Journal of Molecular Liquids 332 (2021) 115852

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Green synthesis of corrosion inhibitor with biomass platform molecule:

Gravimetrical, electrochemical, morphological, and theoretical
investigations
Zhan Chen a, Ahmed A. Fadhil a,b, Tianqi Chen a, Anees A. Khadom b,⁎, Chaoyang Fu a,⁎, Noor A. Fadhil c
a
Hubei Key Laboratory of Materials Chemistry and Service Failure, Key Laboratory of Materials Chemistry for Energy Conversion and Storage, Ministry of Education, School of Chemistry and
Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
b
Department of Chemical Engineering, College of Engineering, University of Diyala, Baquba 32001, Diyala governorate, Iraq
c
Department of Biochemistry, Acharya Nagarjuna University, Nagarjuna Nagar, Guntur, India

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

Article history: Considering the concept of green chemistry and the vision of human sustainability, a new corrosion inhibitor
Received 27 November 2020 named N1-(2-aminoethyl)-N2-(2-(2-(furan-2-yl)-4,5-dihydro-1H-imidazol-1-yl) ethyl) ethane-1,2-diamine
Received in revised form 27 February 2021 (NNED) is synthesized from biomass platform molecules. Both weight loss and electrochemical measurements
Accepted 4 March 2021
demonstrated that the corrosion inhibitor had good anti-corrosion performance for carbon steel in 1 M HCl me-
Available online 9 March 2021
dium, with inhibition efficiency higher than 90% at lower level of inhibitor concentration (5 ppm). The adsorption
Keywords:
of NNED on the steel surface was spontaneous and obeys the Langmuir adsorption isotherm. The corrosion mor-
Corrosion inhibitor phology was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Force-distance
Biomass resource curve directly quantified the adhesion force between the adsorption films and the metal surface. Quantum chem-
Green chemistry ical calculation and molecular dynamics simulation were applied to study the corrosion inhibition mechanism.
Electrochemical measurement © 2021 Elsevier B.V. All rights reserved.

1. Introduction
With the exhaustion of non-renewable fossil energy and the deteri-
oration of the human living environment caused by overexploitation of
nature, the search for alternative resources to achieve sustainability has
attracted widespread attention [1,2]. Biomass energy has a tendency to
become one of the most promising resources in the 21st century due to
its advantages of renewable, low pollution and wide distribution [3,4].
Nowadays three common methods of converting biomass into fuel
and chemicals; gasification, pyrolysis and hydrolysis, after simple treat-
ment with these methods, a series of derivative molecules can be ob-
tained, which is so referred to as biomass platform molecules (BPMS)
[5,6]. The analysis and screening of these platform molecules was orig-
inally implemented by the U.S. Department of Energy in 2004, including
sugars (glucose and xylitol), polyols (sorbitol and xylitol and Glycerol),
furan (furfural and 5-hydroxymethyl furfural) and acids (succinic acid,
levulinic acid, lactic acid) [7,8]. The selection mainly considers two indi-
cators: the potential of molecules to be converted into fuels and
chemicals and the technical availability of commercial industrialization.
At present, there are many researches on the application of biomass in
corrosion inhibitors. Fadhil et al. [9] studied the inhibitory action of Por-
tulaca grandiflora extracts on the corrosion of mild steel in acidic media.
⁎ Corresponding authors.
E-mail addresses: aneesdr@gmail.com (A.A. Khadom), cyfu@hust.edu.cn (C. Fu).
Yaro et al. studied the garlic powder as a corrosion inhibitor in hydro-
chloric acid through a combination of theoretical calculations and
experiments [10]. The above research provides new ideas for the prep-
aration of green corrosion inhibitors, but there are still limitations in the
low yield of extracts and the poor corrosion inhibition performance. The
reason for the low yield is that the extraction technology only takes
the advantage of the trace amounts of natural product ingredients in
the plant such as flavonoids, alkaloids, polysaccharides, volatile oils,
quinones, terpenoids, etc. Lignocellulose with the largest proportion
has not been utilized.
The application of corrosion inhibitors is one of the most practical
and effective methods in metal cleaning, pickling, and the oilfield acid-
ification to protect metal corrosion. Most of industrial equipment were
constructed from steel and its alloys, because it is a mechanically effec-
tive alloy and low-cost. During the use of carbon steel in some pro-
cesses, corrosion products and salt deposits accumulated on steel
surface. The 1 M hydrochloric acid (HCl)solution was used to deposit re-
moval [11–13]. The carbon steel surface is heavily affected by HCl, and
this damage is responsible for high-cost economic restoration and envi-
ronmental issues [14–15]. Pioneering efficient, local, economic and en-
vironmentally friendly inhibitors in corrosion science is currently very
important for solving corrosion problems in the chemical industry
[16,17]. In recent years, many corrosion inhibitors with good perfor-
mance have been synthesized, but they are all synthesized with chem-
ical or petrochemical route [18–20], and the result of research

https://doi.org/10.1016/j.molliq.2021.115852
0167-7322/© 2021 Elsevier B.V. All rights reserved.
Z. Chen, A.A. Fadhil, T. Chen et al.
indicates that most of them have inhibition efficiency in low tempera-
ture medium [21–24]
Alibakhshi et al. [25] investigated the inhibition performance of
Glycyrrhiza glabra extract as a green corrosion inhibitor for steel corro-
sion in 1 M HCl acid. Experimental results showed that the inhibitor
acted as a mixed-type inhibitor with maximum inhibition efficiency of
88% at 800 ppm. Sulaiman et al. [26] studied the performance of citrul-
line (CE), quercetin (QN), and bonducellin (BN) as green compounds.
Based on the obtained theoretical results, the order of inhibition was
QN > BN > CE. Naseri et al. [27] investigated the inhibition action of
Clopidogrel as a green organic molecule for mild steel in sulfuric acid so-
lution. Adsorption studies revealed that Clopidogrel adsorbs both phys-
ically and chemically above the mild steel surface. Most of corrosion
inhibitors are efficient at moderate temperature. When the temperature
rises to 80 °C, the inhibition performance dramatically decreases or ser-
vice failure, the corrosion inhibitor reported in this article still maintains
a corrosion inhibition efficiency over 90% at high temperature.
The purpose of the present work is to promote the utilization of lig-
nocellulose renewable resources in plants in the form of biomass plat-
form molecules, and the main strategy for this research is to use it to
synthesize high-performance corrosion inhibitor. The influence of N1-
(2-aminoethyl)-N2-(2-(2-(furan-2-yl)-4,5-dihydro-1H-imidazol-1-yl)
ethyl) ethane-1,2-diamine (NNED) as a novel/green inhibitor was stud-
ied in the acidic corrosive media using the gravimetrical and electro-
chemical analysis. Surface morphology and characterization methods
such as FT-IR, AFM, and SEM/EDS, were employed to explore the struc-
ture of the inhibiting layer on the steel surface. In addition, quantum
chemical calculations were used as a theoretical tool for understanding
the inhibition mechanism.
2. Experimental work
2.1. Materials
Q235 carbon steel was purchased from Shandong yangxinshengxin
technology Co. LTD (China) and the corresponding chemical com-
positions (wt%) were C (0.17%), Si (0.19%), Mn (0.14%), P (0.04%),
S (0.04%) and Fe (balance). It was used as a working electrode (test sam-
ple) for weight loss and electrochemical measurements. Before each ex-
periment, the working electrode was firstly polished with emery papers
with grades between 400 and 1500, then it was ultrasonically washed
by distilled water and acetone, finally it was desiccated with electric
dryer.
2.2. Synthesis of the inhibitor (NNED)
N1-(2-aminoethyl)-N2-(2-(2-(furan-2-yl)-2,5-dihydro-1H-imida-
zol-1-yl) ethyl) ethane-1,2-diamine was synthesized in the laboratory
Fig. 1. The synthetic route and the molecule structure of NNED inhibitor.
2
Journal of Molecular Liquids 332 (2021) 115852
and the molecular structure was shown in Fig. 1.Firstly, furan-2-
carboxylicacid (40 mmol, 4.847 g) dissolved in toluene (40 mL), then
it was added to tetraethylenepentamine (40 mmol, 4.885 g). In this re-
action toluene served as solvent and water-carrying agent. Then, the
mixture was heated to 120 °C and refluxed for 4 h, the carboxylic acid
reacts with the amine to produce amide, toluene formed azeotrope
with produced water and it was distilled of the reaction system so
that the reaction equilibrium moved to the right. Finally, the mixture
was heated to 220 °C for dehydration and cyclization, and then the re-
action was almost complete and generated a reddish-brown viscous
liquid. The liquid product is purified under reduced pressure in a
rotary evaporator.
2.3. Weight loss measurements
Weight loss method is the most traditional and direct method to
evaluate the performance of corrosion inhibitors [28,29]. In this experi-
ment, Q235 carbon steel with the dimensions of 76 mm × 13 mm
× 1.5 mm (~ 22.4 cm2) was used, the sample was firstly degreased
with ethanol and acetone, then dried by hot air and weighed accurately
(precision 0.1 mg). Then, the sample was suspended and immersed in
450 mL of 1 M hydrochloric acid solution with different concentration
of inhibitor for 8 h at temperatures of 40, 50, 60 and 80 °C. After the ex-
periments the sample was taken out and rinsed with deionized water.
The corrosion product was removed with pickling solution (10% hydro-
chloric acid solution +1% urotropine), and then successively washed
with deionized water, absolute ethanol, acetone, then weighed and
the average corrosion rate was calculated. Each test was repeated in tri-
ple and the average corrosion rate value was taken.
2.4. Electrochemical measurements
The electrochemical measurement was conducted using CS350 elec-
trochemical workstation produced by Wuhan Corrtest company. Corro-
sion cell with three-electrode consisting of working electrode, auxiliary
electrode, and reference electrode was employed for electrochemical
measurements. NNED at concentrations of 0, 5, 10, 20, 40 and 60 mg/L
(ppm) was added to the 1 M HCl corrosive solution. The working elec-
trode is Q235 steel sealed with epoxy resin, a circular working face
with a diameter of 1 cm (working area of 0.785cm2) was exposed to cor-
rosive media. The reference electrode was a saturated calomel electrode
(SCE) with fine Luggin capillary close to the working electrode surface
to minimize Ohms' potential resistance, and a platinum sheet was
used as an auxiliary electrode. Before each electrochemical test, the sur-
face of the working electrode was polished by 400 to 1500 meshes of
emery paper and then it was washed with distilled water. The working
electrode was immersed in the test solution for 20 min at an open circuit
potential until a steady state was obtained. Tafel polarization test was
Z. Chen, A.A. Fadhil, T. Chen et al. Journal of Molecular Liquids 332 (2021) 115852

conducted by changing the voltage from −200 to +200 mV against Table 1

open circuit potential, with scan rate of 0.5 mV/s. Weight loss data for steel in 1.0 M HCl acid with different concentrations of NNED at dif-
ferent temperatures.
The impedance spectra data (EIS) was evaluated using the
ZSimpWin data analyzer software, which provided straightforward C (mg/L) T (°C) Corrosion rate (g m−2 h−1) η(%)
equivalent circuit model fitting. A 10 mV sine wave with frequency Blank 40 35.08 –
range extending from 0.1 Hz to 100 MHz was applied for the impedance 5 2.56 92.7
measurements against open circuit potential. All the measurements 10 2.15 93.9
20 1.5 94.8
were performed at temperatures of 40, 50, 60, and 80 °C.
40 1.63 95.4
60 1.32 96.2
Blank 50 67.12 –
2.5. Surface morphology measurements
5 5.52 91.8
10 3.81 94.2
Corrosion morphology observation was implemented to analyze and 20 3.88 94.3
judge the degree of metal corrosion [30,31]. Q235 carbon steel sheet 40 3.38 95.1
was placed in corrosive medium in the presence and absence of the cor- 60 2.38 96.4
Blank 60 231.23 –
rosion inhibitor, then take it out and rinse with a small amount of dis- 5 14.67 93.7
tilled water and then put it in an oven to dry, and then atomic force 10 13.43 94.2
microscope (AFM) and scanning electron microscope (SEM) were ap- 20 12.07 94.8
plied to observe the microscopic corrosion morphology of metal surface. 40 9.19 96.0
60 9.11 96.1
Shimadzu SPM 9700–Japan and Hitachi SU 8010 – Japan apparatuses
Blank 80 594.7 –
were used for the AFM and SEM measurements, respectively. Both 5 60.11 89.9
SEM and AFM were carried out before and after immersion of steel in 10 51.08 91.4
1 M HCl at 60 °C for 2 h in the absence and presence of NNED (60 ppm). 20 47.81 92.0
40 41.76 92.9
60 41.93 93.0
3. Results and discussion

3.1. FT-IR measurements and inhibitor molecular structure

FT-IR measurements were performed to identify the functional
groups present in the chemical structure of NNED, which ranged
from 400 to 4000 cm−1. Fig. 2 demonstrated that the product contains
an imidazoline ring and an amino group. The peak near 1650.83 cm−1
is the C=N stretching vibration on the imidazoline ring which
proves that the main product has been successfully synthesized,
1357.81 cm−1 is C–N single bond stretching vibration. The peaks near
2824.26 and 2973.17 cm−1 are evidence of CH2 functional group (C–H
stretching vibration peak). The stretching vibration peak of the N–H
bond was observed at 3429 cm−1. These observations clearly reveal
our successful synthesis of inhibitor molecules.
3.2. Corrosion inhibitor performance evaluation
3.2.1. Weight loss measurements
Table 1 summarizes the consequence of weight loss experiment in-
volved Q235 carbon steel corrosion in 1.0 M HCl solution at various
temperatures and concentrations of NNED. The corrosion rate values
were estimated using below equation:
Δm
CR ¼ ð1Þ
St
In the formula, CR is the corrosion rate of carbon steel sample;
Δm (g) represents the mass difference of the sample before and after
corrosion; S (m2) is the surface area of the sample; t (h) is the corrosion
time. Corrosion inhibition efficiency (η) can be calculated according to
the following formula:
C oR −C R
η¼  100% ð2Þ
C oR
Where CoR and CR respectively refer to the rate of corrosion without
and with corrosion inhibitor. The weight loss data indicated that the
corrosion rate increases with the elevated temperature, whereas de-
creases greatly after adding corrosion inhibitor, which manifests that
it has a good protective effect on carbon steel. In addition, it was ob-
served that the corrosion inhibition excessed 90% when the concentra-
tion is low as 5 ppm. According to our information, this efficiency has
not been reported in the literature, suggesting that the synthetic inhib-
itor with a good application prospect and may produce some economic
benefits in the future.

3.2.2. Tafel polarization measurement

Fig. 2. FT-IR spectra of the NNED.
Polarization curves of Q235 steel in 1 M HCl solution containing dif-
ferent concentrations of NNED at different temperature were evaluated.
The test data were shown in Fig. 3a–d. The corresponding fitting param-
eters are shown in Table 2, as can be seen from it, the corrosion current
density of the cathode and the anode decreased after the addition of the
corrosion inhibitor, indicating that NNED simultaneously inhibited the
electrode reaction process of the two electrode. The rate of reduction
of H+ at the cathode decreased after the adsorption of NNED on the
electrode surface. At the same time, the dissolution of the metal at the
anode is hindered. Tafel polarization curves shows that the anode
Tafel slopes (βa) increases significantly in the presence of NNED while
the cathodic ones (βc) do not change clearly, which suggests that

3
Z. Chen, A.A. Fadhil, T. Chen et al.
Fig. 3. Polarization curves for Q235 steel in 1 M HCl solution without and with different concentrations of NNED at different temperatures.
NNED mainly inhibits the anodic process to more extent, and the inhibi-
tion efficiency was calculated according to Eq. (3) [32].
Iocorr −Icorr
η¼  100%
Iocorr
where I0corr and Icorr represents the steel corrosion current densities
of uninhibited and inhibited acidic solution, respectively. According to
the polarization curves of each temperature, with the addition of corro-
sion inhibitor, both cathode and anode processes are inhibited. More-
over, the corrosion potential has no obvious positive or negative
shifting trends, so the corrosion inhibitor is a mixed type of corrosion
inhibitor. With the increase of NNED concentration, the corrosion inhi-
bition efficiency presents an increasing trend, which is consistent with
the weight loss experiment. Furthermore, NNED still has good protec-
tion effect at 80 °C, which is rarely reported in the literature.
3.2.3. Electrochemical impedance measurement
Electrochemical impedance measurement proves a powerful tool for
exploration of the microscopic process of electrode reactions [33,34].
The impedance spectrums were tested in 1 M HCl media with and with-
out different concentrations of NNED. Nyquist plots for different
temperature are shown in Fig. 4a–d, while Bode plots for different
Journal of Molecular Liquids 332 (2021) 115852
temperature are shown in Fig. 5a–d. As can be seen, the shape of the im-
pedance diagram remains unchanged, indicating that the corrosion
mechanism has not changed before and after the addition of NNED,
and the impedance diagram is not a perfect semicircle, which may be
ð3Þ
due to the frequency dispersion caused by the roughness and uneven-
ness of the electrode surface [35,36]. Analysis of the impedance spec-
troscopy reveals that the charge transfer process is the main control
step of the electrode process rather than diffusion, the diameter of the
impedance curve tends to increase with the increase of NNED concen-
tration at different temperatures, which manifests that the charge trans-
fer process is blocked, demonstrating that the corrosion inhibitor has a
good corrosion inhibition effect on carbon steel. One-time constant
was observed in the Bode plots (Fig. 5). At each temperature, the imped-
ance modulus over the entire frequency range increased as increasing
NNED concentrations. Additionally, the frequency ranges with the max-
imum phase angle became larger as the concentration of NNED in-
creased. These results validated the effective inhibitive ability of the
examined NNED for the corrosion of steel in acidic solution.
To evaluate the corrosion inhibition performance of NNED, view
software was adopted to fit the measured impedance data, and the
equivalent circuit was shown in Fig. 6. In this equivalent circuit, Rs and
Rp represent the resistance of the solution and the charge transfer polar-
ization resistance of the metal/solution interfacial corrosion reaction,
4
Z. Chen, A.A. Fadhil, T. Chen et al. Journal of Molecular Liquids 332 (2021) 115852

Table 2 respectively. For metals dissolution process in corrosive environments,

Polarization curve fitting parameters of NNED in 1 M HCl under different conditions. replacement of charge transfer resistance (Rct) by Rp is gives a better ap-
C(ppm) T(°C) Icorr Ecorr βa βc η proximation. Since Rp contains several accompanying resistances along
(mA/cm2) (mV) (mVdec−1) (mVdec−1)
with Rct, such as film (Rf), pore (Rpr), and diffusion resistances (Rd), re-
spectively. In other words, Rp = Rct + Rf + Rpr + Rd.
Blank 25.01 −505 146.6 164.9 –
Since the electrode surface is difficult to achieve ideal smooth and
5 2.31 −476 78.3 124.3 89.3
10 40 1.47 −477 75.4 121.8 94.1 flat state, the double layer capacitance (Cdl) value is influenced by sur-
20 1.46 −476 75 121.6 94.2 face defects, which is simulated by a constant phase element (CPE), re-
40 1.44 −486 95.5 109.9 94.2 placing capacitors with CPE elements can more accurately match the
60 1.41 −482 109.6 119.4 94.3 electrode reaction process [37]. The impedance and admittance of CPE
Blank 33.41 −508 135 206.7 –
5 4.63 −510 100.5 124.3 86.2
are calculated as follows [38]:
10 50 4.27 −484 50.9 154.9 87.4
−518
1
20 3.29 110.9 90.20 90.4 Z CPE ¼ ð5Þ
40 2.18 −493 79.9 128.7 93.7 Y o ðjωÞn
60 1.86 −489 70.8 123.3 94.6
Blank 71.7 −509 184.1 210.6 –
Y CPE ¼ Y o ðjωÞn ð6Þ
5 20.02 −518 116.9 129.2 72.1
10 60 15.15 −500 109.5 148.8 78.9
20 13.33 −504 105.6 145.2 81.4 Where Yo is the magnitude of the CPE, j represents the imaginary
40 10.13 −508 107.2 128.3 85.9 root, ω is the angular frequency, n represents a deviation parameter
60 3.77 −509 66.9 128.9 94.8 and it can quantify different physical phenomena such as surface un-
Blank 125.66 −492 283.8 283.6 –
5 34.25 −505 78.1 75.3 72.7
evenness due to surface roughness, inhibitor adsorption, and the forma-
10 80 30.29 −479 97.6 75.9. 75.8 tion of a porous layer [39]. Literature reports that n takes some special
20 24.45 −501 91.9 96.2 80.5 value, it can stand for some electric components. CPE can serve as a re-
40 11.69 −494 66.9 72.6 90.7 sistor (n = 0), inductor (n = −1), Warburg impedance (n = 0.5), or ca-
60 7.26 −488 46.5 66.3 94.2
pacitor (n = 1) [40]. The double-layer capacitance (Cdl) values can be

Fig. 4. Nyquist plots for Q235 steel in 1 M HCl solution without and with different concentrations of NNED at different temperatures.
Z. Chen, A.A. Fadhil, T. Chen et al. Journal of Molecular Liquids 332 (2021) 115852

Fig. 5. Bode plots for Q235 steel in 1 M HCl solution without and with different concentrations of NNED at different temperatures.

evaluated using Eq. (7). In the equation ωmax= 2πfmax and fmax repre- loss and polarization experiments, at each temperature, with the in-
sents the frequency where imaginary value achieves a maximum on crease of NNED concentration, the charge transfer resistance tends to
the Nyquist plot. According to the impedance measurement diagram
and the fitting data, the following formula (Eq. (8)) can be used to cal-
Table 3
culate the corrosion inhibition efficiency.
The impedance fitting parameters for different temperatures at different NNED
concentrations.
C dl ¼ Y o ðωmax Þn−1 ð7Þ
T(°C) C(ppm) Rs(Ω·cm2) