Exotox

Materials Chemistry and Physics 290 (2022) 126508
Contents lists available at ScienceDirect
Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys
Corrosion inhibition and ecotoxicological assessment of

1,2,3-triazolic alcohols
Caio Machado Fernandes a, Marcos V. Palmeira-Mello b, Mylena C. Leite a,
Joanna A. Macena Oliveira b, Iago I. Martins c, Rebeca G. de Sá c, Lethicia A. de Almeida c,
Alessandra M.T. Souza b, Vinicius R. Campos c, Eduardo Ariel Ponzio a, *
a
Grupo de Eletroquímica e Eletroanalítica, Instituto de Química, Universidade Federal Fluminense, Niterói, RJ, 24020-141, Brazil
b
Laboratório de Modelagem Molecular & QSAR (ModMolQSAR), Faculdade de Farmácia, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ, 21941-170,
Brazil
c
Laboratório de Síntese de Heterociclos (LASINTHET), Instituto de Química, Universidade Federal Fluminense, Niterói, RJ, 24020-141, Brazil
H I G H L I G H T S G R A P H I C A L A B S T R A C T
• Synthesis of triazolic alcohols and eval

uation as corrosion inhibitors.
• Anticorrosive efficiencies of 85.1 (3b)
and 93.1% (3a), at 1.30 mmol L− 1.
• Polarization curves characterize the two
corrosion inhibitors as mixed-type.
• Quantum chemical calculations support
the experimental results.
• In silico ecotoxicity predictions in
aquatic environments.
A R T I C L E I N F O A B S T R A C T
Keywords: Here, it is reported the synthesis of two triazole derivatives (1-phenyl-1H-1,2,3-triazole-4-yl)methanol (3a) and
Triazole derivative (1-(4-nitrophenyl)-1H-1,2,3-triazole-4-yl)methanol (3b)) and their anticorrosive investigation in 1020 mild steel
Corrosion inhibitor in hydrochloric acid. The corrosion inhibition was evaluated via Weight Loss Study, Linear Polarization Resis
Mild steel
tance and Electrochemical Impedance Spectroscopy at different temperatures. Maximum efficiencies of 85.1 (3b)
DFT calculation
In silico toxicity
and 93.1% (3a) were achieved. Atomic Force Microscopy indicates the formation of a protective layer and
QSAR physical-chemical parameters indicate that is a chemisorption process for both molecules. Potentiodynamic
Polarization curves show that the two triazolic alcohols act as mixed-type corrosion inhibitors. Molecular
modeling suggests the electron withdraw effect of nitro group is a crucial factor for the lower efficiency of 3b
compared to 3a. Additionally, in silico ecotoxicity prediction suggest the 3a and 3b are less toxic than com
mercials benzotriazole (BT) and 5-methyl-benzotriazole (5-MeBT).
* Corresponding author.
E-mail address: [email protected] (E.A. Ponzio).
https://doi.org/10.1016/j.matchemphys.2022.126508
Received 12 April 2022; Received in revised form 14 June 2022; Accepted 11 July 2022
Available online 19 July 2022
0254-0584/© 2022 Elsevier B.V. All rights reserved.
C. Machado Fernandes et al. Materials Chemistry and Physics 290 (2022) 126508
1. Introduction
Carbon steel is widely used in the industrial sector due to its inter
esting mechanical properties, such as high strength, weldability, and
ductility. Nonetheless, this material is extremely susceptible to corro
sion, especially in contact with the acid medium through cleaning and
chemical stripping, for example. In addition to the damage to the
environment and operators as well, such process causes numerous direct
and indirect expenses to industries, reaching a cost of 3.5% of the global
Gross Domestic Product according to a NACE report, being estimated at
USD 3 trillion (2020) [1–3].
The usage of corrosion inhibitors is an effective and practical method
in the attempt to overcome this problem [4,5]. There are different types
of inhibitors currently on the market, which may be composed of
organic or inorganic substances. Organic inhibitors have been increas
Scheme 1. Synthetic Route for the Preparation of 1,2,3-Triazole Derivatives.a.
ingly studied due to their low toxicity when compared to inorganic ones
and a similar or better performance at lower concentrations [6–8].
Organic corrosion inhibitors (OCIs) have their efficiency based on methanol (3a) and (1-(4-nitrophenyl)-1H-1,2,3-triazole-4-yl)methanol
the adsorption process. In this context, a protective layer is formed over (3b) derivatives is reported and their anticorrosive action for 1020 mild
the anodic and cathodic areas upon its interaction with the metallic steel in hydrochloric acid. Furthermore, molecular modeling approach
surface. Moreover, the presence of π-electrons and heteroatoms with was employed to access molecular descriptors involved in their corro
non-binding electron pairs in the chemical structure of the compound, is sion mitigation performance and the in silico prediction of ecotoxicity
responsible for the inhibition of the corrosive process [9–11]. It is risk assessment was performed.
important to point out that adsorption can also be influenced by several
parameters, such as the aggressive medium in which the inhibitor is 2. Experimental methods
found, the total charge distribution, and the geometric arrangement as
well [12,13]. 2.1. Synthesis
Different organic nuclei have been studied in the corrosion inhibition
field to mitigate this problem [14–30], but triazole and other All reagents and solvents used were commercially available and were
nitrogen-containing heterocyclic derivatives have stood out over the employed without further purifcation unless specifically indicated.
years [31–40]. In general, derivatives containing this moiety are good Melting points were determined with a Fisher-Johns melting point
inhibitors in acidic medium and present structural and electronic char apparatus instrument and are uncorrected. Infrared spectra were
acteristics well defined [41,42]. In a search for inhibitor derivatives with recorded on a PerkinElmer Fourier-transform infrared spectroscopy
high anticorrosive efficiency, Chaitra and coworkers studied (FTIR), model 1600 series spectrophotometer in KBr pellets. 1H and 13C
triazole-schiff bases hybrid in acid media. For the three derivatives, the Nuclear Magnetic Resonance (NMR) were obtained in solution of
anticorrosive efficiencies lies in the range of 85.6–90.3% [43]. In a deuterated solvents at room temperature using a Varian Mercury
recent work, Nahlé and coworkers investigated the anticorrosive prop 300.00 MHz or Varian Mercury 500.00 MHz. The chemical shift of 1H or
13
erties of several heterocyclic compounds. The authors obtained high C are in units of δ (ppm) downfield from the deuterated solvent and the
inhibition for the 1,2,4-triazoles, which percentages were around 95% coupling constants J 1H–1H are reported in hertz unit, which refer to
for mild steel in 1.0 M hydrochloric acid [44]. apparent peak multiplicities. The progress of all reactions was moni
Molecular modeling is a time-saving and eco-friendly powerful tored by thin layer chromatography (TLC) performed on 2.0 cm × 6.0
approach to explore and establish relationships between molecular cm aluminum sheets precoated with silica gel 60 (HF-254, E. Merck, Sao
structure and corrosion inhibition efficiency. Density Functional Theory Paulo, Brazil) to a thickness of 0.25 mm. The analyses with TLC plates
(DFT) is the most important quantum chemical method used to predict were visualized by using UV light.
stereo electronic properties and support the experimentally determined Arylazides (2a-b) and 1H-1,2,3-triazol derivatives (3a-b) were pre
results for corrosion inhibition [45–47]. pared through a procedure reported previously [32,54–57], as shown in
Benzotriazoles are widely employed as corrosion inhibitors and in Scheme 1.
other industrial activities and their toxicity is well established, being
relevant to highlight the possible acute and chronic toxicity in animal 2.1.1. General procedure for obtaining arylazide (2a-b)
life and human health [48–50]. Considering the global concern about Aniline or p-nitroaniline (10 mmol) was added in a round-bottom
the environmental toxicity of corrosion, the investigation of ecotoxico flask equipped with a magnetic stirring bar and previously containing
logical risk assessment (ERA) of triazole derivatives plays a crucial role, HCl 6 N (10 mL) in an ice bath at 0–5 ◦ C. Afterward, a solution of NaNO2
since allows the identification of important toxicophoric groups present (15 mmol) in 10 mL of water was added dropwise controlling the tem
on these compounds. In this context, in silico toxicology (IST) methods perature at 0–5 ◦ C. The reaction was stirred for 30 min at 0–5 ◦ C and
