Hydrogen Production Induced by A Discharge Over Water

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C: Energy Conversion and Storage; Energy and Charge Transport

Electrosynthesis via Plasma Electrochemistry: Generalist Dynamical
Model to Explain Hydrogen Production Induced by a Discharge over Water
Andressa Mota-Lima, Jailton Ferreira do Nascimento, Osvaldo
Chiavone-Filho, and Claudio Augusto Oller Nascimento
J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.9b04777 • Publication Date (Web): 12 Aug 2019
Downloaded from pubs.acs.org on August 13, 2019
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Page 1 of 58 The Journal of Physical Chemistry
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Electrosynthesis via Plasma Electrochemistry: Generalist Dynamical
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6 Model to Explain Hydrogen Production Induced by a Discharge over
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9 Water
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11 Andressa Mota–Lima,1* Jailton Ferreira do Nascimento,2 Osvaldo Chiavone–Filho3 and
12
Claudio Augusto Oller Nascimento1
13
14
15 1 Department of Chemical Engineering, Polytechnic School, University of São Paulo -
16 USP, Avenue Prof. Luciano Gualberto 380, São Paulo-SP, 05508-010, Brazil
17
18 2 PETROBRAS – Petróleo Brasileiro S.A., CENPES – Research and Development
19 Center, PDDP/TPP, Avenue Horácio Macedo 950 – Cidade Universitária, Ilha do
20 Fundão, Rio de Janeiro-RJ, 21941-915, Brazil
21
22 3 Federal University of Rio Grande do Norte - UFRN, Department of Chemical
23 Engineering, Campus Universitário, Lagoa Nova, Natal-RN, 59078-970, Brazil.
24
25 *mota@usp.br
26
27 Abstract. Electrosynthesis via electrochemical plasma, a discharge over the surface of
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29
liquid water (or plasma cathode), may offer an unprecedented route of synthesis for
30
chemicals and (wind-) solar-fuels. Describing the physical chemical events underneath
31
32
33
plasma/liquid interface (PLI) on a theoretical basis is crucial for enabling a rational
34 designing of chemical synthesis. To address this problem, this work proposes a generalist
35
36 dynamical model for the nano-reactor, a fraction of nano-liters localized beneath the PLI
37
38 ―
that features substantially high concentration of hydrated electrons (𝑒𝑎𝑞 ), and it screens
39
40 chemical reaction networks (CRN) related to the synthesis of hydrogen, a model
41
42 electrosynthesis process. The computational results elucidate two major routes for
43
44 hydrogen production: (a) in very alkaline media, the water reduction via self-
45 ―
recombination of 𝑒𝑎𝑞 ―
[2 𝑒𝑎𝑞 + 2𝐻2𝑂 → 𝐻2 + 2 𝑂𝐻 ― ] consumes the majority of 𝑒𝑎𝑞
―
,
46
47 ―
whereas (b) in very acid media, 𝑒𝑎𝑞 +
is majorly scavenger by the ion 𝐻𝑎𝑞 , generating an
48
49 abnormally high concentration of the radical H∙, a precursor for gaseous hydrogen.
50
51 Additionally, two scenarios are disadvantageous for synthesizing H2. Side reactions with
52
53 aqueous oxygen and aqueous radical ∙OH leads to substantial production of 𝑂2― and OH-
54
55 , respectively. Without loss of generality, the dynamical model proposed in this work is
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57 a powerful theoretical frame for understanding and predicting a variety of plasma-
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59
induced CRNs, assisting to advance the emerging field of plasma electrochemistry.
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The Journal of Physical Chemistry Page 2 of 58
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3 1. INTRODUCTION
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6 Since ever, the potential of chemical synthesis based on a cold plasma has been deposited
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8 on the repeatedly reports about hydrogen production for the discharges either over 1 or in
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10 2-4
11 the liquid water, being such configuration termed herein as electrochemical plasma.
12
13 Mainly because both the plasma and the water connect along a single conductive path in
14
15 between the two metallic terminals of the high-voltage power supply, so the plasma itself
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17
18
acts as an electrochemical cathode. If otherwise, the plasma was the sole conductor in
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20 between the two metallic terminals, the gas injection (jet effect) is required to spread the
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22 discharge over the liquid, promoting the discharge/liquid contact that is termed
23
24
25
plasma/liquid interface (PLI), and such configuration said torch-like plasma. Both the
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28 electrochemical plasma and the torch-like plasma are able to synthetize chemicals,
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31
however in different phases (see Glossary on the Supporting Information for detailed
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33 definitions on those configurations). The plasma effluent in contact with water enriches
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35 the liquid phase with a variety of radicals, 5-8 and despite inducing both oxidation 2,9,10
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38 and radical initiator reactions 11 in the liquid phase, hydrogen production for a torch-like
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41
configuration develops in the plasma phase, as result of either the reforming reaction of
42
hydrocarbon 12-19 or the splitting of water. 4,20-26 Contrariwise, the hydrogen production
43
44
45 steered by an electrochemical discharge is mostly developed in the liquid phase. Aiming
46
47
at elucidating the major facts, the literature spotted in this introduction directs the reader
48
49
50 to the theoretical frame hereby proposed, instead of offering an extensive review.
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52 More recently, the successful reduction of aqueous carbon dioxide to oxalate plus
53
54 formic acid 27 by an electrochemical discharge renewed the belief on such
55
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57 electrosynthesis via electrochemical plasma. It is largely know that a variety of
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59 electrochemical discharges (glow discharge in and over water, jet discharge over water
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1
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3 etc.), or plasma electrolysis as named by the plasma community, are able to reduce a
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6
broad spectrum of aqueous cations such as Cu+ and Pt+ to mention a few. 28 In the recent
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8 years, reduction of cations such as Ag+ 29,30 and Au+31-35 was systematically employed to
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10 mimetically gain information on the mechanism of reduction-like reactions due to the
11
12
13 plasma-liquid interaction. Despite all experimental efforts, the lack of a theoretical frame
14
15
16
about the physical chemical events within the liquid phase directed by the plasma-liquid
17
18
19 interaction greatly limits our ability to make rational design on the chemical routes.
20
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22 Aiming at clarifying possible ways of designing routes for chemical synthesis, this work
23
24 proposes a dynamical model for a confined region in the liquid, describing the physical
25
26 chemical events in it. The mechanism of hydrogen production is unveiled along the task
27
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29 of understanding the chemical route related to its synthesis. For this end, the synthesis of
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31 hydrogen acts as a model process for plasma-based electrosynthesis steered by an
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34 electrochemical discharge.
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36
Figure 1 outlines the PLI, emphasizing the spatial position of the reactor termed nano-
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40
reactor because its volume has a fraction of 10-9 L when pondering differences in the time
41
42 scales for both chemical and diffusion events 36 ―
related to the hydrated electrons (𝑒𝑎𝑞 ).
43
44
45 The electrosynthesis develops mostly within such nano-reactor. An uncontestable proof
46
47
―
48 of a substantially high concentration of 𝑒𝑎𝑞 spatially confined in a region this work terms
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51
nano-reactor was recently accomplished using a spectroscopic method 37. This finding
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53 ―
54 settles 𝑒𝑎𝑞 as the first and most important reactant within the nano-reactor. The
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identification of other essential reactants (essential chemical variables) in the context of
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59 plasma-driven reactions lays on whether their concentrations are near to the order of
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1
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3 ―
magnitude for the 𝑒𝑎𝑞 concentration. An inspection on the radiolysis-based reactions aids
4
5
6 to identify other possible reactants whose classification is found on the second section of
7
8
9 this work, named empirical theoretical basis.
10
11 This work make ample use of the chemical reaction networks (CRN) to propose
12
13 chemical dynamic models. Mainly because the electrosynthesis via electrochemical
14
15 ―
16 plasma develops under a periodic perturbation on the 𝑒𝑎𝑞 concentration within the nano-
17
18
19 reactor. If otherwise, key information would be lose by analyzing the rate law of reactions
20
21 individually or by evaluating the pre-exponential rate constants comparatively.
22
23 Advantageously, CRN-based models deal with the full set of reactions all at once,
24
25
26 treating the chemical mechanism as a dynamical system 38-40. This work engages on a
27
28
29 screening of CRNs by assembling elementary reactions from radiation chemistry of water
30
41. Each experimental scenario of discharge forges its own CRN. The chemical
31
32
33 mechanisms are conveniently represented in so-called network diagram (or set-graph
34
35 38
diagrams) in which the species symbols are connected by arrows according to the
36
37
38 stoichiometric constraints imposed by each reaction. In a network diagram, the number
39
40 of barbs on an arrow pointing to a product indicates the stoichiometric coefficient of this
41
42 product in the respective reaction, while the number of left feathers indicates the
43
44
45 stoichiometric exponent of the reactant. By convention no feathers are shown when the
46
47 stoichiometric and kinetic coefficient of a reactant are both unity. Accurately, the graph
48
49 diagrams without cycles (autocatalytic reactions) are called trees, which differentiate by
50
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52 means of the nomenclature the stability of the network, i.e. the dynamic system associated
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54 with the trees allows only for steady stationary states. The plasma-induced CRNs-trees
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56
―
57 are stable networks despite driven by a periodical perturbation on the 𝑒𝑎𝑞 concentration.
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1
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3 This work unravel CRNs for two major scenarios. The first one considers a discharge
4
5
6
in noble gas over water enriched with either acid, salt or hidroxide, revealing the core
7
8 CRN related to the hydrogen synthesis, cf. section 3.1. The second major scenario depicts
9
10 ―
the drawbacks for hydrogen synthesis in presence of species acting like scavenger of 𝑒𝑎𝑞 .
11
12
13 For examples, the plasma-synthetized species such as nitrate (produced via Birkeland-
14
15
16 Eyde process by discharge over mixture of N2 and O2 gases) and radical ∙OH (produced
17
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19 by discharge over humid gas) are treated in sections 3.1.3 and 3.2, respectively, together
20
21 with the soluble gases (oxygen) treated in sections 3.3. All the scenarios studied herein
22
23 employs the electrical data found in the work of Urabe et al.42 that was employed as a
24
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26 model standard for a pulsed DC-voltage.
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29 2. THEORY
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2.1 Radiolysis–based reactions steered by electrochemical plasma
33
34
35
―
36 In this section, all radiolysis-related reactions involved with 𝑒𝑎𝑞 are gathered. Gonzalez
37
38 ―
et al. 36 overestimates that the instantaneous 𝑒𝑎𝑞 concentration is about 0.6 mol L-1 within
39
40 a time scale as narrow as 1 ns (10-9 s) when considering the volume of some 10-9 Liters.
41
42 ―
Such considerable concentration sets 𝑒𝑎𝑞 as the first and most important reactant, leading
43
44 to a substantial production of gaseous hydrogen
45
46 ―
2 𝑒𝑎𝑞 + 2𝐻2𝑂→𝐻2 + 2𝑂𝐻 ― (1), k1 = 6 × 109 L mol−1 s−1
47
48
49 in connection to a local production of OH-. Reaction 1 is also known as second order
50
51
52 recombination reaction. Over time, it leads to the basification of the liquid body. A strong
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54 signal of validation on this path lays on the findings of Witzke et al. 1 that had detected
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56 gaseous hydrogen into the gaseous plasma effluents, via mass spectroscopy, while
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59 simultaneously observing a global rise on the pH of the liquid body. An incontestable
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1
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3 final validation, however, for this pathway termed herein as via–Self recombination, or
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6
via–Self for short, would be accomplished by simultaneously quantifying the
7
8 stoichiometry between moles of H2, OH- and 𝑒𝑎𝑞
―
. This will be the direction exploit
9
10
11 throughout this work. If the hydrogen production follows strictly reactions 1, the moles
12
13 of H2, OH- and 𝑒𝑎𝑞
―
has to follow a ratio 1:2:2. All other pathways competes with the via–
14
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16 Self for 𝑒𝑎𝑞
―
because the hydrated electron reduces a scavenger (S) species, also in liquid
17
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19 phase, via scavenger-like reaction, or via–S:
20
21 ―
𝑒𝑎𝑞 + (𝑆𝑎)𝑎𝑞→(𝑆𝑎 ― )𝑎𝑞 . (2), k2 ~ 1010 L mol−1 s−1
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24 Several aqueous ions/species takes over the scavenger role. This work targets three
25
26 major classes of scavengers that relates to: (a) the plasma-synthetized species, (b) the
27
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29 supporting electrolyte, a chemical substance whose function is to increases the ionic
30
31 conduction of the liquid electrolyte; and (c) the gases soluble in aqueous phase.
32
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34 Among the scavenger related to the plasma-synthetized species are hydronium
35
36
37 radical (•H), hydroxyl radical (•OH), 𝐻2𝑂2, 𝑁𝑂3― and 𝑁𝑂2― . The former three must be
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39 considered for a humid-based discharge, whereas the latter two for an air-based
40
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42 discharge. Radical species are produced in plasma phase and invariably uptaken by the
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liquid phase 5, thus being unavoidable their presence in the nano–reactor. This work
46
47 targets specifically the humid-plasma-induced species such as •OH radical and 𝐻2𝑂2
48
49
50 that consume 𝑒𝑎𝑞
―
while producing OH-
51
52
53 ―
𝑒𝑎𝑞 + ( ∙ 𝑂𝐻)𝑎𝑞→𝑂𝐻 ― (3), k3 = 3.0×1010 L mol−1 s−1
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―
𝑒𝑎𝑞 + (𝐻2𝑂2)𝑎𝑞→( ∙ 𝑂𝐻)𝑎𝑞 + 𝑂𝐻 ― . (4), k4 = 1.1×1010 L mol−1 s−1
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1
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3 which could not only decreases the yields of hydrogen production but also modifying the
4
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6
stoichiometric proportion between the global molar production of OH– and H2.
7
8 Additionally, the nitrate synthetized via the well-known Birkeland-Eyde process 43 for
9
10
11 an air-based discharge is also considered as a possible scenario. Even if not intentionally
12
13 added to the bulk liquid as 𝐻𝑁𝑂3, nitrate could be uptake by the liquid from the
14
15
16 plasma/gas phase as reported elsewhere 44. The nitrate is reduced by 𝑒𝑎𝑞
―
via
17
18 ―
𝑒𝑎𝑞 + 𝑁𝑂3 ― →𝑁𝑂32 ― . (5), k5 = 9.7×109 L mol−1 s−1
19
20
21 Now on, the scavenger related to the supporting electrolyte are treated. This work
22
23 deals solely with the hydroniums ions (H+) because it is invariable present in pure water.
24
25 The hydroniums ions provide an additional route for H2 production based on two-steps
26
27
28
mechanism 45
29
+
30
―
𝑒𝑎𝑞 + 𝐻𝑎𝑞 →(𝐻 ∙ )𝑎𝑞 (6), k6 = 2.3×1010 L mol−1 s−1
31
32
33
―
𝑒𝑎𝑞 + (𝐻 ∙ )𝑎𝑞 + 𝐻2𝑂→𝐻2 + 𝑂𝐻 ― (7), k7 = 2.5×1010 L mol−1 s−1
34
35 2(𝐻 ∙ )𝑎𝑞→𝐻2 (8), k8 = 1.0×1010 L mol−1 s−1
36
37
―
38 Finally, to complete the description for the mechanism involving 𝑒𝑎𝑞 as reactant in
39
40 the nano–reactor, the scavenger related to dissoluble gases are hereby considered. The
41
42
43 water body is a great reservoir for gases like O2 and CO2 that in SPT conditions are in
44
45 concentrations around 270.0 and 13.6 10-6 mol L-1 respectively. Such values of
46
47
48 scavenger concentration must not be disregarded. For simplicity, only one gas-based
49
50 scavenger is considered, the dissolved oxygen, which introduces the following cascade
51
52
53
of pathways
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55
―
𝑒𝑎𝑞 + (𝑂2)𝑎𝑞→(𝑂2 ― )𝑎𝑞 (9), k9 = 1.9×1010 L mol−1 s−1
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57
58
―
𝑒𝑎𝑞 + (𝑂2 ― )𝑎𝑞→(𝐻𝑂2 ― )𝑎𝑞 + 𝑂𝐻 ― (10), k10 = 2.5×1010 L mol−1 s−1
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1
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3 ―
𝑒𝑎𝑞 + (𝐻𝑂2 ― )𝑎𝑞→( ∙ 𝑂𝐻)𝑎𝑞 + 𝑂𝐻 ― . (11), k11 = 2.5×1010 L mol−1 s−1
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2.2 Defining physical boundaries, transportation rates (𝛤) in the liquid phase
15 and rates for both chemical (𝑞𝑆) and electrical (𝑞𝑒)interactions at PLI
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17
18
19 The first and most important physical boundary for modelling the plasma-induced
20
21 reactions in liquid phase is the definition of the reactor volume, a crucial parameter for
22
23
defining the local concentration of the reactants. Assuming full volume of the liquid body
24
25
26 as a reactor is unrealistic because the discharge over the liquid is a localized event,
27
28 meaning that the chemical events relaxes at shorter time scale than does the transportation
29
30 events. Defining the conceptual boundaries of the reactor is a vital task. The contact area
31
32
33 of the PLI is around a thousand times smaller than the area of gas/liquid contact (for more
34
―
35 details see table S2).The primary plasma-based reactant, the 𝑒𝑎𝑞 , penetrates only a few
36
37 nanometers 37 into the liquid phase. Pondering all, the volume related to the nano-reactor
38
39
40 rarely overpasses some 10-9 liters.
41
42
43 Figure 1 depicts both the relative position between the two metallic terminals with
44
45 respect to the water surface and, by arrows, the flows of species through the boundaries
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47
48
of the nano-reactor as result of either transport events in liquid phase (term 𝛤) or plasma-
49
50 liquid interaction (term 𝒒). The plasma phase takes over the role of working electrode
51
52
53 (WE) whereas the counterpart metallic terminal acts as the counter electrode (CE). In the
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55 configuration depicted in figure 1, a net current of charge flow through plasma and liquid
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57 phase with the same magnitude, which is a prerequisite to classify the cold plasma as
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1
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3 electrical constriction exists for a PLI generated by a torch-like plasma, being the
4
5
6
interaction plasma/liquid ordinarily governed by henry law. Conversely, an electrified
7
8 PLI sets very clear boundary conditions for the electrical charge transportation through
9
10 the PLI, the PLI is an electrical element subordinated to the Kirchhoff’s current law. Such
11
12
condition allows to connect the electrical current (J), gauged somewhere in electrical
13
14
15 section between the power supply and the plasma, to the electrical current flowing
16
17 throughout the PLI. For a cathodic discharge, the division of J by the constant of Faraday
18
19 yields the rate of ballistic electrons (∆𝑛𝑒) that are injected into the nano-reactor per unit
20
21
22 of time (∆𝑡). The term 𝒒𝒆 is defined as the release rate of ballistic electrons into the nano-
23
24 reactor
25
26 ∆𝑛𝑒 𝐽
27 𝒒𝒆 ≡ ∆𝑡 = 96485. (12)
28
29
30
The ballistic electrons transforms into hydrated electrons after injection, increasing
31
―
32 instantaneously the local concentration of 𝑒𝑎𝑞 , i. e. the concentration inside the nano-
33
34 reactor. The action of a localized increase on the concentration creates a gradient of
35
36
37
concentration between the nano-reactor and the bulk liquid, driving two major processes
38
39 in the liquid phase: the chemical reactions and the transportation. The chemical
40
41 phenomenon is captured by the function 𝑓𝐶𝑅𝑁 that will be discussed below, and the
42
43 ―
44 transportation of 𝑒𝑎𝑞 toward the bulk liquid develops via action of concentration gradient
45
46 (diffusion) and electrical gradient (electrical drift). The term 𝛤𝑒 encompasses all the
47
48 ―
natures of 𝑒𝑎𝑞 transportation. The arrows in figure 1 for the term 𝛤𝑒 assumes a single
49
50
―
51 direction because the concentration of 𝑒𝑎𝑞 is invariably always larger at the nano-reactor
52
53 than at the bulk liquid. By convention, the flow of species departing from the nano-reactor
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55
56
toward the bulk liquid ha a negative signal.
57
58 Only scavenger having high solubility into aqueous liquid will attain concentration
59
60 ―
reasonably near to the concentration of 𝑒𝑎𝑞 . The water is in abundance, therefore its

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1
2
3 concentration as reactant disregarded completely. If the scavenger is already part of the
4
5
6
liquid, its initial concentration in the nano-reactor will be considered equal to the
7
8 concentration of the bulk liquid. If otherwise, it will be zero as were the case for plasma-
9
10 induced scavenger, for instance nitrate and radical OH. Additionally, the injection rate of
11
12
13 plasma-induced scavenger into the nano-reactor is driven by the plasma-induced source
14
15
16
term, or 𝒒𝑺, that quantifies the positive variation on the moles of plasma-induced
17
18 scavenger (∆𝑛𝑆) into the nano-reactor per unit of time (∆𝑡)
19
20 ∆𝑛𝑆
21 𝒒𝑺 ≡ ∆𝑡
. (13)
22
23 The value of the plasma-induced scavenger source, 𝒒𝑺, is highly dependent on the
24
25
26 parameters (gas composition and flow) and nature (glow discharge, DBD etc) of the
27
28 plasma source. In this work, plasma-induced scavenger source 𝒒𝑺 is solved for three
29
30
31 scavengers, the radical ∙OH (𝒒𝑶𝑯) plus the Birkeland-Eyde products that includes both
32
33
34 H+ (𝒒𝑯 + ) and NO3- (𝒒𝑵𝑶𝟑), as listed in table 1. After uptake by the liquid, these
35
36
37 scavengers increase their local concentration and suffer both chemical reactions and
38
39 transportation toward bulk liquid. The term 𝛤𝑆 in figure 1 accounts for such transportation
40
41 of scavenger. In general, the scavenger transportation has a positive sign because the
42
43
44 specie departs from outside to inside the nano-reactor. The bulk liquid is the sources of
45
46 scavenger related to both the supporting electrolyte and the aqueous gases, once it has
47
48 high concentration of these scavengers. Exceptionally for scavengers synthetized in
49
50
51 plasma phase (radical ∙OH for instance), a negative sign for the term 𝛤𝑆 could be set,
52
53
54 once the concentration gradient has inverted direction.
55
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57
58 2.3 The generalist dynamical system
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1
2
3 A generic dynamic model to describe the temporal evolution for the concentration
4
5
6 of both 𝑒𝑎𝑞
―
,[𝑒 ― ], and scavenger, [𝑆], in the nano-reactor during a discharger is described
7
8
9 respectively by
10 ―
𝑑[𝑒𝑎𝑞 ] 1
11 = ― 𝑓𝐶𝑅𝑁 + 𝑉 𝑞𝑒 ― 𝛤𝑒, (14)
12 𝑑𝑡
13
𝑑[𝑆] 1
14 = ― 𝑓𝐶𝑅𝑁 + 𝑉 𝑞𝑠 ± 𝛤𝑆. (15)
𝑑𝑡
15
16
17 where the variation 𝑞𝑒 in equation 14 stands for release rate of ballistic electrons per
18
19 discharge that is essentially defined by the level of the current as already discussed in the
20
21
22
section 2.2; the variation 𝑞𝑆 in equation 15 stands for the uptake rate of the plasma-
23
24 induced scavenger by the liquid. Both 𝑞𝑒 and 𝑞𝑆 are continuous functions representing
25
26
source term in the differential equations 14 and 15, a plasma-induced term that is either
27
28
29 zero or positive. 𝑉 is the volume of the nano-reactor at the discharge onset, and i
30
31 ts variation during the discharge period (tp) is assumed neglectful. At last, the terms 𝛤𝑒
32
33 and 𝛤𝑆 stand for the rate of transportation of the main chemical reactants into/from the
34
35
36 nano-reactor. In this work, no transport event is considered, whether diffusion or
37
38
39 convection, thus leading to zero value for both 𝛤𝑆 and 𝛤𝑒.
40
41 The function 𝑓𝐶𝑅𝑁 encompasses the kinetic mechanism described by each CRN-tree.
42
43
44 Each independent chemical variable in the equations 14–15 counts contributions from
45
46
several pathways (i) contained in the CRN
47
48
49 𝑓𝐶𝑅𝑁 = ∑𝑖𝑘𝑖∏𝑗[𝑅𝑗]𝜅𝑖𝑗 (16)
50
51
52 where the Rj is the concentration of j-th reactant, 𝑘𝑖 is the coefficient rate for the i-th
53
54
55 reaction and 𝜅𝑖𝑗 stands for the stoichiometric coefficient for the reactant 𝑅𝑗 in the i-th
56
57 reaction. Each pathway contributes with one term known as the rate of reaction (𝑣𝑖),
58
59
60
𝑣𝑖 = 𝑘𝑖∏𝑗[𝑅𝑗]𝜅𝑖𝑗, (17)

