selectivity orders are in general the same on different oxide
supports. In the high-temperature regime of ammonia oxidation,
bulk PGM wires were tested in both continuous stirred-tank reac-
tors (CSTR) and temporal analysis of products (TAP) reactors to
understand NO production for the Ostwald process [13,14]. Pd
shows the highest rate and Pt shows the highest NO selectivity.
Rh was the least active and selective to NO. Moreover, TAP exper-
iments showed Pd and Rh have lower selectivity to N2O than Pt
[13]. These observations are consistent with the prediction from
the simulated kinetics at zero conversions and in CSTR. The relative
activities predicted from the terraced surface computations do not
correspond with observations over supported nanoparticles or
bulk wires discussed above. Further, predicted TOFs at steps
greatly exceed those at terraces. Thus, observed activities more
likely represent contributions from step-like than terrace-like sites,
especially at low and intermediate T.
3.4. Degree of rate and selectivity control and reaction flow pathways
To identify the elementary steps most responsible for the over-
all reaction rates, we performed degree of rate control (DRC) across
PGMs [48]. We define rate sensitivity to specific reactions in Eq.
(10), where X RC;i is calculated by changing the forward (kþi ) and
backward (ki ) rate constants of step i simultaneously by 1% while
328 H. Ma, W.F. Schneider / Journal of Catalysis 383 (2020) 322–330

holding constant the rate constants of other steps, kj , and the equi-
librium constant, K i , and monitoring the change of the overall rate
(r) with respect to the reference rate, r0 .
 
ki @r ki;0 r  r 0 r  r0
X RC;i ¼   ¼ ð10Þ
r @ki kj–i ;K i r0 ki  ki;0 0:01r 0

Because the predicted TOFs on stepped surfaces are higher than

those on terraced surfaces, and the rate and selectivity trends of
the stepped surfaces match those in experiments, we compare
degree of rate control as a function of T for Pt, Pd and Rh stepped
surfaces in Fig. 6. The DRC values sum to 1, as expected [48]. We
compare the DRC values for different reactions vs T to understand
the dependence of rate on T and metals. Different reactions control
the overall rate on the three metals. At low T, multiple reactions
control the reaction rate on stepped Pt and Pd surfaces. On stepped
Rh, N2 formation is the single rate-determining step. The higher
barrier of N2 formation on stepped Rh surface results in its low
activity at low T. At high T, the reaction rate is controlled by NH3*
activation by O* on all three metals. The reaction rate order, i.e.
Pd > Pt > Rh, is therefore determined by the barrier order of
NH3* + O*.
Similar to the activity, ammonia oxidation selectivity has a
metal and temperature dependence. The temperature dependence
is similar on different PGMs, but selectivity transitions from N2 to
NO at different temperatures on the three metals. To identify the
elementary steps responsible for this selectivity behavior, we com-
puted degree of N2 selectivity control (DSC) (Eq. (11)) by replacing
rate with N2 selectivity in Eq. (10) [48].
  Fig. 7. Steady-state net rates of surface reactions on Pt(2 1 1), Pd(2 1 1) and Rh
ki @sN2 ki;0 sN2  sN2 ;0 sN2  sN2 ;0 (2 1 1) at 500 and 1000 K, presented as a Sankey diagram, in which each segment
X SC;i ¼   ¼ ð11Þ
sN 2 @ki kj–i ;K i sN2 ;0 ki  ki;0 0:01sN2 ;0 indicates an elementary step and the corresponding segment width indicates net
rate normalized to the overall ammonia oxidation rate. The partial pressures of NH3,
O2 and H2O are 0.001, 0.02 and 0.05 bar, respectively.
As expected, the DSC values sum to 0 [48]. DSC as a function of T are
again similar on stepped Pt and Pd surfaces: NH3* activation by O*
and N2 formation contributes positively to N2 selectivity while NO surface N and O positively and therefore improves the N2 formation
formation and O2 adsorption contributes negatively to N2 selectiv- and depresses NO formation. O2 adsorption, however, contributes to
ity. NH3* activation by O* contributes to the relative abundance of the relative abundance of surface N and O negatively and decreases

