Unravelling discharge and surface mechanisms in plasma

assisted ammonia reactions

Paula Navascués,a Jose M. Obrero-Pérez,a José Cotrino,a,b Agustín R. González-Elipe*a and Ana
Gómez-Ramírez*a,b
a
Laboratory of Nanotechnology on Surfaces and Plasma. Instituto de Ciencia de Materiales de
Sevilla (CSIC-Universidad de Sevilla), Avda. Américo Vespucio 49, E-41092 Seville, Spain.
b
Departamento de Física Atómica, Molecular y Nuclear, Universidad de Sevilla, Avda. Reina
Mercedes, E-41012 Seville, Spain
* Corresponding authors
anamgr@us.es
arge@icmse.csic.es

Abstract. Current studies on ammonia synthesis by means of atmospheric pressure plasmas

respond to the urgent needs of developing less environmentally aggressive processes than the
conventional Haber-Bosch catalytic reaction. Herein, we systematically study the plasma
synthesis of ammonia and the much less investigated reverse reaction (decomposition of
ammonia into nitrogen and hydrogen). Besides analyzing the efficiency of both processes in a
packed-bed plasma reactor we apply an isotope exchange approach (using D2 instead of H2) to
study the reaction mechanisms. Isotope labelling has been rarely applied to investigate
atmospheric plasma reactions and we demonstrate for the first time that this methodology
may provide unique information about intermediate reactions that, consuming energy and
diminishing the process efficiency, do not effectively contribute to the overall
synthesis/decomposition of ammonia. In addition, same methodology has demonstrated the
active participation of the interelectrode material surface in the plasma-activated
synthesis/decomposition of ammonia. These unprecedented results about the involvement of
surface reactions in packed-bed plasma processes, complemented with data obtained by
optical emission spectroscopy of the plasma phase, have permitted to unravel key mechanisms
of the ammonia synthesis/decomposition reactions in packed-bed reactors and to propose a
general strategy to increase the yield and energy efficiency of these processes.

Keywords: packed-bed plasma reactors, ammonia synthesis, hydrogen production,

atmospheric pressure plasma, energy efficiency, inefficient plasma processes, ferroelectric
materials.

INTRODUCTION
During the last years plasma and plasma-catalysis reactions carried out in packed-bed
plasma and other type of atmospheric pressure reactors have emerged as a suitable
technology to promote different gas phase processes of high environmental impact.
Examples encompass the removal of contaminants,1–6 the methane, hydrocarbons and
alcohols reforming7–12 or the ammonia synthesis.13–15 Advantages of plasma and
plasma-catalysis for these applications are their low temperature of operation, the
possibility to work at atmospheric pressure or bellow, its straightforward down-scaling
to small reactor sizes or the null induction period required to achieve steady state
conditions, all together enabling a distributed application of the technology directly
connected to the grid.16 However, these good prospects have stubbornly confronted
serious and up no to now unsolved limitations such as a poor energy efficiency and a
low selectivity for the synthesis of given compounds. Different atmospheric plasma
processes (e.g. gliding arcs or dielectric barrier discharges) and reactor designs 17–23 or
the use of different kind of moderator materials for packed-bed discharges (e.g.,
ferroelectrics instead of dielectrics)24–26 have been proposed to overcome energy
efficiency limitations. Conventional and novel (e.g. mesoporous or nanoparticles)
catalysts have been incorporated together with the dielectric material in the inter-
electrode space of packed-bed reactors to improve selectivity and energy
efficiency.20,21,26–31 Herein we will show that, in addition to engineering improvements,
overcoming energy/selectivity bottlenecks require new basic knowledge about the
mechanisms of these atmospheric pressure plasma processes.

The present work is primarily driven by the need of improving the performance of the
plasma synthesis of ammonia in a scenario where, at global scale, the catalytic Haber-
Bosch process is responsible for ca. 1.2% of the global CO2 emissions.16 The requisite of
combining the reduction of energy consumption with the production of ammonia in a
distributed way close to final users has called for an active investigation of a variety or
alternative processes, including plasma-catalysis.13–22,24–39 A second motivation of this
work is the use of ammonia as suitable hydrogen storage vector and the advantages,
with respect to classical catalysis,40–42 of small plasma reactors for its low temperature
decomposition into hydrogen, as required for mobile device applications.

Although a remarkable 7% reaction yield has been reported for the plasma synthesis of
ammonia at atmospheric pressure and ambient temperature,25 this value is still far
from the 10-15% yield of the catalytic Haber-Bosch process. In addition, this plasma
reaction yield is further jeopardized by its comparatively low energy efficiency. Trying
to approach this problem from a new perspective, the present investigation proposes
to study at fundamental level the ammonia synthesis/decomposition reactions
evaluating the extent of intermediate plasma processes which, consuming energy, do
not contribute to increase the yield of final products. Such a conceptual approach has
not been systematically applied in the field of atmospheric plasmas, even though it
would provide critical knowledge for a scientifically founded design of reactors and the
definition of better reaction operational conditions. For this endeavor, we propose an
isotope labelling methodology which, being rather common in conventional catalysis,
has been scarcely utilized in plasma-catalysis.7,35,43 In particular, we have investigated
the isotopic exchange for mixtures NH3+D2 and NH3+N2+D2 to determine the extent by
which the back decomposition reaction (i.e., 2NH3  N2 + 3H2, note that increasing the
performance of this reaction is of interest from the viewpoint of hydrogen storage
applications) and other inefficient hydrogen exchange processes detract plasma
energy and contribute to lower the efficiencies of current processes for the plasma
synthesis of ammonia. In the curse of these investigations, we have also realized that
isotope labelling may also provide information about intermediate processes that,
having been accepted to occur in plasma-catalysis reactions, have not been
experimentally tested. We refer to the direct involvement of the surface of the
moderator and/or catalyst in the reaction mechanisms. With this purpose we have
studied the N2+D2 and N2+H2 plasma reactions, the latter after prolonged exposure of
the inter-electrode material (i.e., lead zirconate titanate – PZT – in our case) to a D2
plasma, and followed the H/D isotope distribution in the produced ammonia. Overall,
the isotope exchange results, together with the analysis of the optical emission spectra
of the plasmas, have permitted to unravel basic mechanisms and the role of
intermediate plasma species in the plasma synthesis/decomposition of ammonia. The
understanding gained about these basic mechanisms has also served to propose
possible solutions to overcome current limitations in the design and functioning of
packed-bed plasma reactors.

EXPERIMENTAL SECTION

Packed-bed reactor and operating conditions

Experiments were carried out in a packed-bed reactor operated at atmospheric
pressure that has been described in detail elsewhere.24,25,35 It mainly consists of a
ferroelectric packed-bed of lead zirconate titanate (PZT) pellets placed between two
parallel plate stainless steel electrodes (75 mm in diameter). The upper electrode was
connected to a high voltage power amplifier (Trek Inc., USA, Model PD05034), coupled
to an AC function generator (Stanford Research Systems, USA, Model DS345), while
the bottom electrode was grounded. More detailed information about the reactor set-
up and its operation can be found in Supporting Information 1. AC voltage amplitude
varied between 2 and 4 kV at a frequency of 5 kHz, if not otherwise stated. Electrical
characterization of the discharge was made by means of an oscilloscope (Agilent Tech.,
USA, Model DSO-X 3924A) directly connected to a high voltage probe (to acquire V(t))
and a series resistance (to acquire I(t)). The average power consumed in the process
(P) was determined by the area of the Lissajous plot recorded for each experiment44
(see Supporting Information 2 for a more detailed description).

All gases utilized, N2, D2, H2 and NH3, were supplied by Air Liquide (Alphagaz, Spain).
Molecules, compounds and molecular fragments will be designated with their
formulas, taking into account the presence of either H or D atoms in their structure
(e.g., HD, ND2H, etc.). However, the terms hydrogen and ammonia in cursive script will
be used when referring to the complete set of labelled molecules of each specific
compound.

To evaluate the effect of residence time on reaction mechanisms, we varied the total
gas flow rate of reactants, but always keeping the same proportion between gas
mixture components. Values of reactant gas flow rates are given in the text. Although
all experiments were performed at ambient temperature, a small thermal drift in
temperature up to 40ºC at the reactor walls occurred after long operating periods.

Gas and isotope exchange monitoring

To analyse the composition of reactor outlet mixtures and to follow isotopic exchange
processes we used a Quadrupole Mass Spectrometer (Pfeiffer Vacuum, Germany,
QMG 220 Prisma Plus). A typical example of the spectrometer response when
analysing isotope exchange processes involved in the ammonia
synthesis/decomposition reactions can be seen in Supporting Information 3. From the
intensity of the different m/z peaks attributed to either hydrogen (i.e., H2, HD, D2) or
ammonia (i.e, NH3, NDH2, ND2H and ND3) species it is possible to quantitatively
determine the percentage of labelled molecules in each product and its evolution with
the utilized experimental conditions (see a previous work35 and the Supporting
Information 3).

Occasionally, mass spectrometry analysis was complemented by results obtained with

an infrared (FT-IR) spectrometer (Agilent Technology, USA, Cary 630 FTIR) located in
series with the reactor and before the quadrupole. The spectra were registered with a
resolution of 1 cm-1. Results by this technique that complement those obtained by
mass spectrometry will be reported only for some of the experiments.

Optical Emission Spectroscopy (OES) was used for in situ plasma diagnosis. The spectra
were measured by a monochromator (Horiba Ltd., Japan, Jobin-Yvon FHR640), with a
resolution of 0.1 nm. An optical fibre feed-trough was situated in the lateral wall of the
reactor to collect the light emitted by the plasma (see Supporting Information 1).

Reaction yield and energy efficiency

For the ammonia synthesis reaction, the so-called chemical yield, YN2 (%), and the
energy efficiency for the production of ammonia, EE-NH3 (gNH3/kWh) are defined as:
𝑀𝑁𝐻3 (𝑜𝑢𝑡)
𝑌𝑁2 = · 100 (𝐸1)
2 · M𝑁2 (𝑖𝑛)

𝑚𝑁𝐻3 (𝑜𝑢𝑡) · 60
𝐸𝐸 − 𝑁𝐻3 = (𝐸2)
𝑃

where MNH3(out) and MN2(in) refer to the flows of these gases in the product and
reactant mixtures, respectively, mNH3(out) is the amount of produced ammonia (in
grams) and P is the average power consumed in the process.

For the ammonia decomposition reaction, the decomposition yield, DYNH3 (%) and the
energy efficiency for H2 production, EE-H2 (LH2/kWh) are defined as:
 M𝑁𝐻3 (𝑖𝑛) − M𝑁𝐻3 (𝑜𝑢𝑡)
𝐷𝑌𝑁𝐻3 = · 100 (𝐸3)
M𝑁𝐻3 (𝑖𝑛)

𝑉𝐻2 (𝑜𝑢𝑡) · 60
𝐸𝐸 − 𝐻2 = (𝐸4)
𝑃

where VH2(out) refers to the volume (in liters) of H2 produced by the decomposition of
ammonia, i.e., discarding hydrogen in the reactant mixture.

Inefficient reaction events

The concept of inefficient reaction event, defined in previous work,35 designates the
occurrence of intermediate processes that are ineffective in producing a valuable
“product” molecule (either ammonia or hydrogen depending on the intended process).
Examples illustrating this type of inefficient intermediate events for ammonia
production are provided in Supporting Information 4

The minimum number of inefficient reaction events (RE) associated to the formation of
ND2H molecules is defined as:
𝑀𝑁𝐻3 (𝑜𝑢𝑡)
𝑅𝐸NHD2 = (%𝑁𝐷2 H · 2) · (𝐸5)
𝑇𝑜𝑡𝑎𝑙 𝑓𝑙𝑜𝑤 (𝑜𝑢𝑡)

where %ND2H refers to the percentage of this molecule within the ammonia molecules
and the multiplying factor 2 refers that this molecule requires at least two
intermediate reactions to be formed in a mixture of D 2 plus NH3. Similar definitions can
be made for NDH2 or ND3 and for the minimum number of inefficient events
associated to the formation of ammonia:
𝑀𝑁𝐻3 (𝑜𝑢𝑡)
𝑅𝐸𝐴𝑚𝑚. = (%𝑁𝐷𝐻2 · 1 + %𝑁𝐷2 H · 2 + %𝑁𝐷3 · 3) · (𝐸6)
𝑇𝑜𝑡𝑎𝑙 𝑓𝑙𝑜𝑤 (𝑜𝑢𝑡)

A similar definition can be made for the various forms of labelled hydrogen (i.e., H2 and
HD if using D2 as reactant) and for the minimum total number of inefficient reaction
events (TRE):
𝑇𝑅𝐸 = 𝑅𝐸𝐴𝑚𝑚𝑜𝑛𝑖𝑎 + 𝑅𝐸𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 (𝐸7)

RESULTS AND DISCUSSION

Ammonia decomposition reactions
In previous works we have shown that, a mixture of nitrogen and hydrogen fed in the
appropriate concentrations into a packed-bed reactor produces a certain amount of
ammonia. This could be maximized up to 7% of nitrogen conversion by properly
adjusting the N2:H2 ratio, the operating electrical parameters, the size and type of
interelectrode material, the distance between electrodes and the residence time of
gases.24,25 These results proved that residence time of reactants is a critical parameter
to control efficiency, although no linear relationship exists between this parameter and
production of ammonia. This deviation from linearity suggested that besides the
ammonia synthesis reaction, there are other plasma processes that are inefficient to
produce ammonia. One of these reaction processes might be the partial
decomposition of the formed ammonia into nitrogen and hydrogen.

If ammonia decomposes into N2 and H2, this process will reduce the ammonia
synthesis rate and the energy efficiency for the ammonia synthesis process. However,
maximizing the decomposition yield would be aimed when hydrogen is the desired
product of ammonia decomposition. Pure ammonia decomposition results are shown
in Figure 1 and Table 1. Data in this figure show that more than 30% ammonia
decomposed in this experiment and that decomposition yield only decreased by 7-8%
for a three times higher flow. It is noteworthy that energy efficiency in this hydrogen
production experiment is similar to that previously reported for the wet reforming of
methane in the same reactor.45

Figure 1. (a) Scheme of the ammonia decomposition reaction indicating that three H2 and one
N2 molecules are formed from the decomposition of two ammonia molecules due to plasma
processes triggered by the interaction with plasma electrons (see the square inset for
illustration). (b) Plots of NH3 decomposition yield and Energy Efficiency for H2 production
represented against NH3 flow, varying from 3 to 9 sccm. The experiment was carried out at a
frequency of 5 kHz and a voltage amplitude of 2 kV (consumed power 10 ± 1 W).

The relatively high-energy efficiency of the ammonia plasma decomposition reaction

supports a high reversibility for the process: N2 + H2  NH3. This assessment was
further confirmed by the decomposition yields and energy efficiencies found in
experiments reported in Table 1 for mixtures NH3+N2 and NH3+H2 (total flow 9 sccm).
Since values of these two parameters were similar for pure NH3 and a mixture NH3+N2
(ratio 1:2), we can conclude that plasma electrons preferentially activate ammonia
over nitrogen molecules. For the mixture NH3+H2, however, experiment revealed a net
loss of energy efficiency, suggesting that hydrogen competes more efficiently than
nitrogen (and as efficiently as ammonia) for the plasma electrons. This inference
agrees with that H2 has a higher electron impact ionization cross section than N2 (e.g.,
for 16 eV electrons values are 0.013 Å2 and 0.034 Å2 for N2 and H2, respectively).46 This
experiments also suggests that hydrogen radicals or excited species may recombine or
become exchanged with hydrogen atoms in ammonia molecules or fragments with null
decomposition of this compound (i.e., what we call inefficient reaction events). In next
sections, using the isotope labelling technique with mixtures NH3+D2 and NH3+D2+N2,
we will study these exchange reactions.
Table 1. Ammonia decomposition. Decomposition yield of ammonia and energy efficiency
associated to H2 production for a plasma of NH3 and mixtures of this gas with N2 or H2 (current
amplitude was fixed constant at 25 mA).
Gas or Total flow rate DY-NH3 EE-H2
mixture (sccm) (%) (LH2/kWh)
3 32 8.0
NH3 6 24 13
9 20 16
NH3 + N2 9 (ratio 1:2) 19 16
NH3 + H2 9 (ratio 2:3) 17 6.0

Ammonia decomposition vs. isotope exchange reactions

The reversibility between ammonia synthesis and decomposition reactions strongly
suggests the occurrence of hydrogen atom exchanges between ammonia and
hydrogen molecules, as well as other intermediate processes. Experiments utilizing a
NH3+D2 reactants mixture (NH3:D2 ratio of 2:3) provided interesting clues to account
for the nature and extent of these intermediate processes. A summary of the results
obtained is reported in Figure 2. Figure 2(a) shows a clear evolution in the intensity of
the recorded m/z peaks as a function of power (i.e., basically a progressive decrease in
the intensity of peaks associated to D2 and NH3 and an increase of those due to H2, HD,
NDH2 and ND2H (c.f., Figure 2)). As illustrated by the schemes in Figure 2(b), this
evolution sustains that a series of isotopic exchange processes of the type:

NH3 + D2  NDXHY + HD (H2) (E8)

progressively increased with the plasma power.

