Antioxidant-induced coating formation by aromatic compounds in plasma

electrolysis for electrochemical stability

Nisa Nashrah, Early Zahwa Alharissa, Chouiki Abdelkarem, Wail Al Zoubi*, Young Gun Ko*

Materials Electrochemistry Group, School of Materials Science and Engineering,

Yeungnam University, Gyeongsan 38541, Republic of Korea
*Corresponding author: E-mail address: [email protected] and @[email protected]

Abstract

The adsorption of antioxidants on a metallic substrate is significant for various applications

related to sensors, catalysis, and corrosion inhibition. The interaction between the metal surface
and antioxidant molecule to form a protective coating during a plasma-assisted electrochemical
reaction is still lacking with regard to the coating formation and its corresponding anti-corrosion
performance. Here we present the investigation of three aromatic compounds, 9H-Pirin-6-amine
(9HP6A), 1H-1.2.3-benzotriazole (1HBTZ), and 1.3.5-triazine-2.4.6-triamine (TATA), with a
tautomeric structure to understand how dynamic isomerism arising from amine (-NH2) and
imine (-NH) groups would affect chemical reaction at the electrolyte-metal interface via
facilitating H2- and suppressing O2-gasses, thereby controlling the growth of coating layer. The
existence of TATA, having several tautomers, was found to significantly modify the defect
morphologies of the coating layer, exhibiting the superior corrosion inhibition effect to their
counterparts even at elevated temperature, 313.5 K, due to their role as both antioxidants and
stabilizers. We ascribed this phenomenon to TATA's thermal stability and adsorption tendency
on the Mg surface, which was in line with theoretical calculation via density functional theory
(DFT) and molecular dynamic (MD) simulation. The adsorption tendency and surface coverage
increased with the number of -NH2 groups reacting with the Mg alloy substrate.

Keywords: antioxidant, organic-metal interaction, density functional theory, coating layer,

corrosion
1. Introduction

Plasma electrolysis (PE) is an eco-friendly wet-coating strategy desirable for adjusting the

compounds and surface structure in different metallic materials, allowing the production of thick,

hard, and well-adherent inorganic coating on light metals (in particular, Mg, Al, and Ti) and their

alloys [1]. The formation mechanism of the coating layer and its structures generated by PE

would depend mainly on electrolyte conditions, including chemical compositions and their

concentration [2,3], as well as the electrical parameter, such as current density, mode, and

frequency regime. Of all processing variables, the role of electrolytes has been reported to

significantly modify the micro-morphology of the coating layers, thereby changing their

electrochemical properties. So far, the inorganic-containing electrolytes, such as silicate [4],

aluminate [5], phosphate [6], and borate [7], with various chemical additives, have been

investigated to be beneficial for modulating the characteristic of the coating layers on the surface

of light metals. In this communication, we describe tautomers as stabilizers and antioxidants in

electrochemical reactions to develop a coating layer on the surface of magnesium alloy and

discover the new phenomena that could be detected in the plasma-enhanced electrochemical

system.

To date, the majority of published works in the PE area regarding the roles of chemical additives

on the chemical reaction during the formation of the coating layer, have focused merely on

donor-acceptor interaction [ref prof Zoubi, other scientist]. At the same time, almost no report

discovered that dynamic isomerism could play an important role in changing plasma and

chemical reactions during PE. For instance, Putri et al. discovered, on the basis of PE of titanium

alloy in phosphate-based electrolyte system, that the addition of 1H-benzotriazole working as

electron donor would allow hydrogen transfer to oxygen radicals as an electron acceptors in the
electrolyte to enhance the chemical incorporation during coating formation [Rosy]. Besides, the

addition of organic additives could decrease the volume of the oxygen gases, which facilitates

the penetration of electrolyte ions into the discharge channels, reducing the formation of denser

and thicker coating layer. Other organic additives, such as triethanolamine, glycerol, and 3-

aminopropyltrimethoxysilane added into the silicate-based electrolyte were found to modify the

chemical reaction during PE since the hydroxyl group of each compounds could be adsorbed on

the Mg surface via hydrogen bond, allowing the Mg surface to be isolated from water. Pak, et al.