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1
2
3 that is embedded into equation 16. The rate of reaction, 𝑣𝑖, express the law of mass action.
4
5
6 On the equations 14-15, the following independent variables are function of time
7
8
9 [𝑆 + ] = 𝑓(𝑡) and [𝑒𝑎𝑞
―
] = 𝑓(𝑡).
10
11 Equation 14-15 represents a generalist chemical dynamic model based on CNR tailored
12
13
14 under realistic boundary conditions. To access the temporal evolution of the independent
15
16
variables, the equation 14 and 15 are solved as linear system of ordinary differential
17
18
19 equations via interactive method carried out with Wolfram language (Wolfram
20
21 Mathematica). Table 01 displays the values of all parameters employed in the numerical
22
23 solution. The source term 𝑞𝑆 was estimated from several papers,5,36,46 and all the rate
24
25
coefficients were extract from elsewhere. 41,47The electrical data from Urabe et al. 42
26
27
28 enables to access a crucial parameter for the kinetic model, the release rate of ballistic
29
30 electrons (the term 𝑞𝑒). Furthermore, the global yields of the main products are computed
31
32
33 by
34
35 𝑑[𝑃]
= 𝑓𝑝𝐶𝑅𝑁. (18)
36 𝑑𝑡
37
38 The differential equation 18 refers to the time evolution for the concentration of a
39
40 given product, called P. Among the main products, P, of a given CRN are the gaseous
41
42
43 hydrogen (H2), OH- ions and reduced scavenger (Sa-), meaning that P={ H2, OH- and
44
45
46 Sa-}. The continuous function 𝑓𝑝𝐶𝑅𝑁 describes the temporal evolution of the concentration
47
48
49 of productions
50
51 𝜅𝑖𝑗
52
𝑓𝑝𝐶𝑅𝑁 = ∑𝑖𝜅𝑖𝑝𝑣𝑖 (19)
53
54 within the i-th balanced reaction in the CRN-tree. Differential equation 18 is defined as a
55
56
dependent variable because it is a linear combination of the chemical variables assigned
57
58
59 to the reactants, the independent variables. The equation 19 is a continuous function that
60

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1
2
3 connects the rate of formation of products to the rate of consumption of reactants
4
5
6
(equation 17) by multiplying the equation 17 by the stoichiometric coefficient of the j-th
7
8 reactant (𝜅𝑖𝑗) and simultaneously dividing it by the stoichiometric coefficient of the
9
10 product (𝜅𝑖𝑝) within the i-th balanced reaction in the CRN-tree.
11
12
13
14
15 3. RESULTS
16
17
18
19
3.1 Dry discharge over oxygen-free electrolyte
20
21
22 This section is subdivide in three sections to understand the CRNs when the discharge
23
24 over liquid occurs in dry gas phases and in a complete absence of oxygen solubilized into
25
26
27
aqueous phase. Such experimental condition imposes clear consequences to solve the
28
29 model in equation 14-15. First, there is no gas-phase source of scavenger, such as soluble
30
31
32 oxygen. Second, the absence of water vapor in the plasma phase suppresses from our
33
34 analysis both H2O2 and radicals •OH because of their negligible concentration relates to
35
36
37
a neglectful mass action of their scavenger-like behavior. Third, two cases related to the
38
39 plasma-synthetized species are considered: the air–based and the air–free plasma phase.
40
41
42 For air–based plasma, the Birkeland-Eyde process of nitrogen fixation 43 produces the
43
44
45 plasma-phase nitrite (𝑁𝑂3 ― ) that dissolves into the liquid body by means of the chemical
46
47
interaction in the surface between water and the plasma–effluents
48
49
50 3(𝑁𝑂2)𝑝𝑙𝑎𝑠𝑚𝑎 𝑒𝑓𝑓𝑙𝑢𝑒𝑛𝑡 + (𝐻2𝑂)𝑠𝑢𝑟𝑓𝑎𝑐𝑒→2𝐻 + 𝑎𝑞 + 2𝑁𝑂3 ― 𝑎𝑞 + 𝑁𝑂𝑔𝑎𝑠. (20)
51
52 The reaction 20 are associated with other fluid dynamic processes developed for a
53
54
55 discharge with jet effect 48. The air-based discharge imposes over the model 14–15 clear
56
57
58 constrains: (a) two nonzero plasma–induced sources of scavenger, i.e 𝑞𝑠→ 𝑞𝐻 and 𝑞𝑠→
59
60 𝑞𝑁𝑂3 where 𝑞𝐻 > 0 and 𝑞𝑁𝑂3 > 0; and, (b) the presence of at least two scavengers, the

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1
2
3
hydronium cation and the nitrite anion, 𝑆 = {𝐻 + 𝑎𝑛𝑑 𝑁𝑂3― }. Contrariwise, the air-free
4
5
6 plasma invalidates these conditions. At last, three supporting electrolytes are tested: HCl,
7
8
9 NaCl and NaOH. On doing so, the water pH moves respectively from acid, neutro to
10
11 basic, which manipulates the concentration of hydronium ion, a scavenger based on the
12
13 electrolyte.
14
15
16
17 3.1.1 Air-free discharge over either neutral (NaCl) or acid (HCl) aqueous electrolyte
18
19
20
21 In air-free dry discharge, the unique class of scavenger present in the nano-reactor
22
23
24 is the supporting electrolyte, and this section analyses two of them: HCl and NaCl. Either
25
26 Cl– or Na+ are inert as scavenger but the hydronium cation (H+) does activate the pathway
27
28 thought reaction 6 to 8. These reactions include the radical H• as an intermediate specie;
29
30
31 see the CNR-tree in figure 2. Such CRN-tree assembles reaction 1 plus 6–8, and the
32
33
34 associated dynamical system is depicted by the temporal evolution of the reactants, which
35
36 is accessed by
37
38 ―
39 𝑑𝑡 = ― {2𝑘1[𝑒𝑎𝑞
― ]2
+ 𝑘6[𝐻 + ][𝑒𝑎𝑞
―]
+ 𝑘7[ ∙ 𝐻][𝑒𝑎𝑞
―]
} + 𝑉 𝑞𝑒 , (21)
40
41 𝑑[𝐻 + ]
42 𝑑𝑡 = ― 𝑘6[𝐻 + ][𝑒𝑎𝑞
―]
, (22)
43
44 Whereas the intermediates species (radical H•) by
45
46 𝑑[ ∙ 𝐻]
47 𝑑𝑡 = 𝑘6[𝐻 + ][𝑒𝑎𝑞
―]
― {2𝑘8[ ∙ 𝐻]2 + 𝑘7[ ∙ 𝐻][𝑒𝑎𝑞
―
]} . (23)
48
49
50
51
The chemical dynamical system encompassed by the equations 21 to 23, when solved,
52
53 allows to access the temporal evolution for the products by
54
55 𝑑[𝐻2]
― 2
56 𝑑𝑡 = 𝑘8[ ∙ 𝐻]2 + 𝑘1[𝑒𝑎𝑞 ―
] + 𝑘7[ ∙ 𝐻][𝑒𝑎𝑞 ], (24)
57
58 𝑑[𝑂𝐻 ― ] ― 2
59 𝑑𝑡 = 2𝑘1[𝑒𝑎𝑞 ―
] + 𝑘7[ ∙ 𝐻][𝑒𝑎𝑞 ]. (25)
60

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1
2
3
Note that, in the CRN-tree from figure 2, there are four species among reactants and
4
5
6 intermediates, but only three are independent variables on the dynamical model in
7
8
9 equations 21-23. Each one of this equations describes the temporal evolution of the
10
11
12 concentrations of 𝑒𝑎𝑞
―
, H+ and •H. The water acting as reactant in reaction 1 is in
13
14 abundance and its concentrations does not vary over time into the nano-reactor, thus this
15
16
reactant disregarded as chemical variable. Note also that the temporal evolution of the
17
18
19 final products, accessed via equations 24-25, depends solely on two independent
20
21
22 variables, the concentration of 𝑒𝑎𝑞
―
and H•. Such comments implicates that (a) equations
23
24 21–23 are solved as linear system of differential equations via numerical methods; and,
25
26
27
(b) the temporal solutions for these three independent variables (concentrations of 𝑒𝑎𝑞
―
,
28
29 H+ and H•), employed to solve equations 24 and 25, the dependent equations. Figure 3
30
31 shows temporal solutions obtained by this procedure. Instead of molarity, this work also
32
33
34
considers the temporal evolution of products in terms of moles, known as yields. For this
35
36 reason, the temporal evolution of products obtained with equations 20 and 21 are
37
38 integrated over full period of discharge that is either 0.1 or 0.2 ms, and then multiplied by
39
40
𝑉. Figure 5 displays temporal solutions obtained by this procedure.
41
42
43 The concentration of hydronium ion is manipulated by the electrolyte pH. For 0.1
44
45 mol L-1 HCl, the electrolyte pH settles around 1 and [H+] equals 0.1 mol L-1. On the other
46
47
48 hand, pH around 7 is obtained with 0.1 mol L-1 NaCl, and [H+] equals 10-7 mol L-1. In
49
50
51 principle, the aqueous NaCl solution must have pH around 7, but in reality it has lower
52
53
54
pH due to the CO2 dissolution. However, the experiments in this work are computational,
55
56 thus, consider pH= 7 for aqueous NaCl solutions is fairly appropriated.
57
58 The concentration of hydronium ion demonstrated a profound impact on the
59
60
preferential routes for hydrogen production. Figure 3 displays the time evolution for the

16/56
1
2
3 concentration of reactant and products for pH 1 and 7, which are respectively a high and
4
5
6
low concentration of hydronium ion. Hydrogen is produced for both pHs, however OH–
7
8 is produced only in neutral pH. Such difference on the distribution of products is
9
10 consistently explained based on the mechanism shown in figure 2. For high concentration
11
12
of H+, the formation of radical-H (H•) via reaction 6 has a substantially high rate, speeding
13
14
15 up all reactions downward. Considering the near zero production of OH– in figure 3 for
16
17 pH 1, the water reduction both via hydrated electron self-recombination (reaction 1) and
18
19
assisted by radical-H (reaction 7) demonstrates to be irrelevant routes, being hydrogen
20
21
22 fully produced via radical-H recombination reaction(reaction 8). Furthermore, this
23
24 interpretation corroborates with the time evolution of reactants for pH 1, cf. figure 3 plate
25
26 a. Neither the concentration of H+ decreases, nor the concentration of 𝑒𝑎𝑞
―
rises above zero,
27
28
29 but the concentration of radical •H rises smoothly, goes from zero to 1.5×10–7 mol L-1.
30
31 Indeed, the concentration of radical H• remains low, despite of a fast hydronium
32
33 scavenger reaction rate (reaction 6), because of its fast recombination rate via reaction 8,
34
35
36 that drags H• out into the substantial formation of gaseous hydrogen as seen on bottom
37
38 plate (a). Additionally, the concentration of 𝑒𝑎𝑞
―
fixed around zero is consistent with
39
40 negligible rates for both reaction 1 and 7. As partial conclusion, the radical-H
41
42
43 recombination reaction is the major route for hydrogen production in highly acid pH.
44
45 Considering the low concentration of H+ in figure 3 (pH 7), the time evolution of
46
47 concentrations of both reactants and products indicate a change on the preferential route
48
49
50 of H2 production. A stiff increase on the OH– concentrations seen in plate b revels that
51
52 both reactions 1 and 6 has a nonzero rate, which is corroborated by a nonzero
53
54 concentration of both 𝑒𝑎𝑞
―
and •H. Further, the maximum on the profile for the •H (an
55
56
57 intermediate specie) associated to a monotonic depletion on the H+ concentration
58
59 indicates that the rate of either reaction 6, 7 or 8 is being reduced progressively. As a final
60

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1
2
3 piece, the rate of reaction 1 has to develop an uninterrupted rise because of the progressive
4
5
6
increase on the 𝑒𝑎𝑞
―
concentration. This view gains precision with a computational
7
8 assessment of the rates of reaction shown in figure 4. The rate of reaction 1 overpass all
9
10 the others over the majority of the discharging time, therefore indicating that the self-
11
12
13
recombination of hydrated electron (reaction 1) is the dominant route of hydrogen
14
15 production in neutral media. In addition, the H• is active intermediate that generates
16
17 hydrogen via reaction 7, being this route the second and last relevant pathway in neutral
18
19
media. As conclusion, the hydrogen generated in neutral media is majorly explained by
20
21
22 the self-recombination of 𝑒𝑎𝑞
―
(reaction 1), and just a minor part by the radical-H assisted
23
24 water reduction (reaction 7).
25
26
Such perception of the dominance of one pathway over another in a real life
27
28
29 experimental is captured by quantifying the stoichiometric proportion between products
30
31 together with the stoichiometric quantity of ballistic electrons. Table 2 summarizes the
32
33 stoichiometric ratio 𝐻2 :𝑂𝐻– : 𝑒𝑏 for the three dominating routes of hydrogen production
34
35
36 according to the pH. The stoichiometric proportion must adhere to one of the extreme
37
38 cases, either pH 1 or pH 7 seen in figure 5, or otherwise, lay in between them for
39
40 intermediate pHs. In addition to the yields of products and the influx of ballistic electron,
41
42
43 figure 5 stress the stoichiometric ratio between those quantities. On one extreme, at pH
44
45 1, each mole of hydrogen relates to zero mole of OH– and around two moles of
46
47
48 ballistic electrons, i.e. ratio 1: 0: ≥ 2. On the other extreme, the
49
50 pH 7 displays a ratio 1: ≤ 2: ≥ 2. In principle, the expected ratio
51
52
53 in acid media is 1: 0: 2 whereas for neutral media 1: ≤ 2: 2. If
54
55
compared to table 2, the ballistic electron ratio deviates
56
57
58 upward 2, which indicates that not all ballistic electrons had
59
60

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1
2
3 reacted in liquid phase under the span time considered in the
4
5
6 particular case of figure 5. When accounting the yields under
7
8
9
full period of discharge, i.e. during 0.2 ms of both closed and
10
11 open sections, the deviation smooths as shown in figure 6. In
12
13
14 abundance of H+ ions as for pH 1, the radical-H is an active intermediate and the
15
16 stoichiometric ratio H2 to OH- follows 1:0 straightforward. Conversely, in scarcity of H+
17
18
19
ion as for pH 7, radical-H continuous to be an active intermediate, but with a rather low
20
21 contribution to the total yield of hydrogen. In addition, the preferential pathway for
22
23 synthesis of H2 via radical-H passes to be the radical-assisted water reduction that
24
25
includes the reaction 6 plus 7 combined into a global reaction
26
27
28
―
2𝑒𝑎𝑞 + (𝐻 + )𝑎𝑞 + 𝐻2𝑂→𝐻2 + 𝑂𝐻 ― , (26)
29
30
31
for which ratio H2 to OH- follows 1: 1. In neutral media, the self-recombination of 𝑒𝑎𝑞
―
is
32
33
34 the major pathway contributing to the total yield of hydrogen , thus the global observation
35
36
37 carries the general tendency for its ratio H2 to OH- that is 1: 2. The contribution of the
38
39 radical-assisted water reduction to the total amount of produced hydrogen, despite minor,
40
41
is sufficient to deviate the ratio H2 to OH- toward 1: ≤ 2. Not only the
42
43
44
direction of deviation can be understood, but also quantified;
45
46
47 however, the concept of faradaic efficiency has to be invoked,
48
49
50 which will be target in future work.
51
52
53 At last but not least, the effect of the term 𝑞𝑒 in equation 14 on the hydrogen
54
55
56 production is discussed based in the context of the results in figure 7. Such figure show
57
58 how the concentration of the major reactant evolves during full period of discharge (0.2
59
60 ms) for the two extremes pHs. For pulsed DC-voltage from Urabe et al., the authors used

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1
2
3 50% duty cycle, therefore the closed electrical circuit last 0.1ms and another 0.1 ms
4
5
6
dispended at opened circuit. Based on results from figure 6, only 13% of the hydrogen
7
8 yield is produced over open circuit, the other 87% produced over closed circuit, even
9
10 though both sections has same span time, 0.1 ms. Such fact highlights the importance of
11
12
the release rate of ballistic electrons (𝑞𝑒) to accelerate rates of reaction for the CNR
13
14
15 proposed in figure 2. In the closed section, the discharge itself closes the electrical circuit,
16
17 a net electrical current flow throughout the plasma toward the liquid surface and such a
18
19
20
fact is connected to a fair large positive value attributed to the term 𝑞𝑒. In the open section,
21
22 opening the electrical circuit is opened and no net current flows throughout the electrical
23
24 circuit; so, the term 𝑞𝑒 acquires zero value. The implication of such time evolution of the
25
26
27 plasma electrical variables connects to the temporal evolution for the concentration of the
28
29 main reactants shown on figure 7. Note that the radical-H is treated as reactant because it
30
31 is a key precursor of hydrogen at low pH. Under the closed section the reactants only
32
33
34
rises, whereas they only depletes under the open section. Engineering the duty cycle
35
36 together with the current level seems to be a future direction to steer better energy
37
38 efficiency for chemical synthesis, since decreasing the period under closed section could
39
40
bring advantages of saving input energy.
41
42
43
44 3.1.2 Air-free discharge over alkaline electrolyte (NaOH)
45
46
47 In alkaline media, the initial concentration of H+ is rather low, between 10–7 to 10–14
48
49
50
mol L-1. Such low concentration of H+ slows down rate of reactions 6, 7 and 8, thus via
51
52
radical •H passes to have minor contribution over the total production of hydrogen. Figure
53
54
55 4 depicts this description for the pH 7. For larger pH, such contribution is even smaller
56
57 as discussed with figure 8 that shows the time profile for the concentration of the hydrated
58
59 electron and for the yields of product considering neutral and alkaline pHs. Such figure
60

20/56
1
2
3 employs the dynamic system represented by the equations 21 to 23. At the extreme case
4
5
6 of pH 8 and all larger ones, the production of OH- has been maximized. The inspection
7
8
9 of ratio H2 to OH- shown in figure 9 demonstrates that a ratio very close to 1: 2 is found,
10
11
12 indicating that the hydrated electrons passes to be the unique reactant, and the self-
13
14 recombination of hydrated electron the main pathway for hydrogen production.
15
16
Considering the CRN-tree in figure 2, the unique relevant via in alkaline media with
17
18
19 pH larger than 8 is the self- recombination of hydrated electron. Therefore, the equations
20
21
22 22 and 23 from dynamic system represented by set of equations from 21 to 23 are
23
24 eliminated because neither H+ nor the •H are chemical variables. In pH larger than 8, the
25
26 chemical dynamical system passes to be a subset of the CRN belonging to acid and neutral
27
28
29 pH seen in the CRN-tree in figure 2 .The chemical dynamic model passes to be
30
31
32 represented only by the equation 27
33 ―
34 = ― {2𝑘1[𝑒𝑎𝑞
― ]2
} + 𝑉 𝑞𝑒 . (27)
35 𝑑𝑡
36
37 And the products, or dependent variables represented by
38
39 𝑑[𝐻2]
― 2
40 𝑑𝑡 = 𝑘1[𝑒𝑎𝑞 ], (28)
41
42 𝑑[𝑂𝐻 ― ] ― 2
43 𝑑𝑡 = 2𝑘1[𝑒𝑎𝑞 ]. (29)
44
45 3.1.3 Air-based discharge over neutral electrolyte (NaCl)
46
47
48
49 This section devotes to analyze CRN in air-based discharge over neutral electrolyte.
50
51 For such boundary condition, two chemical species take over the role of scavenger 𝑆 = {
52
53 𝑁𝑂3 ― and 𝐻 + } resulting in a CNR with three major reactants (𝑁𝑂3 ― , 𝐻 + and 𝑒𝑎𝑞
―
) and
54
55
56 one intermediate specie ( ∙ 𝐻), as summarized by the CNR-tree in figure 10. Additionally,
57
58
59 the air-based discharge brings about two sources terms for scavengers 𝑞𝑠→ 𝑞𝐻 + and 𝑞𝑠
60

21/56
1
2
3 → 𝑞𝑁𝑂3.
4
5
6 The temporal evolution of the reactants are accessed by
7 ―
8 𝑑[𝑒𝑎𝑞 ] 1
𝑑𝑡 = ― {2𝑘1[𝑒𝑎𝑞
― ]2
+ 𝑘6[𝐻 + ][𝑒𝑎𝑞
―]
+ 𝑘7[ ∙ 𝐻][𝑒𝑎𝑞
―]
+ 𝑘5[𝑁𝑂3 ― ][𝑒𝑎𝑞
―]
} + 𝑉 𝑞𝑒 ,(30)
9
10
11 𝑑[𝐻 + ] 1
= ― 𝑘6[𝐻 + ][𝑒𝑎𝑞
―]
+ 𝑉 𝑞𝐻 + ,(31)
12 𝑑𝑡
13
14 𝑑[𝑁𝑂3 ― ] 1
15 𝑑𝑡 = ― 𝑘5[𝑁𝑂3 ― ][𝑒𝑎𝑞
―]
+ 𝑉 𝑞𝑁𝑂3 ,(32)
16
17 Whereas the intermediates species (radical 𝐻 ∙ ) by
18
19 𝑑[𝐻 ∙ ]
20 𝑑𝑡 = 𝑘6[𝐻 + ][𝑒𝑎𝑞
―]
― {2𝑘8[ ∙ 𝐻]2 + 𝑘7[ ∙ 𝐻][𝑒𝑎𝑞
―
]} , (33)
21
22
23 And the products by
24
25 𝑑[𝐻2]
― 2
26
𝑑𝑡 = 𝑘1[𝑒𝑎𝑞 ] + 𝑘8[ ∙ 𝐻]2 + 𝑘7[ ∙ 𝐻][𝑒𝑎𝑞
―
], (34)
27
28
𝑑[𝑂𝐻 ― ] ― 2
29 = 2𝑘1[𝑒𝑎𝑞 ―
] + 𝑘7[ ∙ 𝐻][𝑒𝑎𝑞 ], (35)
𝑑𝑡
30
31
𝑑[𝑁𝑂3 ―2]
32 = 𝑘5[𝑁𝑂3 ― ][𝑒𝑎𝑞
―]
. (36)
𝑑𝑡
33
34
35 The air–based discharge over neutral electrolyte is an extension of the case studied in
36
37 the section 3.1.1. Figure 11 displays the results from numerical solution for a four–
38
39
degree–of–freedom model that includes the equations 30–33 as the core dynamical
40
41
42 system and the equations 34–36 as the dependent variables.
43
44 Interestingly, the presence of two plasma-induced sources of scavengers for the model
45
46 from figure 11 plate a are insufficient to modify the final outcome when comparing to the
47
48
49 findings from figure 3 plate b. Both cases are solved for similar initial conditions expect
50
51 by a nonzero value for 𝑞𝐻 + and 𝑞𝑁𝑂3 on figure 11. The insignificance of the terms 𝑞𝐻 +
52
53 and 𝑞𝑁𝑂3 persists when conferring the yield of products from figure 12 plate a and figure
54
55
56 5 for pH 7. Such similarities indicates that the term 𝑉 ―1 × 𝑞𝑁𝑂3 in equation 32 has
57
58 neglectful value in comparison to the term 𝑘5[𝑁𝑂2― ][𝑒𝑎𝑞
―]
, which results in an invariable
59
60

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1
2
3 concentration of the nitrate as seen in figure 11 plate a. Only if broaden in several folds
4
5
6
the value for 𝑞𝑁𝑂3, as seen in plate a to c, a rise on the nitrate concentration could be
7
8 observed. Despite of such enlargement on the source term 𝑞𝑁𝑂3 impact on the yields of
9
10
11 hydrogen, it is mild. Instead, the stoichiometry of OH- and reduced nitrate (𝑁𝑂32 ― )
12
13
14
assumes an antagonist behavior, the former decreases whereas the latter enlarges, see
15
16 figure 12. Such antagonism reflects an interestingly interference of the scavenger nitrate
17
18 on the preferential route of hydrogen synthesis, favoring the route via radical-H in
19
20
21 detrimental of via-self. As the concentration of nitrate increases with enlarged 𝑞𝑁𝑂3 , 𝑒𝑎𝑞
―
22
23
24 is further consumed by nitrate, decreasing concentration of 𝑒𝑎𝑞
―
that were what in fact
25
26
27 determines a lesser hydrogen produced via-self (reaction 1). As were already mentioned
28
29 on the discussion round table 2, less OH- is produced when accelerating the route of
30
31
32 hydrogen synthesis via radical-H in detrimental of the route via-self. Although on the
33
34
35 switching preference on the routes, the yields of hydrogen is almost maintained, only
36
37 decreasing in a stoichiometric content proportional to the decrease on the concentration
38
39
40 of 𝑒𝑎𝑞
―
by the nitrate. Moreover, the minor impact of the nitrate concentration on the yields
41
42 of hydrogen occurs because of the constrictions set for the model. It were settle that both
43
44 sources 𝑞𝑁𝑂3 and 𝑞𝐻 + acquired similar values because of the stoichiometry of reaction
45
46
47 20. The increasing value of source 𝑞𝐻 + guarantees a continuous supply of H+ to the
48
49 nano-reactor, which sustain an increased rate via radical-H with increased nitrate
50
51
52 concentration, maintaining almost invariable the global production of hydrogen. The
53
54
55 exclusion of air-based discharge from the list of drawbacks for favoring hydrogen
56
57 synthesis is an important point learned with this example.
58
59
60 3.2 Discharge in humid air over oxygen-free electrolyte

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1
2
3 This section devotes to understand the CRN for a discharge through humid noble gas.
4
5
6
Since ever, it has been preconized that hydrogen peroxide is synthesized in plasma phase
7
49 by water decomposition under discharge, followed afterwards by its absorption onto
8
9
10 the liquid surface. This understanding about the nature of the plasma-liquid interaction
11
12
being restricted to an ordinary absorption of plasma precursor H2O2 by the liquid is
13
14
15 reinforced in view of an enlarged yield of H2O2 when the contact area between plasma
16
17 and liquid increases (achieved by flowing of water droplets through the plasma)50. Other
18
19 species such as radicals •OH and •H are also formed by the discharge under water vapour
20
21
22 and their presence is also identified in liquid phase but via the spin-trapping technique 5.
23
24 In view of all said, H+, 𝑁𝑂3 ― , H2O2 plus both radical •OH and •H represent the five
25
26
scavenges considered as chemical variables for the CNR. However, H2O2 is excluded
27
28
29 from this set of chemical variables, being treated instead as dependent variable. Further,
30
31 this work adheres to recent suggestion that only radical •OH is effectively solvated by the
32
33 liquid, being H2O2 locally formed 51 into the nano-reactor by the reaction 37
34
35
36 ( ∙ 𝑂𝐻)𝑎𝑞 + ( ∙ 𝑂𝐻)𝑎𝑞→𝐻2𝑂2. (37), k37 = 5.0×109 L mol−1 s−1
37
38 According to this interpretation, all the locally formed H2O2 is transported through
39
40
41 the liquid toward the bulk, which promotes its dissolution, in turn, weakening scavenger-
42
43 like action of reaction 4. For this reason, reaction 4 fully disregarded in this approach. On
44
45 the other hand, an enlarged concentration of •OH just strengths its scavenger-like action
46
47
via reactions 3. The present approach also test the possible combination between •OH and
48
49
50 •H by reaction 38
51
52 ( ∙ 𝑂𝐻)𝑎𝑞 + ( ∙ 𝐻)𝑎𝑞→𝐻2𝑂 . (38), k38 = 2.5×1010 L mol−1 s−1
53
54
55 Figure 13 presents the CNR after all considerations mentioned above. The temporal
56
57 evolution of the reactants in such CNR are accessed by
58
59 ―
𝑑[𝑒𝑎𝑞 ]
60 𝑑𝑡 =―

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1
2
3
4
{2𝑘1[𝑒𝑎𝑞― ]2 + 𝑘3[𝑒𝑎𝑞― ][ ∙ 𝑂𝐻] + 𝑘5[𝑒𝑎𝑞― ][𝑁𝑂3 ― ] + 𝑘6[𝑒𝑎𝑞― ][𝐻 + ] + 𝑘7[𝑒𝑎𝑞― ][ ∙ 𝐻]} +
5 1
𝑉 𝑞𝑒 ,(39)
6
7
8 𝑑[𝐻 + ] 1
= ― 𝑘6[𝑒𝑎𝑞
― ][ + ]
𝐻 + 𝑉 𝑞𝐻 + , (40)
9 𝑑𝑡
10
𝑑[ ∙ 𝑂𝐻] 1
11 = ― {𝑘3[𝑒𝑎𝑞
―]
[ ∙ 𝑂𝐻] + 𝑘38[ ∙ 𝐻][ ∙ 𝑂𝐻] + 2𝑘37[ ∙ 𝑂𝐻]2} + 𝑉 𝑞𝑂𝐻 , (41)
12 𝑑𝑡
13
14 𝑑[𝑁𝑂3― ] 1
15 𝑑𝑡 = ― 𝑘5[𝑒𝑎𝑞
―]
[𝑁𝑂3 ― ] + 𝑉 𝑞𝑁𝑂3 , (42)
16
17 Whereas the intermediates species (radical 𝐻 ∙ ) by
18
19 𝑑[𝐻 ∙ ]
20 𝑑𝑡 = 𝑘6[𝑒𝑎𝑞 𝐻 ― {𝑘7[𝑒𝑎𝑞
― ][ + ] ―]
[ ∙ 𝐻] + 𝑘38[ ∙ 𝐻][ ∙ 𝑂𝐻]}, (43)
21
22
24
25 𝑑[𝐻2]
― ]2
26 𝑑𝑡 = 𝑘1[𝑒𝑎𝑞 ―
+ 𝑘7[𝐻 ∙ ][𝑒𝑎𝑞 ], (44)
27
28 𝑑[𝑂𝐻 ― ] ― ]2
29 𝑑𝑡 = 2𝑘1[𝑒𝑎𝑞 + 𝑘3[𝑒𝑎𝑞
―]
[ ∙ 𝑂𝐻] + 𝑘7[𝑒𝑎𝑞
―]
[ ∙ 𝐻], (45)
30
31 𝑑[𝑁𝑂23 ― ]
32
𝑑𝑡 = 𝑘5[𝑒𝑎𝑞
―]
[𝑁𝑂3 ― ], (46)
33
34 𝑑[𝐻2𝑂2]
35 = 𝑘37[ ∙ 𝑂𝐻]2. (47)
𝑑𝑡
36
37
38 The five–degree–of–freedom model encompassed by the set of equations 39–43
39
40 includes four source terms: 𝑞𝑒, 𝑞𝐻 + , 𝑞𝑁𝑂3 and 𝑞𝑂𝐻.The values attributed to these source
41
42
terms are found in table 1. Detailed information about the estimations is found in the table
43
44
45 S3 to S5, and the related discussion found in the supporting information. Figure 14
46
47 displays the results from numerical solution for equations 39–43 (reactants) as the core
48
49 dynamical system and the equations 44–47 (products) as the dependent variables.
50
51
52 Figure 14a display results for discharge in gases containing water vapor that
53
54 commensurate with general trends already observed in figure 11a for discharge in dry
55
56 gases. Despite the mechanism in figure 13 incorporates the radical OH as a chemical
57
58
59
variable, the low value assigned to the term 𝑞𝑂𝐻 allows for such similarity. The
60

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1
2
3 plasma/liquid interaction for a torch-like discharge observed by Gorbanev et al. 5 renders
4
5
6
a term 𝑞𝑂𝐻 almost nine digits lower in the order of magnitude than a term 𝑞𝑂𝐻 estimated
7
8 from the work of Lit et al. 46 for an anodic electrochemical discharged, cf. table 1. Using
9
10 the large term 𝑞𝑂𝐻 from anodic plasma is senseless in the context of this work because it
11
12
13 analyses the chemical effects from a cathodic plasma. On the order hand, the electrical
14
15 datum used in this work is among the largest current ever observed for a pulsed cathodic
16
17 discharge, rendering the largest possible value attributed to source term of electrons (𝑞𝑒).
18
19
Conversely, for steady cathodic discharge 27,29, the current rarely overpass 15 mA,
20
21
22 rendering much lower values related to the term 𝑞𝑒. To cover the case of low current,
23
24
25
some fractions of the current 150 mA are analyzed in figure 14.
26
27 Respectively, a progressive and a sharp reduction on the generation of hydrogen is
28
29 seen in figure 14 when the current 150 mA helves in plate (b) and reduces to one tenth in
30
31 plate (c). The tendencies of the temporal behaviors for the reactants on the plate b is
32
33
34 maintained (i.e. a maximum on the radical-H profile, a substantial decay on the H+
35
―
36 concentration and a substantial increase on the 𝑒𝑎𝑞 concentration), meaning that the
37
38 ―
reaction 1 still is the major route for 𝑒𝑎𝑞 consumption. Such conclusion agrees well with
39
40
41 the minor variation on the stoichiometric proportion of products (ratio𝐻2:𝑂𝐻–:𝑒𝑏) seen in
42
43 figure 15, when comparing such case (75 mA) to the 150 mA. Furthermore, the larger
44
45
46 deviation on the ballistic electron ratio upward 2 for the current 75 mA corroborates well
47
―
48 with the fact that more 𝑒𝑎𝑞 had reacted with the nitrate, once the yield of reduced nitrate
49
50 enlarges at 75mA, cf. fig 15. On the other hand, the current of 15 mA displays an out of
51
52
53 proportionality reduction on the hydrogen yield, together with a change on the general
54
55 tendency on the temporal evolution of reactants, strongly suggesting a change on the
56
57 ―
preferential route of the 𝑒𝑎𝑞 consumption. The rise on the radical-OH concentration is
58
59
60 again very distinct from the other two larger currents whereas the concentration of

26/56
1
2
3 ―
radical-H and 𝑒𝑎𝑞 traces back each other. An assertive understanding on the preferential
4
5
6 ―
route of 𝑒𝑎𝑞 consumption could only be perceive if analyzing the rate of reactions as
7
8
9 shown in figure 16. An inversion on the dominant rate of reaction in relative terms is seen
10
11 for the lowest current. The reaction 6 is the fastest one among all in the CNR, leading to
12
13 a substantial rise on the concentration of radical-H in the nano-reactor along the discharge
14
15
16 because very little amount of radical-H is consumed by the slow-rate reaction 7.
17
18 This example sediments the relevance of the current as a key parameter to modify the
19
20 ―
routes of 𝑒𝑎𝑞 consumption. As seen in this case, the scavenger-like action of the ion H+
21
22
23 via reactions 6 is relevant only if in very low values of current.
24
25
26 3.3 Discharge in humid gas over electrolyte enriched with dissoluble oxygen
27
28
29 This section envisions understanding the CRN for a discharge through humid air over
30
31
32 a liquid body (aqueous electrolyte) that is enriched with soluble oxygen. It is well known
33
34 that liquid solubilizes gases throughout the gas-liquid interface; liquid water operates as
35
36 solvent (or reservoir) for both oxygen and carbon dioxide. Taking into account the oxygen
37
38
39
partial pressure in a humid air at sea level, 0.2095 atm, the concentration of oxygen is
40
41 around 0.27 10-3 mol L-1, which is substantially high in comparison to the 𝑒𝑎𝑞
―
42
43
44 concentration seen throughout this work. Conversely, the carbon dioxide has a very low
45
46 partial pressure in air (0.0004 atm at sea level) that leads to concentration around 13 10-
47
48
49 6 mol L-1, which is very more diluted than oxygen and could possibly scavenger 𝑒𝑎𝑞
―
in an
50
51
52 extension relatively similar to the behavior found in figure 3 for ions H+ at pH 7. Given
53
54
55 the high concentration of oxygen in water at sea level, solely the scavenger-like action of
56
57 oxygen is considered in this section.
58
59 The presence of soluble oxygen in aqueous phase introduces reaction 9 to 11 to the
60

27/56
1
2
3 CNR previously considered in figure 13. Besides, the reactions 38 and 5 are disregarded
4
5
6
from this CNR. Reaction 5 effectively changes the distribution of products only if a source
7
8 term qNO3 is unrealistically high, thus it is disregarded. Reaction 38 does play negligible
9
10 roles for a high value of current ( 150 mA) since the distribution of products for this
11
12
current at figure 15 does adhere to stoichiometry related to a major domination of reaction
13
14
15 1, hence this reaction 38 is eliminated. Taking all these considerations, the CNR proposed
16
17 for the electrochemical discharge over an oxygen-enrich electrolyte for humid air-based
18
19 gas phase is shown in figure 17.
20
21
22 Temporal evolution of the reactants for the CNR in figure 17 are accessed by
23 ―
24 𝑑[𝑒𝑎𝑞 ]
𝑑𝑡 =―
25
26 { ― ]2
2𝑘1[𝑒𝑎𝑞 + 𝑘3[𝑒𝑎𝑞
―]
[ ∙ 𝑂𝐻] + 𝑘6[𝑒𝑎𝑞
―]
[𝐻 + ] + 𝑘7[𝑒𝑎𝑞― ][ ∙ 𝐻] + 𝑘9[𝑒𝑎𝑞― ][𝑂2] + 𝑘10[𝑒𝑎𝑞― ][𝑂2 ― ] + 𝑘11[𝑒𝑎𝑞― ][𝐻
27 1
28 + 𝑉 𝑞𝑒 , (48)
29
30 𝑑[𝐻 + ]
31 𝑑𝑡 = ― 𝑘6[𝑒𝑎𝑞
―]
[𝐻 + ] , (49)
32
33 𝑑[ ∙ 𝑂𝐻] 1
34 𝑑𝑡 = ― {𝑘3[𝑒𝑎𝑞
―]
[ ∙ 𝑂𝐻] + 2𝑘37[ ∙ 𝑂𝐻]2 + 𝑘38[ ∙ 𝐻][ ∙ 𝑂𝐻]} + 𝑉 𝑞𝑂𝐻 , (50)
35
36 𝑑[𝑂2]
37 𝑑𝑡 = ― 𝑘9[𝑒𝑎𝑞
―]
[𝑂2] , (51)
38
39 Whereas the intermediates species by
40
41 𝑑[𝐻 ∙ ]
42 𝑑𝑡 = 𝑘6[𝑒𝑎𝑞
―]
[𝐻 + ] ― {𝑘7[𝑒𝑎𝑞― ][ ∙ 𝐻] + 𝑘38[ ∙ 𝐻][ ∙ 𝑂𝐻]}, (52)
43
44 𝑑[𝑂2 ― ]
45 𝑑𝑡 = 𝑘9[𝑒𝑎𝑞
―]
[𝑂2] ― 𝑘10[𝑒𝑎𝑞― ][𝑂2 ― ], (53)
46
47 𝑑[𝐻𝑂2 ― ]
48
𝑑𝑡 = 𝑘10[𝑒𝑎𝑞
―]
[𝑂2 ― ] ― 𝑘11[𝑒𝑎𝑞― ][𝐻𝑂2 ― ] , (54)
49
50
52
𝑑[𝐻2]
53 ― 2
= 𝑘1[𝑒𝑎𝑞 ] + 𝑘7[𝑒𝑎𝑞
―]
[ ∙ 𝐻], (55)
54 𝑑𝑡
55
56 𝑑[𝑂𝐻 ― ]
57 𝑑𝑡
― 2
= 2𝑘1[𝑒𝑎𝑞 ] + 𝑘3[𝑒𝑎𝑞
―]
[ ∙ 𝑂𝐻] + 𝑘7[𝑒𝑎𝑞
―]
[ ∙ 𝐻] + 𝑘10[𝑒𝑎𝑞
―]
[𝑂2 ― ] + 𝑘11[𝑒𝑎𝑞― ]
58 [𝐻𝑂2 ― ], (56)
59
60

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1
2
3 𝑑[𝐻2𝑂2]
4 𝑑𝑡 = 𝑘37[ ∙ 𝑂𝐻]2. (57)
5
6
7
8
9
Figure 18 shows the impact of partial pressure of oxygen (pO2) on the time evolution
10
11 of reactants and products for the closed section of our model pulsed plasma. The oxygen
12
13 concentration in the liquid is determined by the composition of the gas phase, measured
14
15
in terms of pO2. The values attributed to the pO2 corresponds to the real life situations. For
16
17
18 pO2 = 0.2019 atm, air composes the gas phase. For a pO2 = 0.0005 atm, gas phase has
19
20 99.95 % of Helium or Argon, which corresponds to the real situation where the head of a
21
22 closed chamber is filled with jet-plasma effluents as it has been largely employed by
23
24
25 recent researches using a electrochemical discharge. Finally, a pO2 = 10-10 atm correspond
26
27
28 to an unrealistic experimental situation at atmospheric pressure, being more likely for
29
30 unusual combinations of temperature and pressure. Figure 18a shows time evolution of
31
32
33
reactants (top) and products (bottom) for 0.2095 atm pO2. It demonstrates that OH- is the
34
35
major final product and that the high oxygen concentration barely depletes during the
36
37 ―
38 discharge, indicating that oxygen scavengers all 𝑒𝑎𝑞 , i.e. reaction 9 majorly dominates the
39
40 ―
consumptions of 𝑒𝑎𝑞 . As the pO2 decreases to 0.0005 atm, see panel b, the productions of
41
42
43 OH- folds more than a hundred times whereas two significant changes happens to the
44
45 ―
46 reactants concentrations: the concentration of 𝑒𝑎𝑞 folds a thousand times and the
47
48 concentrations of oxygens halves. Further, the yields of final products displayed by this
49
50 condition in figure 19, exhibits a stoichiometric ratio 𝐻2 :𝑂𝐻–: 𝑒𝑏 that equals to 0:1:(1.5)
51
52
53 or, in terms of inter numbers, 0:2:3. Interestingly, such stoichiometric ratio fairly traces
54
55 back the ratio expected for a global reaction that combines reactions 9, 10 and 11
56
57 ―
3𝑒𝑎𝑞 + (𝑂2)𝑎𝑞 + ( ∙ 𝑂𝐻)𝑎𝑞→2𝑂𝐻 ― . (58)
58
59
60

29/56
1
2
3 This evidence vividly indicates that for 0.0005 atm pO2 the hydrated electron has fully
4
5
6 depleted toward OH- (the final product) via global reaction 58. Finally, for unusual 10-10
7
8
9 atm pO2, the scavenger-like action of aqueous oxygen has weakened because of its low
10
―
11 concentration in liquid phase, enabling a substantial rise on the concentration of 𝑒𝑎𝑞 that
12
13 follows up by a detectable production of hydrogen. However, as shown by the yields in
14
15
16 figure 19, this condition synthesizes hydrogen in a very inefficient way given that a large
17
18 deviation on stoichiometric ratio 𝐻2: 𝑒𝑏 is found, that is, the results display ratio equal
19
20
1: 9.4 against 1: 2 that is expected for one hundred efficiency of hydrates electrons
21
22
23 consumptions toward hydrogen.
24
25 Beyond the distribution of products, the cases studied in this section also elucidates
26
27 the dramatic impact of soluble oxygen on the spectrum of products. The neglectable
28
29
30 production of both OH- and H2 seen for 0.2095 atm pO2 in figure 19 indicates a change
31
32
33 in the spectrum of final products. As reaction 9 majorly dominates the consumptions of
34
35 ―
𝑒𝑎𝑞 for 0.2095 atm pO2, the superoxide O2- is massively produced, an intermediate for the
36
37
38 full mechanism but a product related to the reaction 9. The yields of superoxide O2- is
39
40
41 account in figure 20. Interestingly, its productions exhibits a ratio 𝐻2: 𝑒𝑏 equals to 1:1
42
43
44 which does confirm that the hydrated electrons has been fully depleted toward superoxide
45
46 O2- for 0.2095 atm pO2. Such massive production of superoxide O2- predicted in this work
47
48
supports very much the recent findings of Shirai et al. [25] The authors had detected
49
50
51
superoxide O2- in liquid phase for a electrochemical discharge whose gas/liquid interface
52
53
54 exposes an large area for the gas/liquid surface at 0.2095 atm pO2.
55
56
57
58 4. DISCUSSION
59
60

30/56
1
2
3 Incontestably, experimental validation for the mechanism of hydrogen production
4
5
6
proposed in this wok depends on the simultaneous quantification of the stoichiometry
7
8 proportion between H2 , OH– and ballistic electrons (the number of ballistic electrons that
9
10 effectively crossed the PLI, in turn, converted into hydrated electrons). These three
11
12
quantities (𝐻2 :𝑂𝐻– : 𝑒𝑏) have to follow the stoichiometry 1 :2 :2, if hydrogen is majorly
13
14
15 formed via self-recombination of hydrated electrons, as seen for the case of alkaline
16
17 electrolyte (pH values above 8). If the electrolyte is strongly acid (pH around 1), those
18
19
20
three quantities has to follow the stoichiometry 1 :0 :2, because hydrogen is majorly
21
22 synthetized via radical-recombination reaction. For all the other cases in between these
23
24 two extremes cases (i.e. 1 < 𝑝𝐻 < 8) the stoichiometric 𝐻2 :𝑂𝐻– : 𝑒𝑏 tends to follow
25
26
27
1 :𝑥 :2, where 0 < 𝑥 < 2. Up to date, the experimental assessment to the stoichiometry 𝐻2
28
29 :𝑂𝐻– : 𝑒𝑏 has been verified only partially. Using a salt as supporting electrolyte, so
30
31
presumably at pH 7, Sengupta et al. [4] have verified a stoichiometric ratio 𝐻2 :𝑒𝑏 equal
32
33
34 to 1 :1. cf. figure 3 into reference [4] (findings that resembles the cathodic polarity). The
35
36 results of Sengupta et al. strongly indicates that twice more hydrogen had been produced
37
38
than expected by the chemical mechanism hereby proposed. Notoriously, some “water
39
40
41 splitting” is developed on the plasma phase21,22,26 allowing for an excess of hydrogen
42
43 production. Such plasma-induced radiolytic synthesis of hydrogen contributes to the
44
45 global production of hydrogen under electrochemical discharge. Ultimately, experimental
46
47
48 validation of the mechanism proposed in this work must circumvent plasma-phase
49
50 radiolysis contribution; quenching of excited state water 23 could be a suitable strategy.
51
52
53 5. CONCLUSIONS
54
55
56
57
This paper deals with computational experiments employing chemical reactions
58
59 networks (CRN) as a theoretical framework to explain events at the plasma-liquid
60

31/56
1
2
3 interface for an electrochemical discharge, emphasizing the hydrogen synthesis as well
4
5
6
as the drawbacks for its production. The generalist dynamic model for the plasma
7
8 electrochemistry bases on the ordinary differential equations and includes a continuous
9
10 function describing the chemical mechanism named function of the chemical reaction
11
12
network (CRN). It also includes a source term (𝑞), accounting for the plasma-liquid
13
14
15 interaction, which could be of two nature, electrical (term 𝑞𝑒) and chemical (term 𝑞𝑆).
16
17 Term 𝑞𝑒 accounts for the injection of plasma-free electrons into the liquid, whereas term
18
19
20 𝑞𝑆 accounts for the quantity of the species synthetized in the plasma phase that is
21
22
23 absorption by the liquid. The physical boundary conditions enables to solve CNR-
24
25
26 function for an infinitesimal volume containing approximately ~1018 molecules of liquid
27
28 water, termed nano-reactor. The model is solved for different CRN via numerical
29
30
31 methods.
32
33
34
The screening of CRN allows identifying two major pathways for gaseous hydrogen
35
36
37 production. In strong acid media, ion H+ reacts with hydrated electrons forming radical-
38
39 H (∙H), an intermediate (and precursor) of gaseous hydrogen, whereas in strong alkaline
40
41
42 media the second-order recombination reaction of the hydrated electron predominantly
43
44
originates the gaseous hydrogen. These paths are the “plasma version” of the hydrogen
45
46
47 evolution ration (HER) observed on standard solid/liquid interface for an electrochemical
48
49 cathode. Any other side reaction consuming hydrated electrons competes with one of
50
51 these two paths, decreasing the efficiency of hydrogen production.
52
53
54
55 Further, this work identifies two disadvantageous experimental conditions for
56
57 synthesizing hydrogen, which extends to other electrosynthesis routes. For a water-
58
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60 vapor-based discharge, the radical-OH produced in plasma-phase is uptaken by the

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3 liquid, decreasing yields of hydrogen in an extension very much dependent on the level
4
5
6
of the electric current (term 𝑞𝑒 in the model). However, the great villain against large
7
8 yield of hydrogen is the soluble oxygen. At room temperature and atmospheric pressure,
9
10 the oxygen content in the air (around 0.21 atm of oxygen partial pressure) solubilizes into
11
12
13 liquid phase, resulting in a concentration very high of soluble oxygen. A massive
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15 production of superoxide O2- and null production of hydrogen results from the complete
16
17
18 consumption of the hydrated electrons by the aqueous oxygen. If, otherwise, 0.9995 atm
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20 of either He or Ar composes the gas phase ( or 0.0005 atm of oxygen partial pressure),
21
22
23
production of H2 persists null, however all 𝑂2― fully depletes toward the final product
24
25 that is OH-. Tentatively, other techniques has to be used in association with low partial
26
27
28 pressures of oxygen in order to circumvent the drawbacks related to the mass action of
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30 soluble oxygen in liquid phase.
31
32
33
34 Finally, the computational experiments elucidates the interesting impact of the
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36 electrical current (or term 𝑞𝑒) and the rate of acidification (term 𝑞𝑆) on the hydrogen
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38
yields. These two terms, together, connect the properties of the plasma with the plasma-
39
40
41 induced reactions in liquid phase, being the key parameters the developers of plasma
42
43 source must target. At last, the assessment gained with the dynamical model, without loss
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45 of generality, can be extended to set of reaction (or CNR-trees) for other routes of
46
47
48 chemical synthesis on the emerging field of plasma electrochemistry.
49
50
51 ASSOCIATED CONTENT
52
53
54 Supporting Information. glossary plus estimations on the parameters such as 𝑞𝑒 and 𝑞𝑆, Table S1-S5.
55
56
57 AUTHOR INFORMATION
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59
60
Corresponding Author

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1
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3 *mota@usp.br
4
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6 Author Contributions
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8
9 The manuscript was written through contributions of all authors. All authors have given approval to the
10
11 final version of the manuscript.
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13
14 Notes
15
16
17 The authors declare no competing financial interest.
18
19
20 ACKNOWLEDGMENTS
21
This work was sponsor by CNPq (155046/2018-7). AML is very much in debit to
22
23
24 both Prof. Naoki Shirai and Prof. David Go for valuable discussions.
25
26
27
28
29 REFERENCES
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31
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Liu, Q. H. Direct synthesis of hydrogen peroxide from plasma-water interactions.
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33 implications for aqueous targets. J. Phys. D: Appl. Phys. 2015, 48, 424007-424021.
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36 formation of hydrogen peroxide by electrolysis with a glow-discharge anode.
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38 J.Chem. Soc. 1934, 1772-1773.
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43 20, 034006-034021.
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45 (51) Paul, R.; David, M. B.; David, B. G. The penetration and concentration of solvated
46
electrons and hydroxyl radicals at a plasma-liquid interface. Plasma Sources Sci.
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48 Technol. 2018, 27, 115013-115029.
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53 TOC GRAPH
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41 FIGURES
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23 Figure 1. Out of proportion sketch of the electrochemical nano-reactor generated during
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26 an electrochemical discharge.
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47 Figure 2. CRN-tree (or mechanism) for an air-free dry discharge over water containing
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50 either HCl or NaCl as supporting electrolyte.
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Figure 3. Temporal evolution of reactants and products accessed by computational
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33 experiments solving equations 21–23 as independent variables of the dynamical system
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35 and considering two initial concentrations of hydronium (a) [H+]0 = 10-1 mol L-1 and (b)
36
37
38 [H+]0 = 10-7 mol L-1. Initial condition: [𝑒𝑎𝑞
―
]0 = [•H]0 = 10-17 M whereas [H+]0 =[H+]bulk.
39
40
41 The values for all other parameters are listed in table 1.
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23 Figure 4. Rate of reactions for all the steps in the CNR from figure 2 accessed by
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―
25 computational experiments solving equations 21–23. Initial condition: [𝑒𝑎𝑞 ]0 = [•H]0 =
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28 10-17 M whereas [H+]0 =[H+]bulk= 10-7 mol L-1. The values for all other parameters are
29
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listed in table 1.
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56 Figure 5. Yields of gaseous hydrogen and aqueous OH- when solving equations 21–23
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58 by computational experiments for the period of closed section, i.e. 0.1 ms. The red dashed
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60 line represents the total amount of ballistic electrons (𝑒𝑏) converted into hydrated

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Figure 6. Bar graph for yields of gaseous hydrogen and aqueous OH- when considering
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29 the period of closed section plus the open circuit period of a pulsed DC-voltage discharge
30 (total of 0.2 ms) when solving equations 21–23. The red dashed lines represent the values
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32 of ballistic electrons (𝑒𝑏) converted into hydrated electrons on top and half of this quantity
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34 on bottom.
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32 Figure 7. Temporal evolution for the major precursor of hydrogen in (a) pH =1 and (b)
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34 pH =7, accessed by computational experiments for solving equations 21–23 as
35
36
―
independent variables of the dynamical system. Initial condition: [𝑒𝑎𝑞 ]0 = [•H]0 = 10-17 M
37
38 whereas [H+]0 =[H+]bulk. The values for all other parameters are listed in table 1.
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32 Figure 8. Effect of alkaline pH on the temporal evolution for the hydrated electron (top)
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34 along with the products such as hydrogen (center) and OH- (bottom), accessed by
35
36 ―
computational experiments when solving equations 21–23. Initial condition: [𝑒𝑎𝑞 ]0 =
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38 [•H]0 = 10-17 M whereas [H+]0 =[H+]bulk. The values for all other parameters are listed in
39
40
table 1.
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23 Figure 9. Effect of alkaline pH on the temporal evolution for ration yield of OH- to yields
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25 of hydrogen, when solving equations 21–23 computationally.
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Figure 10. CRN-tree (or mechanism) for an air–based dry discharge over water
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containing NaCl as supporting electrolyte.
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Figure 11. Temporal evolution of reactants (top) and products (bottom) accessed via
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33 interactive solution of the equations 30–33 for initial concentrations of hydronium [H+]0
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35 = 10-7 mol L-1 (for pH 7), but employing different values of the plasma-based source
36
37
38 term 𝑞 = {𝑞𝐻 𝑎𝑛𝑑 𝑞𝑁𝑂3} : (a) q = 1× q, (b) q = 1000×q and (c) q = 5000×q. Initial
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40
41
―
condition: [𝑒𝑎𝑞 ]0 = [•H]0 = [𝑁𝑂3 ― ]0 = 10-17 M. The values for all other parameters are
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44 listed in table 1.
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28 Figure 12. Yields of gaseous hydrogen, aqueous OH- and NO32- for pH 7 when solving
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30 equations 30–33 by computational experiments for the period of closed section, i.e. 0.1
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32 ms, and considering multiplied values for 𝑞𝑁𝑂 and 𝑞𝐻. Upper and bottom red dashed lines
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represent the values for full and half quantity of ballistic electrons (𝑒𝑏) that had effectively
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47 Figure 13. CRN-tree (or mechanism) for an air–based humid discharge over NaCl-
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34 and considering three values for the level of current (a) 150 mA, (b) 75 mA, and (c) 15
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36
―
mA.. Initial condition: [𝑒𝑎𝑞 ]0 = [•H]0 = 10-17 mol L-1 whereas [H+]0 =[H+]bulk=10-7 mol
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38 L-1. The values for all other parameters are listed in table 1; a torch-like value was
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40 attributed to the term qOH.
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28 Figure 15. Yields of gaseous hydrogen, aqueous OH- and NO32- when solving equations
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30 39–43 by computational experiments for the period of closed section, i.e. 0.1 ms, and
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32
considering multiplied values for the level of current, or alternative for the term 𝑞𝑒. The
33 values of moles for the ballistic electrons (𝑒𝑏) that had effectively crossed the plasma–
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35 liquid interface are indicated for each current.
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Figure 16. Rate of reactants accessed by computational experiments solving equations
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29 39–43 for the level of current (a) 150 mA, (b) 75 mA, and (c) 15 mA. Initial condition: [
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31 ―
𝑒𝑎𝑞 ]0 = [•H]0 = 10-17 mol L-1 whereas [H+]0 =[H+]bulk=10-7 mol L-1. The values for all
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33 other parameters are listed in table 1; a torch-like value was attributed to the term qOH.
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48 Figure 17. CRN-tree for air–free humid discharge over NaCl-containing water enriched
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50 with gaseous-O2.
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34 and considering three values for the level of current (a) 150 mA, (b) 75 mA, and (c) 15
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―
mA.. Initial condition: [𝑒𝑎𝑞 ]0 = [•H]0 = 10-17 mol L-1 whereas [H+]0 =[H+]bulk=10-7 mol
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38 L-1. The values for all other parameters are listed in table 1.
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1
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3 H2 OH H2O2
4
5 1.6 # ballistic electrons (eb)
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7 H2 : OH : eb # 1.56 109
8 1.4
0 : 1 : 1.5
yields per 0.1 ms / 109 mol
1.03x10-9
10 1.2
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13 1.0
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15 0.8
16 H2 :OH: eb
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18 0.6 1 : 1 : 9.4
19 H2:OH: eb
20 0.4 0 : 1 : 300 1.65x10-10
1.65x10-10
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22
9.59x10-12
4.99x10-12
7.78x10-17
0.2
4.90x10-18
1.95x10-18
3.48x10-19
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25 0.0
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27 0.2095 0.0005 1010
28 oxygen partial pressure / atm
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30 Figure 19. Yields of gaseous hydrogen, aqueous OH- and hydrogen peroxide when
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33
solving equations 48–54 by computational experiments for the period of closed section,
34 i.e. 0.1 ms, and considering different values for the partial pressure of oxygen, which
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36 means alternatively to depart from different initial concentrations of oxygen that is
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38 soluble in aqueous phase.
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28 Figure 20. Yields of superoxide O2- when solving equations 48–54 by computational
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30 experiments for the period of closed section, i.e. 0.1 ms, and considering different values
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32 for the partial pressure of oxygen.
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35 Table 1: Parameters employed to solve, via interactive method, the equations (14) and
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37 (15) across different CRN.
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39 Parameter Value Unit
40 Release rate of ballistic electrons 𝑞𝑒 (a) mol s-1
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1,555.0×10-9
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43
1 659.00×100 mol L-1 s-1
× 𝑞𝑒
44 𝑉
45 Release rate of the Birkeland- (b) mol s-1
𝑞𝑁𝑂3 = 𝑞𝐻 + 293.34×10-12
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47 Eyde products 1 1
48 × 𝑞𝑁𝑂3 = 𝑉 × 𝑞𝐻 + 12.43×10-2 mol L-1 s-1
𝑉
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1
50 Release rate of radical OH × 𝑞𝑂𝐻 (c) 25.39×10-6 mol L-1 s-1
𝑉
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52 (torch-like interaction)
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Release rate of hydrogen 𝑞𝑂𝐻(e) 20,000.0 ×10-9 mol s-1
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55 peroxide (Anodic plasma / 1
56 × 𝑞𝑂𝐻 (e) 8,470.00×100 mol L-1 s-1
𝑉
57 electrochemical discharge)
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59 Volume of the Nanoreactor (b) V 2.36 ×10-9 L (at STP)
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1
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3 Rate coefficients k1 (d) 6.0 ×109 L mol−1
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5 k2 (d) 1.1×1010 s−1
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7 k3(d) 3.0×1010
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9 k4(d) 1.1×1010
10 k5(d) 9.7×109
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12 k6(d) 2.3×1010
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14 k7(d) 2.5×1010
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16 k8(d) 1.0×1010
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k9(d) 1.9×1010
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19 k10 = k11(d) 2.5×1010
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21 k37 (d) 5.0×109
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23 k38(d) 2.5×1010
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25
Initial concentrations for the [H+]0 / pH = 1 1.0×10-1 mol L−1
26 scavengers at the time zero
27 [H+]0 / pH = 7 1.0×10-7
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29 [H+]0 / pH = 8 1.0×10-8
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[H2O2]0 (c) 5.0×10-8
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34 [(O2)aq]0 at 0.20 atm(f) 2.7×10-4
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36 [(O2)aq]0 at 0.0005 atm(f) 6.5×10-7
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39 [(O2)aq]0 at 0.10-10 atm(f) 1×10-12
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41 (a) Estimated by this work based on the discharge extracted from the work of Urabe
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43 et al., see Table S1.
44 (b) The largest acidification rate observed on the data from the work of Gonçalves
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46 et al.
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48
(c) Real concentration expect for the time window of the DC–pulse estimated from
49 the data found on the work of Gorbanev et al.
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51 (d) In general, the rate constant for all the reactions were gathered from Garrett et al.
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53 and Buxton et al.
54 (e) Estimated from Liu et al.
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56 (f) Molar solubility of oxygen in water at the sea level (1 atm) estimated by using
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58 the Henry law constants for oxygen in water at 298 K and considering different
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5 Table 2: Stoichiometry proportion between several pathways for hydrogen production
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7 via electrochemical plasma.
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Routes of hydrogen production Domain Ratio
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10 range 𝐻2 :𝑂𝐻– : 𝑒𝑏
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12 Reaction 1 via–Self pH ≥ 7 1:2:2
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14 ―
2 𝑒𝑎𝑞 + 2𝐻2𝑂→𝐻2 + 2𝑂𝐻 ―
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16 Reaction 6+7 via–Radical-H 1 < pH < 7 1:1:2
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18 ―
2𝑒𝑎𝑞 + (𝐻 + )𝑎𝑞 + 𝐻2𝑂→𝐻2 + assisted water
19 𝑂𝐻 ― reduction
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21
22
Reaction 6+8 via–Radical-H pH ≤1 1:0:2
23 ―
2𝑒𝑎𝑞 +2(𝐻 + )𝑎𝑞→𝐻2 recombination
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