From the analysis of the intensity of the different m/z peaks (see Supporting
Information 3), it is possible to estimate the partition of the difference labelled
molecules in a given compound (i.e., H2, HD and D2 for hydrogen and NH3, NDH2, ND2H
and ND3 for ammonia). The histogram plots in Figures 2(c) and 2(d) represent the
percentages of the different labelled molecules as a function of plasma power for a
fixed flow of reactants (9 sccm), or as a function of the total flow of reactants at
constant power (9 ± 1 W).

Figure 2. (a) Series of mass spectra recorded for plasma activated NH3+D2 mixtures at
increasing powers from 9 to 23 W (total flow fixed at 9 sccm). (b) Scheme showing the plasma
exchange processes leading to the formation of ammonia and hydrogen molecules labelled
with deuterium. (c) Histogram from (a), showing the percentage of the different deuterium
and ammonia labelled molecules as a function of plasma power. (d) Idem as a function of total
flow (power fixed at 9 ± 1 W). The experiments were carried out at a frequency of 5 kHz and a
variable voltage amplitude from 2.5 to 4 kV.

A first evidence regarding these column plots is that NH3 and D2 progressively decrease
in the outlet gas mixture because they progressively exchange their constituent H/D
atoms according to processes such as those represented in (E8). According to Figures
2(c) and (d) these exchange reactions are more frequent when increasing power and
residence time (i.e., decreasing the reactant flow) and may produce up to 60%
reduction of D2 molecules in the total amount of hydrogen in the outlet mixture. In
next sections, analyzing the evolution of ternary N2+D2+NH3 mixtures, we will show
that plasma energy may induce exchange processes and no net
synthesis/decomposition of ammonia.
In the present experiment with NH3+D2 we found a little but progressive increase with
power in the m/z=28 peak intensity (see Supporting Information 5). This evidence,
joined to the observed decrease in the amount of ammonia molecules between inlet
and outlet flows proved that a fraction of ammonia was effectively decomposed into
nitrogen and hydrogen. Table 2 summarizes the results for various experimental
conditions. Data include the NH3 decomposition yield (i.e., according to (E3)) and the
partition between the decomposed NH3 molecules leading to N2 (and hydrogen) and
the NH3 molecules that have exchanged H by D. In other words, this partition
quantifies the ammonia molecules decomposed into hydrogen and N2 (fourth column)
or those that have undergone H by D exchange (fifth column).
Table 2. Evolution of the decomposition yield of ammonia and estimation of fractions of
ammonia decomposed molecules and H--D exchange processes as a function of ammonia flow
rate and plasma power

NH3 flow rate Power DY-NH3 Fraction of Fraction of reacting NH3

(sccm) (±1 W) (%) decomposed NH3 molecules that have
molecules exchanged H by D
9 0.24 0.03 0.97
9 17 8.9 0.40 0.60
23 17 0.49 0.51
5 9 12 0.47 0.53
3 5 11 0.58 0.42

Moreover, this table shows that both ammonia decomposition yield and fraction of
NH3 molecules decomposed into N2 and hydrogen (HD may be formed through
secondary processes) increase with power and residence time, while the fraction of
ammonia molecules that undergo inefficient H--D exchanges follows an opposite
behavior. From a practical point of view, these opposed tendencies show that
operating packed-bed plasmas at high input powers favor the decomposition of the
ammonia into hydrogen and nitrogen with respect to hydrogen exchange reactions.

Isotopic exchange events under steady state conditions

Mixtures Nitrogen + Hydrogen + Ammonia represent the typical composition of outlet
gases during ammonia synthesis/decomposition experiments. To quantitatively
estimate to which extent hydrogen exchange and similar intermediate processes waste
energy without contributing to the formation/decomposition of ammonia we studied a
ternary inlet mixture N2+D2+NH3 with adjusted molecular ratios such that no net
formation/depletion of nitrogen occurs after plasma ignition, i.e., the inlet ratio
N2/NH3 is the same than the outlet ratio N2/(NH3+ NDH2+ND2H+ND3). Such conditions
were found for inlet mixtures with a N2:D2 constant ratio of 1:3, a NH3 constant flow of
3.7 sccm and total flows of 15, 27 and 38 sccm.

The bar diagrams in Figure 3 show the partitions of the different labelled molecules in
each compound (i.e. hydrogen or ammonia), either as a function of the power or for
three total flows of reactants. These latter conditions were selected to check the
influence of residence time in the exchange processes. The diagrams indicate that the
relative concentrations of NDH2 and ND2H, as well as hints of ND3, increase with the
applied power (Figure 3(a)) and for smaller flow rates (Figure 3(b)). A similar tendency
was found for the evolution of H2 and HD molecules.

Figure 3. Percentages of the different labelled molecules in hydrogen and ammonia detected
for the ternary reactants mixture NH3+D2+N2 as a function of (a) the applied power (for V=2.5
kV, flow rate of 15 sccm and frequency between 1 and 5 kHz) and (b) the total input flow of
reactants (i.e., 38, 27 and 15 sccm) for a power of 11 W (2.5 kV, 5 kHz).

These results confirm that, under the investigated conditions, H--D exchange reactions
are massively taken place with zero energetic efficiency for the
production/decomposition of ammonia.

To more precisely assess how plasma energy is consumed in promoting plasma

exchange reactions we apply the reaction events concept proposed in the
experimental section. Figure 4 shows representations of the evolution of the number
of events for ammonia and hydrogen as a function of the total flow rate for an applied
power of 11 W (same conditions than for the histogram in Figure 3(b)). In these plots,
overall data are also provided for hydrogen (i.e., sum of events associated to HD and
H2), ammonia (i.e., sum of events associated to NDH2, ND2H and ND3) and the sum of
these two (TRE, see (E-7)). Clearly, there is a progressive decrease in the number of
events when the total flow rate increases (i.e. residence time decreases). Similarly, a
progressive increase in the number of events was found when increasing the plasma
power (see Supporting Information 6 showing the reaction events dependence on
power). Interestingly, Figure 4 also shows that hydrogen is more likely to undergo
exchange events than ammonia. From a practical point of view, this evidence suggests
that a suitable strategy to increase the energy efficiency for the synthesis of ammonia
would consist of properly adjusting the hydrogen flow, while if the objective is to
decompose ammonia, produced hydrogen should be removed from reaction medium
immediately after its formation (e.g., using selective diffusion membranes).47

Figure 4. Representation of the number of events for (a) ammonia and (b) hydrogen molecules
detected in the outlet mixture during the analysis of the stationary mixture NH3+D2+N2 as a
function of total flow rate (applied power of 11 ± 1W).

Intermediate plasma species during plasma synthesis/decomposition of

ammonia

The isotopic exchange reactions must involve different excited plasma species. Typical
OES spectra as a function of power for the NH3+D2 mixture above are shown in Figure
5(a), where the emission lines can be attributed to N2* and NH* (ND*) species.48 This
assignment relies on similar plasma investigations where peaks between 290-385 nm
were attributed to the second positive system of N2* species [𝐶 3 Π → 𝐵 3 Π], and the
peak at 336 nm to NH* species.24,25 Interestingly, unlike the spectra recorded for
mixtures N2+H2,24,25 only hints of a peak at 391.4 nm usually attributed to N2+ species
[𝐵 2 Σ𝑢+ → 𝑋 2 Σ𝑔+ ] can be detected in the spectrum taken at maximum power. Also, a
slightly increase in the spectral background at lower wavelengths observed in this high
power spectrum can be related with the presence of excited deuterium (hydrogen)
species in the plasma gas (see the background in Figure 5(a) at 23 W and Supporting
Information 7).49

Figure 5. (a) Series of OES recorded for a NH3+D2 plasma mixture (9 sccm) as a function of the
applied power. (b) Plot of the percentage of ammonia molecules containing deuterium (data
taken from Figure 3(c)) against the intensity of the 336-337 band (associated to NH*) for the
indicated applied power.

The progressive formation of NH* (ND*) species as the power increases and its
correlation with the percentage of labelled molecules NDH2 and ND2H (c.f., Figure 3(b))
suggest that D exchange reactions are involved in the formation of NH* (ND*) and
NH2* (ND2* or NDH*) intermediate radicals via processes E9-E13: 13

NH3 + e-  NH* + 2H* (E9)

NH3 + e-  NH2* + H* (E10)

Once NH* and NH2* radicals are formed it is likely their interaction with D2 according
to:

NH* + D2  NDH* + D* (E11)

NH2* + D2  NDH2 + D* (E12)

or, in a second step:

NDH* + D2  ND2H +D* (E13)

Since OES detects line emissions from NH*(ND*) but not from NH2* (ND2*, NDH*), this
suggests a higher reactivity and a shorter life time for NH2* species; in other words,
that reactions (E10, E12 and E13) are very fast and drastically contribute to lower or
remove these intermediate species from the plasma. Previous investigations in other
type of plasmas as inductively coupled radiofrequency discharges50 or plasma jets, 51
also support a higher stability of NH* species.

In addition, D* radicals formed by electron impact dissociation:

D2 + e-  2 D* (E14)

are expected to react with NH3 (NDH2, ND2H) molecules and contribute to isotopic
exchange processes such as:

NH3 + D*  NDH2 + H* (E15)

The drift in the spectral background in Figure 5(a) is an indirect evidence of deuterium
(hydrogen) radicals formation.49 In this figure, it is noteworthy the absence of spectral
features around 391.4 and 427.8 nm due to N2+ species. The formation of this
molecular ion has been reported in previous works dedicated to synthesis of ammonia
in nitrogen rich conditions.24,25 Their absence in Figure 5 is due to the small
concentration of nitrogen formed and the aforementioned low electron impact
ionization cross section of N2.46

Surface vs. plasma intermediate reactions

A key feature in plasma and plasma catalysis reactions is to determine the involvement
of plasma-surface processes. Although evidences of surface activated processes exist
for low pressure plasmas52 and are a common assumption in plasma-catalysis,53,54
there are few direct experimental evidences confirming that plasma-surface processes
participate in the reaction.36 Herein, we have proved that surface processes actively
participate in the ammonia synthesis and decomposition reactions.

In a first experiment, using a mixture N2+D2 (flow ratio 1:3), we found that besides the
expected ND3 molecules (i.e. equivalent to NH3), labeled molecules such as NH3, NDH2
and ND2H (together with HD) were detected by mass spectrometry and FT-IR analysis
in the outlet flow. The series of mass spectra in Figure 6(a) taken before and after
igniting the plasma (5kHz; 3.5 and 4 kV) clearly show the formation of these labelled
molecules. Analogously, the FT-IR spectra in Figure 6(b) shows the appearance of
bands at 2420, 2505 and 2558 cm-1, attributed to labelled species of ammonia55–57 and
whose intensity increases with the applied power.
Figure 6. (a) QMS spectra taken at increasing powers (total flow rate 12 sccm). (b) Idem, FT-IR
spectra of the outlet gas flow recorded simultaneously. The experiments were carried out at a
frequency of 5 kHz and voltage amplitudes of 3.5 and 4 kV.

In this experiment, we also found that the partition of labelled molecules changed with
the total flow of gases (c.f., Table 3). For the lowest flow the concentration of H
containing molecules was higher, showing that H isotopes from an unknown source
inside the reactor intervene in the ammonia synthesis reaction. We propose that these
H atoms proceed from the surface and bulk of ferroelectric pellets placed in the inter-
electrode space.
Table 3. Percentages of the different ammonia deuterium-labelled molecules detected one
hour after igniting the plasma (applied power of 42 W) for experiments carried out for two
input flow rates of N2+ D2.

Total flow rate of N2+D2 12 sccm 34 sccm

Molecular Specie Relative (%) Relative (%)
ND3 7 60
ND2H 22 28
NDH2 42 1
NH3 29 11

Another experiment complementing the previous one was carried out as follows. First,
the ferroelectric pellets were exposed for 3 hours to a deuterium plasma (1.5 sccm of
pure D2 at 4 kHz and 3.7 kV). During this pre-treatment mass spectrometry analysis
showed the formation of HD molecules (see Supporting Information 8), indicating the
existence of a H--D exchange process when PZT pellets were exposed to a plasma of
pure D2. This experiment also suggested that there were H atoms incorporated in the
pellets before plasma ignition. The experiment continued with the ignition of a plasma
of 3 sccm of N2, followed by that of a N2+H2 mixture. Supporting information S9 (figure
S9(a)) shows that no traces of either HD or D2 molecules were detected when exposing
the D2 plasma treated PZT pellets to a N2 plasma.

However, when shortly thereafter a N2+H2 plasma was ignited again (total flow rate of
34 sccm; 5 kHz, 3.3 and 4.1 kV), NDH2, and ND2H molecules were detected by mass
spectroscopy (see Figure S9(b) in Supporting information S9). These findings confirm
the involvement of deuterium, likely incorporated in the ferroelectric pellets, in the
generation D-labelled ammonia molecules and suggest that i) a source of hydrogen
exists in the PZT pellets used for plasma ammonia reactions, ii) this hydrogen can be
mobilized when the pellets are exposed to a plasma containing H2 or D2 and iii) H/D
exchange reactions involving ammonia molecules may take place for N2 +H2(D2)
plasmas.