[8] suggested that the specific organic moieties, such as silanol group in glycerol would be

adsorbed around silicate ions in the electrolyte, decreasing the surface tension which make the

arrangement of ions near anode/electrolyte interface, thereby leads to a smaller discharge center

[8] and finally reduce the cracks and pores on the coating layer. Another organic compound like

phytic acid (C6H18O24P6) was also reported to increase the value of breakdown and the coating

growth rate while controlling their pore uniformity and corrosion protection [9].

Dynamic isomerism or tautomerism are isomers of organic molecules, such as 9H-pirin-6-amine

(C5H5N5, 9HP6A), 1H-1.2.3-benzotriazole (C6H5N3, 1HBTZ), and 1.3.5-triazine-2.4.6-triamine

(C3H6N6, TATA), which represent the mobility of a hydrogen ion from one atom to another in

the molecule with a double-bond rearrangement. Tautomer exist in equilibrium in the liquid state

and are predicated to exist as a planar structure with a uniform/even distribution of electron

density over the molecular backbone, which gives extra stabilization to the compounds itself.

The carbon-nitrogen (C-N) or carbon-oxygen double (C=O) bonds are expected to be in an anti-

orientation in the form of isomer, which needs a twisted geometry which bent around the central

atom of C atom. This bent geometry of the E/Z isomerization of imines lacked an extended

delocalized electron, thus the physical-chemical properties of this tautomeric species is expected
to change. The tautomeric stability of amino in 2-chloro9HP6A for instance, was calculated

using a scaled quantum mechanics (SQM) approach [ 10.1016/S1386-1425(00)00252-3]. More

recently, the experimentally observed electronic properties have been associated perfectly to the

tautomeric structures (hydroxyphenyl) using time-dependent density functional theory study

[ACS Omega 2022,7,16, 14222]

These electrochemical reactions were established as donor-acceptor that raised the unresolved

question on whether the existence of dynamic isomerism or tautomerism would be an

opportunity for coating growth behavior and to understand how a reaction mechanism occurs

experimentally and theoretically between organic additives and metal-electrolyte interfaces

during PEO. The information of structure-property on how the additions of imines and amines,

such as 9HP6A, 1HBTZ, and TATA, to alkaline silicate will affect the surface morphology and

electrochemical performance of the inorganic layers deposited on metal surface subjected to PE

strategy has been reported yet. In this protocol, the influences of as 9HP6A), 1HBTZ, and TATA

on PE strategy, phase composition, coating morphology, and corrosion protection of metal alloy

as well as reaction mechanism using DFT and MD is discussed.

2. Experimental

2.1. Fabrication and characterization

2.1.1 Material’s fabrication

A plate-type sample of AZ31 Mg alloy with nominal composition (wt.%) of 3.08 Al, 0.76 Zn,

0.15 Mn, and balanced Mg was used as anode (substrate) with a dimension of 15 mm (L) × 25

mm (W) × 4 mm (T). Prior PE process, the anode was polished mechanically with SiC papers,

cleaned ultrasonically with pure ethanol, and finally dried in a stream of warm air. Subsequently,
plasma-assisted electrochemical reactions were performed for 5 min in alkaline electrolyte

composed of aromatic compound with different tautomer having different amine-based

functional group, such as TATA, 1HBTZ, and 9HP6A. PE was performed in a glass vessel

containing electrolyte equipped with stainless steel as the cathode, stirring unit, and cooling

system to maintain electrolyte temperature at 15 °C under alternating current with current density

and frequency of 100 mA.cm−2 and 60 Hz, respectively. To evaluate the effect of amine-based

functional group on the formation of coating layer, we optimized at least three different

concentration, of 3, 5, 10, 15 mmol which reflected as 1, 2, 3, and 4 respectively.