Fig. 6. Degree of rate control on (a) Pt(2 1 1), (b) Pd(2 1 1) and (c) Rh(2 1 1). Degree of N2 selectivity control on (d) Pt(2 1 1), (e) Pd(2 1 1) and (f) Rh(2 1 1). The partial
pressures of NH3, O2 and H2O are 0.001, 0.02 and 0.05 bar, respectively.
 H. Ma, W.F. Schneider / Journal of Catalysis 383 (2020) 322–330
the N2 selectivity. On stepped Rh, reactions start to show observable
DSC values only at high T, indicating its high N2 selectivity at low
and intermediate T is not controlled by any single elementary reac-
tion. Rh shows much higher N2 selectivity over a wide range of T
than both Pt and Pd. The high formation barrier of NO from N*
and O* on stepped Rh prevents the formation of NO and increases
the N2 selectivity.
To compare the relative contribution of each reaction step to
the overall rate, we report the net rate of each reaction step nor-
malized to the overall rate in the form of Sankey diagrams [49].
Unlike Scheme 8, where the segment widths are arbitrary, segment
widths in Fig. 7 indicate the contribution of each elementary reac-
tion to the overall ammonia oxidation rate. NH3 decomposition
shows negligible contribution to the overall rate compared to
NH3 activation by O* and OH*. The net rate of the first step of
ammonia activation is always dominated by the O* pathway. At
low T, OH* pathway contributes more than O* pathway for NH2*
and NH activation. At high T, the contribution of OH* pathway
decreases.
The reaction fluxes are generally comparable but there are still
differences among PGMs. At 500 K, the contribution of OH* path-
way to the oxidation of NH* follows Rh > Pd > Pt. At 1000 K, OH*
pathway shows observable contribution to the oxidation of NH2
on Pd while the contribution is negligible on the other two metals.
The Sankey diagrams show the unity N2 selectivity at 500 K on all
three metals. At 1000 K, high NO selectivity is observed on Pt and
Pd while Rh shows high N2 selectivity.
4. Conclusions
Both rates and selectivities are predicted to be functions of plat-
inum group metals. DFT and microkinetic models show that the
NH3 oxidation rate is lower and selectivity to N2 is greater over
Rh and Pd than over Pt. The choice of PGMs metals for ammonia
slip catalysis is therefore a trade-off between rate and selectivity.
Currently, a layer of selective catalytic reduction (SCR) catalyst is
often placed on top of supported Pt in ammonia slip catalysis
[50]. The zeolite-based SCR catalysts reduce NO with NH3 to N2
to compensate the low N2 selectivity of Pt [51]. The dual layer cat-
alyst increases the N2 selectivity but reduces the overall rate [52].
Combining Pt with Rh or Pd may achieve similar performance of
the dual layer catalyst for ammonia slip control. For the Ostwald
process, NO selectivity is the highest on Pt. However, a small per-
centage of N2O is still generated on Pt. Models predict N2O forma-
tion to be negligible on Pd(2 1 1) and Rh(2 1 1), suggesting Pd and
Rh may be beneficial to reduce the reaction selectivity to N2O. In
the Ostwald process, Rh-doped Pt gauze needs to be reinstalled
periodically because platinum is lost from the formation of PtO2
vapor. After the loss of Pt, increased formation of unwanted nitro-
gen is observed. We show here Rh selectively catalyzes ammonia
oxidation to N2 [53]. The depletion of Pt and enrichment of Rh
likely leads to the decrease of NO selectivity during operation.
Surface coverage plays a significant role in determining product
selectivity when formation energies of products are comparable.
When significant differences among product formation energies
exist, screening of high-selectivity materials may benefit from
the comparison of product formation energies. Except for Rh
(2 1 1), the selectivity is highly dependent on the surface coverage
on both (2 1 1) and (1 1 1) surfaces of PGMs: NO selectivity
increases with surface O but decreases with surface N. On Rh
(2 1 1), however, high N2 selectivity is observed even at high O cov-
erage, because the N2(g) formation barrier is significant less than
the NO(g) barrier. It is therefore promising to search for catalysts
with high NO(g) formation barrier and low N2(g) formation barrier
to increase the N2 selectivity for ammonia slip control.
329
Data statement
Raw data and Python codes are available at https://doi.org/10.
5281/zenodo.3620943.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgment
This research was supported by the U.S. Department of Energy,
Office of Science, Office of Basic Energy Sciences, under Award DE-
FG02-06ER15830. The computing resources and technical support
for this work were provided by the Notre Dame Center for Research
Computing and National Energy Research Scientific Computing
Center, a DOE Office of Science User Facility supported by the Office
of Science of the U.S. Department of Energy under Contract No. DE-
AC02-05CH11231. We thank Craig Waitt for comments and
discussions.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.jcat.2020.01.029.
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