A condition enabling these three working hypotheses is the incorporation of

deuterium/hydrogen into the PZT pellets when they are exposed to a plasma
containing hydrogen. Under these conditions the direct interaction of PZT with H*(D*)
radicals and, possibly, other excited species of hydrogen, should promote the
incorporation of H(D) onto the surface and likely also the interior of the PZT pellets.
Large amounts of atomic hydrogen incorporation is known to occur in PZT treated
either thermally with hydrogen or activated electrochemically with a Pt electrode in a
water solution.58,59 Similarly to the incorporation of hydrogen atoms in these
experiments, we assume that activated hydrogen (deuterium) plasma atoms will
readily interact with PZT and become incorporated both onto its surface and in its
bulk. According to different works in literature, the capacity of PZT to incorporate
hydrogen is very high and can amount to one atom per structural octahedral unit of its
structure (maximum 1H:1Pb ratio).60,61

Therefore, assuming the availability of H(D) atoms incorporated in the PZT after
hydrogen plasma activation (see Supporting Information S10 for a rough estimate of
H/D incorporated in the pellets), we propose that surface reaction processes of the
type E16-E18 take place during ammonia synthesis/decomposition reactions
(equations written for the N2+D2 experiment):

ND* (plasma) + -H (surf.)  NH* (plasma) + -D (surf.) (E16)

ND* (plasma) + -H (surf.)  NDH* (plasma) (E17)

NDH* (plasma) + -H(surf.)  NDH2 (gas) (E18)

Where long living ND* species interact with the surface and may take or exchange D by
H atoms from the PZT. Note that formation of NH* species by direct interaction of long
living N2* or N2+ plasma species with PZT must be discarded because no ammonia was
detected when pellets were exposed to a plasma of pure nitrogen (see Supporting
Information S9(a)).

In summary, based on the OES spectra and deuterium exchange reactions, we propose
that, in the plasma phase, the most active (and short living) NH2* radical participates
actively in the plasma synthesis/decomposition of ammonia (and laterally in H(D)
exchange processes). In addition, we also propose that the interaction of longer living
ND* species and the PZT-H rich surface may yield NH* (or the reverse reaction
rendering ND*), NDH* or NDH2 species and contribute to the observed isotopic
exchange processes.

CONCLUSIONS
The series of experiments carried out in the present work have provided valuable
information regarding the ammonia plasma synthesis and decomposition reactions
and other parallel exchange processes that do not give rise to valuable products. We
have proved that, plasma promoted decomposition of ammonia in a packed-bed
reactor can be an energetically efficient process, provided that reaction mechanism
and operating conditions are properly handled and controlled. To this end, isotopic
exchange experiments using D2 as labelling molecule have shown that besides main
reaction pathways, there is panoply of intermediate hydrogen exchange reactions that
consume energy but are energetically inefficient regarding the formation of either
ammonia or hydrogen, depending on the desired final product. Valuable information
regarding operating conditions, reactant flows, selective separation of given reactants
or products, etc. can be deduced from isotope exchange experiments, thus
contributing to improve reaction yields and energy efficiencies.
In addition, we have proved that the combined use of plasma diagnosis and isotopic
exchange constitutes a powerful methodology to unravel plasma reaction
mechanisms. In this line, we have shown that plasma-surface interaction processes
directly intervene in the ammonia synthesis/decomposition reactions. We have arrived
to this conclusion verifying that hydrogen incorporated in the PZT pellets may appear
in the outlet gases as resulting from surface exchange processes involving
intermediate N-H(D) plasma species.

Acknowledgements
We thank EU-FEDER funds and the MINECO (projects MAT2016-79866-R and CSIC
201860E050) and Junta de Andalucía (project P12-2265 MO and US-1263142) for
financial support.
Supporting Information. 1. Schematic of the reactor and experimental setup. 2.
Electrical diagnosis. 3. Determination of the partition of labelled molecules 4. Examples
of inefficient intermediate reactions. 5. Formation of N2 from a plasma of NH3+D2. 6.
Reaction events as a function of power (ternary mixture N2+NH3+D2). 7. Evidence of
the presence of excited species of deuterium in a N2+D2 mixture. 8. Formation of HD
and H2 molecules during D2 plasma activation. 9. QMS analysis. Involvement of the PZT
in the reaction processes. 10. Estimation of the amount of H/D incorporated in the PZT
pellets.

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 TABLE OF CONTENTS
Isotope labelling identification of discharge and surface reaction mechanisms lessening
the efficiencies of plasma-driven hydrogen or ammonia synthesis