Table 1. Electrolyte composition of each sample during PE process

Sample KOH K3PO4 Glycerol TATA 1HBTZ 9HP6A

name (g/L) (g/L) (g/L) (g/L) (g/L) (g/L)
PE 4 3 1.5 – – –
TATA-1 4 3 1.5 0.189 – –
TATA-2 4 3 1.5 0.315 – –
TATA-3 4 3 1.5 0630 – –
TATA-4 4 3 1.5 0.945 – –
1HBTZ-1 4 3 1.5 – 0.178 –
1HBTZ-2 4 3 1.5 – 0.298 –
1HBTZ-3 4 3 1.5 – 0.59 –
1HBTZ-4 4 3 1.5 – 0.890 –
9HP6A-1 4 3 1.5 – – 0.203
9HP6A-2 4 3 1.5 – – 0.338
9HP6A-3 4 3 1.5 – – 0.675
9HP6A-4 4 3 1.5 – – 1.000

2.1.2 Material’s characterization

Microstructural observations were performed using field-emission scanning electron microscopy

(FE-SEM; S-4800, HITACHI) equipped with Energy dispersive X-Ray spectroscopy (EDS,

HORIBA). The chemical composition of the coating was evaluated in details via X-ray

photoelectron spectroscopy (XPS, VG Microtech, ESCA 2000), and further was deconvoluted by

using XPSPEAK41 software. The phase composition and crystal structure of the obtained
coating was investigated by X-Ray diffraction (XRD, RIGAKU, D-MAX 2500) with step size of

0.05° and scan range of 20-90°. Fourier transform infrared spectroscopy (FT-IR, PERKIN

ELMER, Spectrum 100) was used within the range of 4000-500 cm -1 to identify each surface

functional groups of the coating with the addition of organic compound.

2.2. Electrochemical assessment

The electrochemical behavior of the coating layer was evaluated in a 3.5 wt % NaCl solution

(pH=7) at 25 °C using three-electrode system: coated sample as the working electrode, Ag/AgCl

solution as reference electrode, a platinum plate as counter electrode. The electrochemical

properties of the samples was investigated by a potentiodynamic polarization (PDP) test and

electrochemical impedance spectroscopy (EIS) measurements. PDP tests were measured from -

0.25 to +0.4 V with respect to the open circuit potential (OCP) at a scan rate of 1 mV·s-1

whereas the EIS experiments were performed from 10 6 to 10 -1

Hz at an interval of 10

points/dec9HP6A with a 10 mV rms. To further evaluate the stability of each coating, corrosion

assessment was carried outs for 8 h at different temperatures ranging 25 to 60 °C. The

temperature of the aggressive solution was maintained in thermostatically controlled water bath.

2.3. Theoretical calculation by DFT and MO

Theoretical calculations were performed using the principles of conceptual density functional

theory (DFT) to examine the interactions between Mg and the following three antioxidant: 9H-

pirin-6-amine (9HP6A), 1H-1.2.3-benzotriazole (1HBTZ), and 1.3.5-triazine-2.4.6-triamine

(TATA). For this purpose, the interaction between Mg 2+ and each antioxidant molecule was

modeled using Gaussian 16 W software. The geometries of each system was optimized using

the B3LYP functional with the 6–311 ++ G (d,p) basis set in water by implementing the
polarizable continuum model (PCM) model in the Gaussian package [40]. Frequency

calculations were performed at the same level of theory to ensure that the modelled systems

corresponded to a local minimum potential energy. Furthermore, additional electronic structure

analysis density of states (DOS) of the studied systems were calculated using the Multiwfn 3.8

code on the optimized systems [43] Finally, quantum chemical (QC) descriptors such as the

highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)

energies, and energy gap (Eg) were calculated within the framework of molecular orbital

theory to predict the chemical relativities of the inhibitor compounds. These QC parameters

have been mathematically described in detail elsewhere within the framework of finite

difference approaches [REF].

E ads=E total −( E surf +water + E inh+ water ) + E water (1)

Etotal, Esurf+water, Ewater, Einh+sol are used to represent the total energy of the molecule-metal system, single-

point energy of Mg surface and water, the potential energy of the water molecules, energy of the organic

molecule and water, respectively.

3. Results

3.1. Fabrication of the coating layer

Figure 1 describes voltage response with respect to time during surface modification of Mg alloy

via plasma electrolysis showing a different tendency due to the addition of aromatic compound,

such as TATA, 1HBTZ, and 9HP6A into the phosphate-based electrolyte (Base). Based on the

linearity of the curve, two regions can be easily distinguished, such as region (i) showing a

linear curve where the responding voltage increased sharply with time obeying ohms rule, until it

reach the inclination point. This point determine the transition from region (1) to region (ii)
where the linearity decreased significantly and the voltage response is no longer obeying ohm’s

rule. This transition is estimated to be the initial breakdown phenomenon because the passive

film formed earlier due to interaction between Mg and electrolyte could not stand the electrical

charge any longer. The ignition phenomenon (voltage and time) was varied depending upon the

electrolyte composition. In comparison to the base electrolyte, the ignition phenomenon occurred

slower at higher ignition voltage from TATA followed by 1HBTZ and 9HP6A respectively.

Following the ignition voltage occur in base electrolyte, addition of TATA was found to reach

ignition fastest followed by 1HBTZ and 9HP6A. Stojadinovic [REF] correlate the ignition

phenomenon with the conductivity of electrolyte because if the applied voltage is sufficiently

high, an avalanche of electron at the oxide-electrolyte interface would cause breakdown, thus

making the ignition voltage directly proportional to the logarithm of the reciprocal of the

electrolyte conductivity as follows:

1
U 1=α + β log ( )
k

Where α and β are constants for materials of interest and electrolyte composition, and U1 and k

are the ignition voltage and the electrolyte conductivity, respectively. Hence, the values of

breakdown voltage were likely to increase as the electrolyte conductivity decrease. At higher

conductivity, conduction current increases, ohmic heating increases, requiring a lower

breakdown voltage. On the contrary, at lower conductivity, the resistance in the solution

becomes higher so that conduction current decreases, the ohmic heating decreases, thus

breakdown occur at a higher voltage. Interestingly, Although the breakdown voltage decreases,

the discharge energy in plasma formation will increase as the conductivity of the electrolyte
increases due to the resistivity between the anode (Mg substrate) and the electrolyte ( T Sukreni et

al 2018 IOP Conf. Ser.: Earth Environ. Sci. 105 012009)

The low responding voltage would be due to the side reaction occur during the coating process. To

confirm this rationale, the electrolyte was filtered and the precipitate was analyzed via FTIR and XRD.

FTIR show the new peak which is likely to be the complex of Mg-NH2 IN both adenine and BTO sample

as the product of the reaction as shown in Fig S1. This could be impurities that obstruct the incorporation

and growth of the coating layer. [REF showing that Metal complex is disadvantage could be impurities].

The reaction between ADE and BTO with Mg to form complex compound indicated the low stability of

both compound during plasma electrolysis. Considering high surrounding temperature, this result is in

line with the analysis of TGA/DTA showing that ADE and BTO has the less and least stability,

respectively in comparison to MEL as depicted in Fig. S2. Due to the distinctive responding voltage

among four different electrolyte conditions, the final voltage is also varied, in which MEL and Base, ADE

with BTO, has similar trends. Accordingly, it can be anticipated that the microstructure features of each

sample would shows different characteristics due to different chemical phenomena affecting the growth

rate of the coating.

3.2. Microstructural-compositional analysis

Figure 2 describes the surface features of each coating layer on Mg alloy with the addition of

TATA, 9HP6A, and 1HBTZ with different concentration of 3, 5, 15 mmol. Upon the addition of

each compound at low concentration shown in Fig 2 a-c for adenine, BTO and MEL

respectively, the surface structure shows similar characteristics identical to that in base

electrolyte (Fig. S2). It is apparent from Fig. 2 d-i that, with the increasing in concentration, the

addition of adenine and BTO shows the substantial increase in surface compactness as the

porosity decrease while different tendency was found in MEL sample. Although the pore size is
unlikely affected by concentration, micro-pores on some area was sealed as indicated by the

yellow dash line in the Fig 2. c, f, and i. Interestingly, upon the 15 mmol addition of adenine, the

number of pores was almost unseen along with the deposition of white precipitates on the surface

as indicated by the yellow arrows. The white precipitate was clearly observed on the mostly

whole part of the surface in 9HP6A sample while in some part on 1HBTZ as Figures 3 a and b

would confirm. Unlike the structure in 9HP6A sample where the white precipitate cover the

topmost layer of the coating, the sealed pores is more dominant in MEL surface as indicated by

yellow-dash circle in Fig. 3 c. More interestingly, coating thickness of BTO and ADE sample

was similar each other which is found to be thinner than that of MEL sample which is likely

identical to the base counterpart shown in Figure S4. Although the in TATA sample seemed to

be incorporated through the pores and discharge channels as shown in EDS mapping of cross

sectional morphologies in Fig. 2 d-i.

3.3. Electrochemical performance in respect to temperature

The electrochemical assessment was conducted for all samples varying the concentration of

aromatic compounds during PEO to evaluate microstructure-properties relationship. The

electrochemical behavior of three different samples

3.4. Theoretical calculation by DFT and MD simulation

Isolated molecules

Interest in adsorption of 9HP6A, 1HBTZ, and TATA on the Mg (001) surface arises from the fact that

heterocyclic compounds significantly modify the chemical and physical properties of the atoms at the

surface by donating (accepting) electrons []. To explain this phenomenon on the Mg (001) surface during

high-temperature plasma, we combine DFT studies and experimental results. The molecular orbitals and
the physical and chemical properties coordination of the isolated molecules to form complexes with Mg

(II) ions are shown in Fig. The results indicate that the calculated energy gap (E gap) (Egap =ELUMO-EHOMO)

values obtained from DFT calculations of studied molecules follow the order: 9HP6A˂1HBTZ˂TATA,

elucidating the 9HP6A exhibits the most prominent role in the complex reaction with metal ions because

9HP6A donates electrons via N lone pair electrons to Mg ions easier than TATA and 1HBTZ and acts

more as an electron donor than other electron acceptors during complex reactions.

In order to investigate the molecule-metal interaction, the PDOS for valence electron orbitals of organic

molecule, i.e., 9HP6A, 1HBTZ, TATA, and Mg surface, before and after adsorption were studied, as

shown in Fig. After physical adsorption, the overlapping continuous PDOS between 9HP6A, 1HBTZ, and

TATA molecules and Mg- SP-orbitals is exhibited in Figure. The higher overlapping PDOS, which is

attributed to light decreases in intensities of peaks compared to peaks prior to adsorption, of the modified

and combined organic molecule-Mg adsorption systems, shows the stronger adsorption ability, i.e.,

9HP6A, 1HBTZ, and TATA exhibit the significant protection performance for Mg surface.

DFT calculations for organic molecules on Mg (111)

The adsorption of 1HBTZ, 9HP6A, and TATA on Mg surface in different adsorption configurations at

low coverage by means of parallel and vertical was methodically studied using DFT calculations. In the

parallel configuration, 1HBTZ, 9HP6A, and TATA are located on the Mg surface, where the donor

heteroatoms, polar functional groups, and π-current of the aromatic ring are bonded onto the Mg surface

with adsorption energy -2.10 eV, -2.48 eV, and -2.89 eV, respectively. The N atom in 1HBTZ, 9HP6A,

and TATA is adsorbed and bonded to Mg atoms with Mg-N bond lengths of 2.24 Å, 2.29 Å, and 2.34 Å,

respectively. On the other hand, the molecules can be adsorbed and ordered monolayer by standing

perpendicular orientation to the Mg surface in the most stable configuration at high coverage. All organic

molecules, 1HBTZ, 9HP6A, and TATA, form a covalent bond between the N atoms and Mg atoms with a
bond length of 2.11 Å, 2.42 Å, and 2.32 Å, and adsorption energy are -2.89 eV, -4.15 eV, and -5.77 eV,

respectively.

Interestingly, molecules adsorbed parallel on the Mg surface have higher adsorption energy of -3.89 eV, -

4.15 eV, and -5.77 eV. These results indicate that the parallel configuration of the molecule is consistent

with an enhanced electrostatic force, which is due to an attraction between the N atoms and the Mg

atoms, and the π-π repulsion is minimized. In addition to that, these results show that the formation of a

full organic monolayer is much favored compared to chemisorption adsorption at low coverage, therefore;

the adsorption of 1HBTZ, and 9HP6A via N atoms on the Mg surface is less stable than TATA as shown

Fig. To explain this point fully, stronger interaction between TATA and Mg surface by means of

adsorption energy shows that the TATA is probably to remain longer attached to the Mg surface during

plasm reaction, whereas

in the case of weak 1HBTZ- Mg surface interaction, the 1HBTZ is probably to detach from the Mg atoms

at the surface because of weak calculated adsorption energy.

Density of states (DOS) reflect hybridization of the substrate and adsorbates orbitals and the degree of

bonding that occurs upon adsorption.

Molecular dynamic simulations

A molecular dynamic simulation was conducted to attention to the interactions of the targeted molecule

with magnesium atoms at the surface amid an aqueous solution, containing ….., at the microscopic level.

It clarifies the adsorption equilibrium configurations of 1HBTZ, 9HP6A, and TATA on Mg (001), as

shown in Fig. As a result, the most stable configuration to maximize contact and surface coverage on the

Mg surface is almost planar orientation. According to equation (1), the interaction strength between the

targeted molecule and Mg surface was obtained [].

E ads=E total −( E surf +water + E inh+ water ) + E water (1)

Etotal, Esurf+water, Ewater, Einh+solu are used to represent the total energy of the molecule-metal system, single-

point energy of Mg surface and water, the potential energy of the water molecules, energy of the organic

molecule and water, respectively. The obtained interaction energy (adsorption energy Eads) was calculated

from the average adsorption energy of the equilibrium configurations at various temperature, such as 298,

500, 800, and 1200 K as tabulated in Table.x. At 298 K which is considered as room temperature, the

adsorption energy are -121.28, -128.57, and -204.51, for 1HBTZ, 9HP6A, and TATA, respectively. The

results indicate that the interaction energies on the Mg surface are negative and thus adsorption of the

studied molecules are spontaneous. The adsorption value of 1HBTZ is lower than TATA and 9HP6A,

demonstrating that the physical adsorption of 1HBTZ with less active sites compared to TATA and

9HP6A which is due to the non-polar of aromatic hydrocarbons. Upon increasing The theoretical findings

confirm the results found in DFT calculations in term of not only imine functional groups but also the

amine groups.

4. Discussion

4.1. Effect of amine on the formation mechanism of oxide layer

The presence of amine The effect of amine in electrolyte conductivity due to dipole which

determine the electronic mobility of each ion.

1) The effect of amine, or in particular N atom on the production of Hydrogen and the

number of oxygen. Both are correlated to the competitive reduction-oxidation reaction

2) The side reaction which occurs during PE resulting in the formation of precipitation in

the electrolyte not on the surface of metal. This can be correlated with the stability of

each organic upon high temperature. (Considering high temperature of plasma discharge)

The presence of amine affect the electrolyte conductivity. It is observe that the conductivity

decrease with the addition of amine into the electrolyte. We attributed the decrease in electrolyte
conductivity to the electrical mobility of each ionic species (cation and anion) in electrolyte according to

Kohlrausch’s law of independent ionic migration

k =( α × c ) × ¿

both [REF how conductivity decrease with organic additives] (Energies 2022, 15, 7508). It is interesting

to note that the presence amine critically affect the conductivity of electrolyte which correlate strongly

with the breakdown phenomenon at the substrate (anode)- electrolyte interfaces. In addition, melamine

with triple-NH2 would be maintain the voltage response of the system although the conductivity decrease

due to the presence of ionic mobility of amine. This can be correlated with the role of N as the electron

donor which may facilitate the growth of coating film during plasma electrolysis. On the contrary, the

addition of Adenine with one –NH2, N-H, and three N with free electron, and BTO with no –NH2, N-H

and N=N, with the number of N atom is likely to disturb/ distract the growth of coating film (this is result,

the cause should be stated in advance before this sentence).

1) The effect of amine, or in particular N atom on the production of Hydrogen and the

number of oxygen. Both are correlated to the competitive reduction-oxidation reaction

2) The side reaction which occurs during PE resulting in the formation of precipitation in

the electrolyte not on the surface of metal. This can be correlated with the stability of

each organic upon high temperature. (Considering high temperature of plasma discharge)

It is important to maintain oxidation reaction dominant during PE process so that the coating growth can

also be maintained. Adding some additives, including organic compound or inorganic compound

Based on TGA/DTA curve of 9HP6A, 1HBTZ, and TATA

4.2. Stability of TATA

5. Conclusion
Tables
Table 1. The dependency of conductivity of the electrolyte on the ignition phenomenon occurs on the
anode substrate describing the responding voltage and time to reach the first ignition
Electrolyte Conductivity (mS·cm-1) Ignition voltage (V) Ignition time (s) Final voltage (V)
Base 15.07 196.7 10 365.4
9HP6A 12.37 230.4 30 208.2
TATA 13.92 208.4 12 361.6
1HBTZ 12.11 215.4 21 223.9

Table 2 Electrochemical impedance parameter of 9HP6A, TATA, and 1HBTZ measured from 106 to 101
Hz with 10 mV rms perturbation in 3.5 wt. % NaCl solution
Immersio CPEo (S·sn·cm- CPEi (S·sn·cm-
Sample Rs (Ω·cm2) Ro (Ω·cm2) 2 Ri (Ω·cm2) 2
n time ) )
9HP6A 1 23.6 1.83×104 2.15×10-12 1.91×106 9.69×10-10
4
8
TATA

1HBTZ

Table 3 Electrochemical impedance parameter of 9HP6A, TATA, and 1HBTZ measured from 106 to 101
Hz with 10 mV rms perturbation in 3.5 wt. % NaCl solution at 298 K after different immersion times.

Immersion Rs Ro CPEo Ri CPEi

Sample
time (h) (Ω·cm2) (Ω·cm2) (S·sn·cm-2) (Ω·cm2) (S·sn·cm-2)
9HP6A
1 TATA
1HBTZ
4 9HP6A
 TATA
1HBTZ
9HP6A
8 TATA
1HBTZ

Table 4 Electrochemical impedance parameter of 9HP6A, TATA, and 1HBTZ measured from 106 to 101
Hz with 10 mV rms perturbation in 3.5 wt. % NaCl solution at 338 K after different immersion times.

Immersion Rs Ro CPEo Ri CPEi

Sample
time (h) (Ω·cm2) (Ω·cm2) (S·sn·cm-2) (Ω·cm2) (S·sn·cm-2)
9HP6A
1 TATA
1HBTZ
9HP6A
4 TATA
1HBTZ
9HP6A
8 TATA
1HBTZ

Table 5 Electrochemical impedance parameter of 9HP6A, TATA, and 1HBTZ measured from 106 to 101
Hz with 10 mV rms perturbation in 3.5 wt. % NaCl solution at 348 K after different immersion times.

Immersion Rs Ro CPEo Ri CPEi

Sample
time (h) (Ω·cm2) (Ω·cm2) (S·sn·cm-2) (Ω·cm2) (S·sn·cm-2)
9HP6A
1 TATA
1HBTZ
9HP6A
4 TATA
1HBTZ
9HP6A
8 TATA
1HBTZ

Table 6 Electrochemical impedance parameter of 9HP6A, TATA, and 1HBTZ measured from 106 to 101
Hz with 10 mV rms perturbation in 3.5 wt. % NaCl solution at 358 K after different immersion times.

Immersion Sample Rs Ro CPEo Ri CPEi

 time (h) (Ω·cm2) (Ω·cm2) (S·sn·cm-2) (Ω·cm2) (S·sn·cm-2)
9HP6A
1 TATA
1HBTZ
9HP6A
4 TATA
1HBTZ
9HP6A
8 TATA
1HBTZ

Table 7 The theoretical parameters constructed from density functional theory, showing each samples
alone (isolated one) and when it makes complex with metal
Molecule EHOMO ELUMO Eg η  ΔN
Isolated molecule
9HP6A -3.88 -1.00 2.88 1.44 2.44 0.122
TATA -6.98 -0.27 6.71 3.35 3.62 0.008
1HBTZ -6.95 -1.70 5.25 2.62 4.32 -0.044
Complex molecule
Mg-9HP6A -4.59 -1.62 2.97 1.48 3.10 0.059
Mg-TATA -7.55. -1.73 5.81 2.91 4.64 -0.065
Mg- 1HBTZ -7.38 -2.47 4.90 23.45 4.92 -0.092

Figures