are alternative and valid tools to reduce chemical waste and animals in next a solution of NaN3 (20 mmol) in 10 mL of water was added, slowly,
experiments [51,52], besides being recommended in regulation related under vigorous stirring for another hour. The reaction was followed by
to the registration, evaluation, authorization and restriction of chem thin layer chromatography (TLC) and the mixture was extracted with
icals (REACH), issued by the European Chemical Agency (ECHA) [53]. ethyl acetate and the combined organic extracts were washed with H2O,
Although the literature discusses the importance of environmental- dried over anhydrous Na2SO4, filtered, and concentrated in vacuo. The
friendly corrosion inhibitors, IST is not a tool usually utilized in the residual crude product was used without further purification in next
manuscripts of the area. A simulation to ERA in an aquatic environment step.
is of highly importance, since the oil and gas industry for example makes
extensive use of acidic medium for the opening and treatment of 2.1.2. General procedure for preparation of 1H-1,2,3-triazole derivatives
offshore wells, thus requiring the use of OCIs and carrying out its (3a-b)
disposal in sea waters. To a suspension of arylazide (2a-b) (5 mmol) in terc-butanol (3 mL)
Herein, green synthesis of (1-phenyl-1H-1,2,3-triazole-4-yl) was added, along with propargyl alcohol (4 mmol), a mixture of ascorbic
2
acid (0.5 mmol), CuSO4.5H2O (0.3 mmol) in 3 mL of water in a round- 2.5. Quantum chemical calculations
bottom flask. The reaction mixture was kept in ultrasonic bath for 24h at
room temperature and subsequently extracted with ethyl acetate. The The three-dimensional structures of 1,2,3-triazole derivatives 3a and
combined organic extracts were washed with H2O, dried over anhydrous 3b, as well both derivatives reported elsewhere, namely 3c and 3d [44,
Na2SO4, filtered, and concentrated in vacuo. The residual crude product 45], in neutral and protonated forms were constructed and optimized
was purified via silica gel column chromatography using a gradient through quantum chemical DFT calculations using B3LYP/6-311G++**
mixture of hexane-ethyl acetate to obtain the pure derivatives 3a-b. basis set implemented in the Spartan’10 Program (Wavefunction, Inc.,
(1-phenyl-1H-1,2,3-triazole-4-yl)methanol (3a). White solid, mp = Irvine, CA, USA). Stereoelectronic properties were obtained for these
108–110 ◦ C (lit. [55]. 109–110 ◦ C). 79% yield. IR νmax (cm− 1): 3302, compounds such as HOMO (Highest Occupied Molecular Orbital) and
3152, 2961. LUMO (Lowest Unoccupied Molecular Orbital) energy values and orbital
(1-(4-nitrophenyl)-1H-1,2,3-triazole-4-yl)methanol (3b). Brownish coefficient, the GAP energy between the HOMO and LUMO (ΔE), ioni
solid, mp = 198–200 ◦ C (lit. [55]. 201–202 ◦ C). 88% yield. IR νmax zation potential (I = –EHOMO), electron affinity (A = –ELUMO) and the
(cm− 1): 3527, 3099, 1505, 1341. dipole moment (μ, Debye). Additionally, χ (electronegativity), η (hard
ness) and ω (electrophilicity) were calculated following the definitions
below:
2.2. Weight Loss Study
χ = – (EHOMO + ELUMO)/2 = (I + A)/2
All gravimetric analysis were performed with 1020 mild steel (C
0.21, Mn 0.58, Si 0.02, P 0.03, S 0.05, Fe 99.11) specimens in hydro η = – (EHOMO – ELUMO)/2 = (I – A)/2
chloric acid medium (HCl 1 mol L− 1), following the rules of the Amer ω = (–χ)2/2η
ican Society for Testing Materials (ASTM G1-03).
The measurements were performed without and with different con The three-dimensional isosurfaces of the molecular electrostatic
centrations of PTM and NPTM, at different temperatures for the pre potential maps (MEPs) at the van der Waals contact surface were ob
determined immersion time of 5 h. The steel was ground with Emery SiC tained and represent electrostatic potentials superimposed onto a sur
papers of different grain sizes and then measured using a digital caliper. face of constant electron density (0.002 e/au3). MEPs were generated at
It was washed with distilled water, surfactant, ethanol, and acetone. a range of − 160 to +220 kJ mol− 1.
Afterward, it was dried in a thermal dryer and its mass was weighed.
After the immersion time, the steel is removed from the aggressive
2.6. In silico ecotoxicity prediction
media and again chemically washed, this time also with Clark’s solution
(HCl pa, Sb2O3, SnCl2). Afterward, the mass was measured again and
Quantitative structure–activity relationship (QSAR) models were
corrosion rate and anticorrosive efficiencies were calculated.
applied to predict the ecotoxicity risk assessment (ERA). In the present
study, acute aquatic toxicity of triazoles on Daphnia magna, fish and
2.3. Electrochemical measurements green algae was predicted using the EPA’s Ecological Structure Activity
Relationships (ECOSAR) Model v.2 [58] and the 2D chemical structures
Electrochemical measurements were performed using an Autolab of 3a and 3b as input data to compare with commercials benzotriazole
PGSTAT 128 N potentiostat/galvanostat and a three-electrodes system. and 5-methyl-benzotriazole. Moreover, the bioconcentration (BCF fac
Open Circuit Potential (OCP) was monitored during 3600 s. Electro tor) and biodegradation of both molecules were predicted using ADMET
chemical Impedance Spectroscopy (EIS) was performed in the range of Predictor™ (Simulation Plus Inc., Lancaster, CA, USA) program, at pH
100 kHz-10 mHz (amplitude of 10 mV), the same potential variation to 7.4.
execute the Linear Polarization Resistance (LPR). Polarization curves
were obtained after varying the potential in the range of ±300 mV (scan 3. Results and discussion
rate of 1 mV s− 1). All measurements were carried out at the OCP in the
absence and presence of different concentrations of the potential 3.1. Synthesis and characterization
corrosion inhibitors (CI).
Synthetic route proposed to obtain triazoles compounds was pre
sented in Scheme 1 and based on the Huisgen 1,3-dipolar cycloaddition
2.4. Atomic Force Microscopy (AFM)
reaction between azide and alkyne [R. Huisgen, Kinetics and mechanism
of 1,3-dipolar cycloadditions [59,60]. The stepwise version of this
To verify the difference in the topography of the steel surface, AFM
cycloaddition with high regiosselectivity for the 1,4-disubstituted iso
was performed with a Nanosurf easy Scan 2 Controller. The images were
mer was developed by Sharpless and coworkers with the use of copper
taken after grounding the steel and after immersion for 5 h in hydro
(I) as a catalyst [61]. Briefly, the reaction of aniline (1a) or 4-nitroani
chloric acid medium without and with the presence of the maximum
line (1b) with sodium nitrite in acidic medium at 0–5 ◦ C to form dia
concentration of the inhibitors.
zonium salts was subsequently followed by aromatic electrophilic
substitution with sodium azide to obtain arylazides 2a-b (Scheme 1).
Table 1 Aromatic azides (2a-b) were obtained as brownish solids with yields
Gravimetric results at 298 K. ranging from 65% to 75%. 1-azidobenzene (2a) and 1-azido-4-nitroben
Compound Concentration (mmol Corrosion Rate (mm η θ zene (2b) arylazides 2a-b were used directly without further purifcation
L− 1 ) year− 1) (%) in next step to prevent degradation. Their chemical structures were
- 0.00 2.017 ± 0.105 0.00 0.000 confirmed by analyzing the crude product using FTIR. Analysis showed a
3b 0.13 1.182 ± 0.063 41.4 0.414 strong absorption band at 2100-2125 cm− 1, referring to the stretch vi
0.52 0.941 ± 0.074 53.3 0.533
brations of the N3 bond of the azido group.
0.91 0.660 ± 0.048 67.3 0.673
1.30 0.468 ± 0.008 76.8 0.768 The methodology for obtaining the triazoles (3a-b) involved the 1,3-
3a 0.13 0.674 ± 0.070 66.6 0.666 dipolar cycloaddition reaction between propargyl alcohol and aromatic
0.52 0.547 ± 0.052 72.9 0.729 azides previously synthesized. Copper sulfate (CuSO4) and sodium
0.91 0.401 ± 0.021 80.1 0.801 ascorbate were utilized to increasing the reaction rate and to obtain only
1.30 0.290 ± 0.029 85.6 0.856
the 1,4-regioisomers by click chemistry reaction conditions. Reactions
3
Table 2 Table 3
1,2,3-triazole derivatives reported on the literature as corrosion inhibitors. Weight Loss data at 318 and 338 K.
Compound Concentration Average Reference Temperature 318 K 338 K
(mmol L− 1) efficiency
Compound Concentration Corrosion η Corrosion η
(%)
(mmol L− 1) Rate (mm (%) Rate (mm (%)
1.00 82.0 [62] year− 1) year− 1)
- 0.00 6.059 ± 0.00 17.739 ± 0.00

0.074 0.233
1.00 82.9 [63] 3b 0.13 3.211 ± 47.0 8.663 ± 51.2
0.088 0.107
0.52 2.393 ± 60.5 6.464 ± 63.6
3.28 94.0 [36] 0.032 0.134
0.91 1.564 ± 74.2 3.974 ± 77.6
0.069 0.120
1.30 1.194 ± 80.3 2.643 ± 85.1
0.055 0.091
3a 0.13 1.812 ± 70.1 4.452 ± 74.9
0.092 0.153
2.13 81.7 [64] 0.52 1.312 ± 78.3 3.207 ± 81.9
0.101 0.085
0.91 0.851 ± 86.0 2.110 ± 88.1
0.046 0.120
1.30 0.607 ± 90.0 1.224 ± 93.1
0.013 0.044
1.30 85.6 This work
between efficiency and concentration of the compound proposed in this

work.
Most corrosion inhibitors derived from triazoles reported on the
literature [36,65–71], as you raise the temperature of the aggressive
media, have a significant drop in their anti-corrosive efficiencies. As
observed in Table 3, 3a and 3b have a completely different behaviour.
were performed under ultrasonic bath for 24h at room temperature and The corrosion rate goes from 2.017 to 6.059 to 17.739 as the tempera
were protected from light due to the photosensitivity of the aromatic ture increases from 298 to 318–338 K, respectively. For 3a, the anti
azides. After purification in a column, triazole compounds were ob corrosive efficiency shows great results even at low concentrations (from
tained as white or brownish crystals with yields ranging from 79% to 66.6% to over 70%). At the highest concentration, this organic corrosion
88%. Triazoles (3a-b) were identified using FTIR and showed the inhibitor reaches 90.0 and 93.1% at 318 and 338 K, respectively, thus
absence of stretching vibrations of the azide group and the presence of being an excellent option for industrial application in processes at high
bands related to axial deformation of the OH bond. temperatures. With the presence of a nitro group in the molecular
structure, it is also observed an improvement in the anticorrosive effi
3.2. Gravimetric studies ciency, reaching more than 50% of corrosion inhibition at 338 K in the
lowest concentration. At 1.30 mmol L− 1, 3b achieves 80.2 and 85.1%
The first test performed to evaluate the two triazole alcohols de efficiency, also being a great choice of corrosion inhibitor at different
rivatives as corrosion inhibitors was the Weight Loss Study. The data temperatures.
obtained at 298 K regarding corrosion rate (CR), anticorrosive efficiency
(η), and surface coverage (θ) are shown in Table 1. 3.3. Physical-chemical parameters
It can be observed that, for the two compounds, the increase in
concentration leads to a diminishing in the corrosion rate compared to Some isotherm theories (Langmuir, Freundlich, Flory-Higgins, Kise
the blank solution. 3a and 3b are both great corrosion inhibitors, but it is lev, Temkin, Frumkin, Dubinin-Radushkevich, Hill-de Boer) were
very clear that the addition of a nitro group (-NO2) to the aromatic ring mathematically simulated using the gravimetric results to investigate
substantially harms the anticorrosive property of this particular com which one of the adsorption process of 3a and 3b follow. It was seen that
pound. Even though 3b mitigates corrosion in a significant value at both of them fitted better the Langmuir isotherm (Eq. (1)), defined as a
lower concentrations (0.13 mmol L− 1), there is a drop of about 26% monolayer without adsorbate-adsorbate interaction [72,73].
compared to 3a. At the highest concentration (1.30 mmol L− 1), 3a is
Cinh 1
around 10% better as a CI compared to 3b, reaching 85.6% efficiency = Cinh + (1)
θ Kads
versus 76.8%.
Table 2 evidences the results obtained for similar structures of 1,2,3- Using the graphs presented in Fig. 1, via inverse value of the linear
triazole derivatives reported on the literature as corrosion inhibitors for coefficient, the adsorption constants were calculated. It is possible to
mild steel in HCl 1 mol L− 1. Comparing 3a to the first and second organic observe (Table 4) that, for both 3a and 3b, Kads increases with the raise
molecules presented in Table 2, it can be seen that our compound pre of temperature, meaning that the system is more favorable to the
sents an economy of atoms with a greater efficiency. The methoxy adsorption of organic molecules on the mild steel surface and desorption
group, as reported, does not statistically modify the anticorrosion effi of water, helping to understand the better anticorrosive efficiency at
ciency at the same concentration. The addition of an aromatic ring re higher temperatures.
quires more than 100% of the usual concentration to achieve the same It was possible to calculate the standard free energy of adsorption
82% of efficiency. On the other hand, the morpholine ring efficiently (ΔGads) using the constant values and Gibbs’ equation (Eq. (2)). It is well
improves the anti-corrosive property of that derivative although it re defined in the literature that ΔGads values less negative than − 20 kJ
quires significantly more concentration. Comparing to the molecule 3a, mol− 1 represent physisorption while ΔGads more negative than − 40 kJ
it is evident that although the efficiency has an increase of 9%, to reach mol− 1 represent chemisorption [74]. The values obtained for 3a and 3b
that, there is a 152% increase in concentration, showing the best benefit indicate a mixed-type (chemical and physical) adsorption process with
4
1
Fig. 1. Langmuir isotherm plots for 3b (left) and 3a (right) in 1 mol L− HCl.
Table 4
Thermodynamic adsorption parameters.
Compound Temperature (K) R2 Kads (L mol− 1) ΔGads (kJ mol− 1) ΔHads (kJ mol− 1) ΔSads (J K− 1
mol− 1)
3b 298 0.9924 3901.7 − 30.4 7.5 127.5

318 0.9953 5268.4 − 33.3
338 0.9938 5639.5 − 35.5
3a 298 0.9951 11711.0 − 33.1 6.3 132.5
318 0.9972 13633.3 − 35.8
338 0.9971 15639.7 − 38.4
( *) ( )
Table 5 RT ΔS − ΔH *
CR = exp exp (5)
Corrosion kinetic parameters. Nh R RT
Compound Concentration Ea (kJ A (mm ΔH* ΔS* (J K-1
(mmol L− 1) mol− 1) year− 1) (kJ mol-1) where A is the pre-exponential factor, R is the universal gas constant, N
mol-1) is Avogadro’s number, and h is Planck’s constant.
- 0.00 45.5 ± 1.85 × 42.8 ± − 95.8 ± From the results shown in Table 5, there is a slight diminishing in Ea
5.2 108 3.4 1.6 values in the presence of the organic molecules, indicating the chemi
3b 1.30 36.2 ± 1.02 × 33.6 ± − 138.3 ± sorption of a protective layer. That statement is supported by the pre-
4.9 106 2.6 2.8
exponential factor in the Arrhenius equation. As observed, A is lower
3a 30.1 ± 5.49 × 27.5 ± − 163.0 ±
5.4 104 4.1 2.0 in the solution with 3b and even lower in the solution with 3a, proving
the smaller electroactive area exposed to corrosion in the heterogeneous
reactions. Positive values of ΔH* demonstrate that the corrosion reac
predominance of chemisorption, explaining the better anticorrosive ef tion is an endothermic process, explaining the higher corrosion rates at
ficiency at higher temperatures [75]. elevated temperatures, while more negative values of ΔH* in the pres
ΔGads = − RTln(55.5 × Kads ) (2) ence of the corrosion inhibitors characterize an orderly film formed on
the metal surface, decreasing the state of disorder [77,78].
Next, the Gibbs’ function (Eq. (3)) and the graph presented in Fig. S1
were used to calculate enthalpy (ΔHads) and entropy (ΔSads) variation.
From Table 4, it is observed that ΔHads is positive for both molecules, 3.4. Atomic Force Microscopy
explaining why at higher temperatures 3a and 3b present better
corrosion efficiencies. ΔSads values are really close for both molecules, To analyze the surface topography of the mild steel at different
indicating an algebraic sum of adsorption and desorption processes [76]. moments, the Atomic Force Microscopy (AFM) was used. At first, as
shown in Fig. 2a, the marks from the grounding process with SiC abra
ΔGads = ΔHads − T × ΔSads (3)
sive paper are present in a very smooth surface. After 5 h in contact with
Regarding the corrosion kinetic parameters, the Arrhenius equation hydrochloric acid, it is possible to observe a highly attacked surface
(Eq. (4)) was used to calculate the activation energy (Ea) and the (Fig. 2b), damaged by metallic corrosion. In different experiments, in
Transition State Theory equation (Eq. (5)) was used to calculate the presence of 3a and 3b at 1.30 mmol L− 1, a much smoother surface
enthalpy (ΔH*) and entropy (ΔS*) variation, with the help of the graphs (Fig. 2c and d, respectively) is now seen when compared to the blank
displayed in Fig. S2. solution, including the presence of grounding marks, evidencing the
formation of an organic protective layer on the mild steel surface [79,
Ea
lnCR = lnA − (4) 80].
RT
To confirm this hypothesis, electrochemical measurements are
shown next. In addition, there is a segment, as shown for the first time by
5
1
Fig. 2. Atomic Force Microscopy 3D images of (a) grounded mild steel and after 5 h immersed in 1 mol L− HCl (b) without corrosion inhibitor, (c) with 1.30 mmol
L− 1 of 3b, and (d) with 1.30 mmol L− 1 of 3a.
Fernandes et al. [64], where data crossing with gravimetric results is capacitor, hence the presence of CPE (defined by Y0 and n). Table 6
discussed to ratify the adsorption of organic molecules on the surface presents the results obtained [86–88].
and formation of a protective film. It is known from the literature that the values of n can vary from − 1,
With the adsorption data, it is observed that the Kads for the 3a is representing an inductor, to 1, representing a pure capacitor. If n = 0,
triple when compared to 3b, indicating that more organic molecules are CPE is said to be a pure resistor. M. Abouchane, N. Dkhireche, M. Rbaa
adsorbed on the mild steel surface. This is evidenced in Fig. 2c and d, et al. [89] showed that higher n values in the presence of CI occur due to
where for molecule 3b a protected surface is observed but with a decrease in the heterogeneity of the surface. On the other hand, M. Rbaa
corrosion points, while for the 3a only a smooth and well protected et al. [90] reported no significant change in n value in the presence of an
surface is seen. 8-Hydroxyquinoline derivative polymer when compared to the blank
solution. In this study, it is also not seen such discrepancy in those values
in the presence of 3b and 3a, indicating that the organic compounds
3.5. Electrochemical Impedance Spectroscopy (EIS) may interact with the mild steel surface and the formed oxides, as re
ported previously by Fernandes et al. [91], maintaining the in
EIS was performed to investigate the mechanism of reaction. The homogeneity [92].
Nyquist plots (Fig. 3) for 3a and 3b present one-loop depressed semi Brug’s formula (Eq. (6)) is used to calculate the double layer
circles. The single curves indicate that kinetic of corrosion, in this case, capacitance (Cdl) when the corrosive process is controlled by slow
is controlled by electrochemical charge transfer processes and remain charge transfer in the presence of a non-ideally polarized electrode [93].
unaltered in the absence and presence of the different compounds. Due ( )(n− 1)/n
to roughness and inhomogeneity of the surface, it is possible to observe Cdl = Y0
1/n
×
1
+
1
(6)
non-perfect semicircles, in a phenomenon known as frequency disper Rs Rct
sion. [81]. From the results shown in Table 6, it is possible to observe a signif
It is well described in the literature of corrosion inhibitors that the icant drop in Cdl values from the uninhibited solution to the inhibited
diameter of the Nyquist plots is associated with the charge transfer ones. The explanation comes from the Helmholtz model (Eq. (7)) for
resistance of a certain metallic material in the presence of organic double layer capacitance. As the organic molecules adsorb on the mild
molecules in an alloy-electrolyte interface [20,82–84]. From Fig. 3, it is steel surface, forming a protective layer, they reduce the local dielectric
noticed that an increase in 3a and 3b concentrations led to larger di constant (ε) by displacing water molecules and diminish the electrode
ameters, thus indicating a higher charge transfer resistance and, surface (S) exposed to the electrolyte, while also increasing film thick
consequently, a better protection of the mild steel surface against ness (d) [94–96].
corrosion [85].
Due to the interface alloy-corrosive medium and the phenomena that Cdl =
ε0 × ε × S
(7)
occur in it, an electrochemical cell works similarly to an electrical cell. d
Thus, an electrical equivalent circuit was used to model the system and Our research group proposed in 2019 [64] a crossing data between
simulate the accurate data obtained via EIS experiments. The Randles gravimetric and electrochemical results to better understand the lower
circuit (Fig. 4) consists of a solution resistance (Rs) in series with con Cdl values with increasing inhibitor concentration. Using the Helmholtz
stant phase element (CPE) and a charge transfer resistance (Rct), that are model, a plot of double layer capacitance versus exposed surface, where
parallel to each other. Since frequency dispersion occurs, resulting in S is substituted by 1 – θ obtained in the WLS, is displayed in Fig. 5. A
non-perfect semicircles, it is not possible to use the element of a pure
6
great linear fit is observed for both 3a and 3b, suggesting that ε/d is
constant, characterizing the formation of a protective monolayer,
corroborating the Physical-Chemical Parameters from section 3.3
[97–100].
For both molecules, in the Bode Modulus (Figs. S3a and c) is possible
to see a higher total impedance at low frequencies, indicating the
adsorption on the metal surface and formation of a protective film by 3a
and 3b. In addition to that, the format of the graphs remains the same
regardless of the presence of organic molecules or their concentration,
proving that the mechanism of corrosion is not significantly altered,
corroborating the adsorption by blockage theory. From the Bode Phase
(Figs. S3b and d), higher values of the one-peak plots in the presence of
3a and 3b confirms the enhanced protection of the metal surface facing
corrosion [101,102].
As aforementioned, the Nyquist diameter is associated with charge
transfer resistance and this is proven by the results displayed in Table 6.
Higher concentrations of 3b and 3a lead to enhanced values of Rct,
reaching anticorrosive efficiency of 78.4 and 88.1%, respectively,
demonstrating the better protection of the mild steel surface.
3.6. Linear Polarization Resistance (LPR)
By varying the potential (±10 mV vs OCP) and acquiring the current

density of the system, using Ohm’s Law, it is very easy to obtain the
polarization resistance (Rp) of the mild steel surface. The data exhibited
in Table 7 show that, for both substances, higher concentrations in the
electrolyte lead to superior values of Rp, proving that those organic
molecules act as great corrosion inhibitors. Resistance values are very
similar to the ones obtained via EIS, confirming the results. The
maximum anticorrosive efficiency achieved by 3b was 78.1% and by 3a
was 87.6%, both at 1.30 mmol L− 1 [103,104].
3.7. Potentiodynamic Polarization (PP)
The polarization curves help understand where a substance acts to

suppresses corrosion: in the anodic, in the cathodic or in both branches.
In this case, it is not possible to use the Tafel extrapolation method due
to the high speed utilized to obtain the curves (1 m Vs− 1), leading to an
inconclusive assessment. Thus, PP was performed to qualitatively show
the influence of the CIs on the current density and evaluate the mech
anism of protection.
From Fig. 6, it is possible to notice that both 3a and 3b lower the
values of anodic and cathodic currents when compared to the blank
solution. So, these results indicate that the organic molecules act
inhibiting iron oxidation and hydrogen ion reduction [105,106]. That
fact is proven by the different curves obtained at different concentra
Fig. 3. Nyquist plots for the absence and presence of different concentrations of
tions of 3b and 3a, not appearing at all parallels with the blank solution,
3b and 3a (at 298 K) for mild steel in hydrochloric acid.
showing that the organic molecules affect directly both anodic and
cathodic reactions, preventing iron dissolution and impeding hydrogen
gas evolution [107].
From the results displayed in Table 7, it is noteworthy that the four
different concentrations of both molecules shifted the corrosion poten
tial (Ecorr) to values less negatives. That shift for 3b is from +9 to +29
mV and for 3a is from +9 to +26 mV. These ranges of Ecorr variation are
less than +85 mV, thus, characterizing the two triazolic alcohols as
mixed-type corrosion inhibitors [108–110].
3.8. Quantum chemical studies
Computational methods have been successfully employed to corre

late the corrosion inhibitor potential and its chemical structure [111].
Firstly, the microspecies distribution of inhibitors 3a and 3b, consid
ering the acidic medium (pH ~1) (Figs. S4 and S5), were evaluated. The
Fig. 4. Randles electrical equivalent circuit. structures of derivatives in its neutral (3a and 3b) and protonated (3a′
and 3b’) forms were investigated, since both forms may exist in acidic
medium.
7
Table 6
EIS data.
Compound Conc. (mmol L− 1) Rs (Ω cm2) CPE Cdl (μF cm− 2) Rct (Ω cm2) ɳ (%)
− 1 n − 2
Y0 (μΩ S cm ) n
Blank 1.07 ± 0.30 233.0 ± 3.5 0.906 ± 0.008 95.8 ± 11.5 135.0 ± 7.0 –
3b 0.13 0.76 ± 0.18 160.7 ± 2.0 0.890 ± 0.006 52.8 ± 8.3 219.6 ± 9.5 38.5
0.52 1.62 ± 0.26 188.0 ± 1.8 0.846 ± 0.004 43.0 ± 5.2 304.0 ± 8.3 55.6
0.91 0.87 ± 0.20 190.0 ± 2.9 0.831 ± 0.011 32.6 ± 9.3 402.7 ± 12.9 66.5
1.30 0.38 ± 0.09 168.1 ± 1.9 0.831 ± 0.006 23.6 ± 4.9 625.4 ± 20.6 78.4
3a 0.13 0.52 ± 0.10 112.6 ± 1.6 0.856 ± 0.005 21.9 ± 3.6 391.8 ± 4.8 65.5
0.52 0.40 ± 0.06 108.6 ± 3.0 0.854 ± 0.016 20.0 ± 6.7 501.7 ± 7.9 73.1
0.91 1.50 ± 0.25 98.7 ± 3.2 0.835 ± 0.009 17.4 ± 4.5 747.4 ± 6.5 81.9
1.30 0.86 ± 0.14 72.5 ± 0.7 0.862 ± 0.002 15.4 ± 1.4 1.137.4 ± 50.8 88.1
1
Fig. 5. Cdl vs (1 – θ) plots for (a) 3b and (b) 3a in 1 mol L− HCl.
obtained for 3c′ and 3d’ which are 2.291 Å and 2.293 Å. Hence, the
Table 7 nitrogen electron pairs are compromised in this protonated form, which
LPR and PP data. may hamper the interaction with the d-orbitals of iron metal [112].
Compound Conc. (mmol L− 1) Ecorr (V) Rp (Ω cm2) η (%) The reactive ability of the corrosion inhibitor is closely related to
Blank 0.00 − 0.444 ± 0.004 135.7 ± 2.9 – their frontier molecular orbitals (HOMO and LUMO) and other param
3b 0.13 − 0.416 ± 0.008 228.5 ± 6.5 40.6 eters, such as Lewis acid/base hardness and softness [46]. Thus,
0.52 − 0.415 ± 0.005 296.1 ± 1.4 54.2 different quantum chemical parameters such as frontier molecular or
0.91 0.435 ± 0.010 419.2 ± 13.1 67.6
−
bitals (HOMO and LUMO) energy band gap (ΔE) and dipole moment (μ),
1.30 − 0.429 ± 0.003 620.0 ± 15.8 78.1
3a 0.13 − 0.420 ± 0.009 403.5 ± 14.6 66.4 were computed. For the neutral triazole derivatives, HOMO density is
0.52 − 0.425 ± 0.011 509.2 ± 5.1 73.4 localized over all chemical structure. In protonated forms, with the
0.91 − 0.435 ± 0.003 711.1 ± 22.2 80.9 electron pair of the nitrogen atom compromised, the HOMO density is
1.30 − 0.418 ± 0.008 1089.8 ± 20.7 87.6 concentrated on the benzene ring, except for 3b′ which has the
electron-withdrawing nitro substituent. This substituent drastically
Results obtained via DFT calculations showed that, as expected, the changes the nucleophilic profile of the molecule and, consequently, its
rigid skeleton is maintained in both neutral and protonated forms due anticorrosive property (Fig. 7).
the conjugated pi-system (Fig. 7). The same pattern was observed for Regarding HOMO and LUMO energies, high EHOMO values involve a
two additional triazoles reported as corrosion inhibitors (Table 2) [44, trend of an organic compound in donating electrons to empty d-orbital
45]. These compounds containing methyl and methoxy groups at para of the metal surface atom. In contrast, low ELUMO indicates a tendency of
position, namely 3c and 3d, respectively, were also investigated in an organic compound to accept electrons from an occupied orbital of the
attempt to obtain better correlations between the electronic effects of metal atom. The presence of electron-donating substituents on aromatic
different substituents on aromatic ring and the anticorrosive properties ring, as CH3 (3c) and OCH3 (3d) causes an increase on HOMO energy of
of the triazole derivatives. these derivatives (− 6.84 and − 6.47 eV, respectively) in comparison to
For all derivatives studied (3a-3d, R = H, p-NO2, p-CH3 and p-OCH3, non-substituted compound 3a (− 7.05 eV) (Table 8). In the same direc
respectively), different orientations were adopted for the hydroxyl tion, derivatives 3c and 3d present higher LUMO energy in comparison
group when comparing their neutral and protonated forms (Fig. 7). In to 3a (− 1.44, − 1.28 and − 1.56 eV respectively). Additionally, the
the protonated forms, an intramolecular hydrogen bond is observed presence of a strong electron-withdrawing group causes a decreasing on
between the oxygen of the hydroxyl group and the hydrogen of pro this descriptor. In fact, the LUMO energy of 3b is the mostly affected due
tonated nitrogen from triazole ring with distances of 2.288 Å and 2.279 the introduction of NO2 group (− 3.27 eV). This same tendency was
Å, for 3a′ and 3b′ respectively. These values are similar to those observed for the protonated forms of triazole derivatives (3a′-3d′),
showing the importance of these substituents in modulation of HOMO-
8
Fig. 6. Polarization curves for the absence and presence of different concentrations of 3a and 3b (at 298 K) for mild steel in hydrochloric acid.
Fig. 7. Optimized structures with dipole vector, HOMO coefficient orbital of triazole derivatives, in its neutral (3a-3d) and protonated (3a′-3d′) forms.
Table 8
Chemical parameters of triazole inhibitors 3a-3d (R = H, p-NO2, p-CH3 and p-OCH3) in its neutral and protonated forms.
EHOMO (eV) ELUMO (eV) ΔE I A μ χ η ω
3a − 7.05 − 1.56 5.49 7.05 1.56 4.18 4.30 2.75 3.38
3b − 7.65 − 3.27 4.38 7.65 3.27 3.16 5.46 2.19 6.81
3c − 6.84 − 1.44 5.40 6.84 1.44 4.76 4.14 2.70 3.17
3d − 6.47 − 1.28 5.19 6.47 1.28 4.91 3.88 2.60 2.90
3a’ − 10.87 − 6.12 4.75 10.87 6.12 5.11 8.49 2.38 15.14
3b’ − 11.24 − 6.66 4.58 11.24 6.66 14.81 8.95 2.29 17.49
3c’ − 10.41 − 5.99 4.42 10.41 5.99 6.10 8.20 2.21 15.25
3d’ − 9.72 − 5.88 3.84 9.72 5.88 6.79 7.80 1.92 15.84
LUMO energy orbitals. Since our experimental results revealed 3a and 3b and 3d present a dipole moment vector pointed to triazole moiety. As
3b with great anticorrosive potential, 85.6% and 76.8% respectively, expected, an opposite behavior is observed for 3b, which vector is
the data suggests that the HOMO-LUMO energies is not the only pointing to aromatic ring. In addition, all protonated derivatives present
parameter related to a better inhibition property. the vector pointed to substituted aromatic ring. Still considering the
The dipole moment provides information about molecular electronic dipole descriptor, 3b present the lower value (3.16 Debye) compared to
distribution and is reported as an important descriptor for the anticor other triazole derivatives. When comparing all protonated forms, the
rosive property [113]. Considering their neutral forms, derivatives 3a, greater value is observed for 3b’ (14.81 Debye). This behavior may be
9
Fig. 8. Molecular Electrostatic Potential map (MEP) of the triazole derivatives 3a and 3b generated in the energy range of − 160 to 220 kJ/mol.
disposed during toxicological tests [114]. In silico toxicology prediction

Table 9
was conducted in attempt to assess more information about the harmful
Concentrations (mg/L) and Bioconcentration factor (BCF) predicted for triazoles
effects caused by triazoles on the aquatic environment [52]. The ECO
3a and 3b using ECOSAR and ADMET Predictor programs. Acute and chronic
effects were considered. BT: benzotriazole; 5-MeBT: 5-methyl-benzotriazole.
SAR software, considered as one of the best reliable programs to esti
mate aquatic toxicity [115–117], was used to calculate the toxicity of 3a
Endpoints 3a 3b BT 5-MeBT
and 3b in different organisms as Daphnia (48h, LC50), fish (96h, LC50)
Daphnia (LC50, 48 h) 300.65 486.28 244 96.3 and green algae (96h) for both acute and chronic tests, as shown in
Fish (LC50, 96 h) 922.48 1606.73 40.7 21.6
Table 9.
Green Algae (EC50, 96 h) 31.49 38.45 8.19 4.82
Daphnia (chronic) 37.54 63.23 3.86 1.94
It should be highlighted that the organisms studied were more sen
Fish (chronic) 1.51 2.44 4.61 2.13 sitive to 3a, which implies in a reduction of toxicity by the introduction
Green Algae (chronic) 5.65 8.26 1.53 1.05 of nitro substituent. Studies conducted by Madeira and coworkers with
BCF 2.27 2.53 1.78 2.095 two 1,2,4-triazole-based derivatives indicated that the compound con
taining the nitro group is less toxic to aquatic organisms when compared
attributed to the presence of p-NO2 substituent, which change signifi to its amine analogue [118].
cantly the electronic profile of the molecule (Fig. 7, Table 8). The environmental persistence was evaluated by the bio
The HOMO-LUMO descriptors play an important role on reactivity of concentration and biodegradation of the corrosion inhibitors. The bio
inhibitors and can be used to calculate different parameters, such elec concentration is measured by bioconcentration factor (BCF) which is the
tronegativity (χ) and hardness (η), which in turn are employed to obtain partition coefficient between fish tissues and environmental water at
the electrophilicity (ω). As expected, electrophilicity value results are steady state. The BCF obtained for 3a and 3b were 2.27 and 2.53,
dependent of the electronic density over the triazolic derivatives, which respectively (Table 9), suggesting that the compound with nitro sub
change according to the group attached over the ring. Derivative 3b has stituent is easier absorbed by organisms when present in the environ
the highest value of ω. This result suggests that the presence of the NO2 ment. Furthermore, BT and 5-MeBT present BCF values lower than 3a
group makes it more susceptible to receiving electrons through π* back- and 3b. Finally, regarding the biodegradation prediction, which in
bonding from the metal surface. dicates the likelihood of biodegradation in the environment expressed as
The molecular electrostatic potential maps (MEPs) play an important relative biological oxygen demand, our analysis indicated that none of
role on interaction between different species. These color-coded iso the triazoles is biodegradable.
surface values provide an indication of the overall molecular size and Considering the Daphnia acute toxicity, the LC50 values predicted
location of negative (red) and positive (blue) electrostatic potentials. were 300.65 mg/L and 486.28 mg/L for 3a and 3b, respectively,
The MEPs are in accordance with the dipole vector, showing that the showing that the non-substituted triazole compound is more toxic when
presence of p-NO2 substituent clearly affect the electronic profile of 3b compared to its nitro analogue. Having been approximately 250 mg/L
(Fig. 8), which implies on interaction between the inhibitor and the the maximum concentration of both corrosion inhibitors, the calcula
metal surface. The presence this substituent also causes a reduction of a tions suggest that there would be no problems related to Daphnia with
negative potential over the triazole ring. As expected, this feature is not the usage of those molecules. Benzotriazole (BT) and 5-methyl-benzo
observed in other derivatives, and implies in a decreasing of the triazole (5-MeBT) were also used in this analysis, since they are
adsorption potential caused by 3b. commonly employed as corrosion inhibitor. For these compounds, the
Since results obtained from our experimental techniques indicated LC50 predicted were 244 mg/L and 96.3 mg/L, respectively, thus indi
the best inhibition performance for 3a (85.6%, R = H) in comparison to cating their toxicity as well other triazole-based compounds. Seeland
3b (76.8%, R = p-NO2), our data point out the presence of this group as and coworkers evaluated the toxicity of benzotriazoles into aquatic or
important factor that not favors the anticorrosive efficiency of these ganisms [119]. The authors obtained EC50 values of 15.8 mg/L and 8.58
triazole derivatives (Table 2). mg/L (D. galeata) and 107 mg/L and 51.6 mg/L (D. magna) for BT and
5-MeBT, respectively. Since the model implemented in ECOSAR pro
gram is composed to different species, discrepancies into predictions are
3.9. In silico ecotoxicological risk assessment expected. The results indicated a pattern, since 5-MeBT was predicted to
me more toxic than BT; moreover, one may infer that these compounds
In silico toxicology tools are referred as green toxicology since they are more toxic than 3a and 3b derivatives.
reduce animal testing as well as the amounts of chemicals used and The same pattern was observed for green algae acute toxicity where
10
Fig. 9. Schematic representation of the possible adsorption mechanism of 3b and 3a.
LC50 values obtained for 3a and 3b were 31.49 mg/L and 38.45 mg/L, 338 K, proving to be better CIs at higher temperatures. Both molecules
respectively (Table 9). These concentrations are higher than those pre followed the Langmuir adsorption theory and physical-chemical pa
dicted for BT and 5-MeBT, which concentrations were 8.19 mg/L and rameters point to chemisorption. AFM micrographs depicted smoother
4.82 mg/L. Moreover, this prediction agrees with experimental results surfaces in the presence of the two compounds and suggested the for
demonstrating that benzotriazoles are harmful for several algal species, mation of a protective film. Data crossing between gravimetric and
such as D. subspicatus and S. capricornutum [119,120]. electrochemical measurements confirmed the presence of a monolayer
The acute toxicity on fish showed that 3b may be almost 2-fold less protective barrier and the polarization curves characterized the two
toxic for fish than 3a. Despite this, the two molecules were used at a corrosion inhibitors as mixed-type. Theoretical calculations supported
maximum concentration well below the determined values for fish and confirmed experimental results and in silico ecotoxicity prediction
toxicity, suggesting that both compounds can be used in the off-shore oil suggested that both 3a and 3b are harmless to Daphnia and fish in the
and gas industry, for example, being harmless in aquatic environments. maximum concentration used.
For this endpoint, the predicted LC50 values for BT and 5-MeBT were
40.7 mg/L and 21.6 mg/L, respectively. These results are in line with Data availability
experimental tests with fathead minnow (P. promelas) conducted by
Pillard and coworkers [48]. The raw/processed data required to reproduce these findings cannot
be shared at this time due to legal or ethical reasons.
3.10. Corrosion inhibition mechanism
CRediT authorship contribution statement
The discussions found in literature for this topic argue that organic
Caio Machado Fernandes: Investigation, Validation, Data curation,
molecules act adsorbing on the metal surface, forming a protective layer
and, Writing – original draft. Marcos V. Palmeira-Mello: Software,
and diminishing the corrosion phenomenon. The experimental mea
Investigation, and, Writing – original draft. Mylena C. Leite: Investi
surements and theoretical studies performed at this work demonstrate
gation, Validation, and, Writing – original draft. Joanna A. Macena
just what literature discusses the most, and the adopted adsorption
Oliveira: Software, and, Investigation. Iago I. Martins: Investigation,
mechanism related to the interactions between the inhibitor species and
Validation, and, Data curation. Rebeca G. de Sá: Investigation, and,
the active centers on the steel surface can occur via [121,122]:
Validation. Lethicia A. de Almeida: Investigation, and Validation.
Alessandra M.T. Souza: Conceptualization, Software, and, Writing –
• Physical adsorption between the protonated nitrogen of the triazole
review & editing, and, Supervision. Vinicius R. Campos: Conceptuali
ring of 3b and 3a with Cl− anions attracted to the mild steel surface
zation, Writing – original draft, Writing – review & editing, and .
by Fe2+ cations originated due to corrosion.
Eduardo Ariel Ponzio: Conceptualization, Writing – review & editing,
• Chemical adsorption due to n and π-electrons from N, O, and aro
and .
matic rings present in 3b and 3a with vacant d orbitals from Fe
present in the mild steel composition.
Declaration of competing interest
• In addition, π backbonding (also known as retrodonation) can occur
between aromatic ring of those two molecules with occupied d or
The authors declare that they have no known competing financial
bitals from Fe present in the mild steel composition.
interests or personal relationships that could have appeared to influence
the work reported in this paper.
With that in mind, Fig. 9 exhibit the different ways 3b and 3a can
interact with the mild steel surface in 1 mol L-1 HCl environment and
Acknowledgements
form a protective barrier on the metal surface that significantly mitigate
corrosion from happening.
C.M.F. would like to thank Conselho Nacional de Desenvolvimento
Científico e Tecnológico (CNPq) for the scholarship received. E.A.P
4. Conclusions acknowledge Fundação de Amparo à Pesquisa do Estado do Rio de
Janeiro (FAPERJ, E-26/102.971/2012 and E-26/111.407/2013) for all
Two triazolic alcohols (1-phenyl-1H-1,2,3-triazole-4-yl)methanol their support. This study was financed in part by the Coordenação de
and (1-(4-nitrophenyl)-1H-1,2,3-triazole-4-yl)methanol) were synthe Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Finance
tized and tested by different techniques as corrosion inhibitors for 1020 Code 001.
mild steel in acidic media (HCl 1 mol L− 1). The two compounds are great
corrosion inhibitors for mild steel in acidic media, with an average
maximum efficiency of 77.8 and 87.1%, respectively, at 1.30 mmol L− 1
via WLS, EIS and LPR at 298 K. 3b and 3a reached 85.1 and 93.1% at
11
Appendix A. Supplementary data experimental and theoretical study, Colloids Surf. A Physicochem. Eng. Asp. 643
(2022), 128745.
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Materials Chemistry and Physics 290 (2022) 126508

Contents lists available at ScienceDirect

Materials Chemistry and Physics

Corrosion inhibition and ecotoxicological assessment of

• Synthesis of triazolic alcohols and eval

- 0.00 6.059 ± 0.00 17.739 ± 0.00

between efficiency and concentration of the compound proposed in this

3b 298 0.9924 3901.7 − 30.4 7.5 127.5

3.6. Linear Polarization Resistance (LPR)

By varying the potential (±10 mV vs OCP) and acquiring the current

3.7. Potentiodynamic Polarization (PP)

The polarization curves help understand where a substance acts to

3.8. Quantum chemical studies

Computational methods have been successfully employed to corre

disposed during toxicological tests [114]. In silico toxicology prediction

Fig. 9. Schematic representation of the possible adsorption mechanism of 3b and 3a.

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Exotox

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Exotox

Uploaded by

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Share this document

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Did you find this document useful?

Is this content inappropriate?

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Materials Chemistry and Physics 290 (2022) 126508

Contents lists available at ScienceDirect

Materials Chemistry and Physics

Corrosion inhibition and ecotoxicological assessment of

• Synthesis of triazolic alcohols and eval­

- 0.00 6.059 ± 0.00 17.739 ± 0.00

between efficiency and concentration of the compound proposed in this

3b 298 0.9924 3901.7 − 30.4 7.5 127.5

3.6. Linear Polarization Resistance (LPR)

By varying the potential (±10 mV vs OCP) and acquiring the current

3.7. Potentiodynamic Polarization (PP)

The polarization curves help understand where a substance acts to

3.8. Quantum chemical studies

Computational methods have been successfully employed to corre­

disposed during toxicological tests [114]. In silico toxicology prediction

Fig. 9. Schematic representation of the possible adsorption mechanism of 3b and 3a.

You might also like

• Synthesis of triazolic alcohols and eval

Computational methods have been successfully employed to corre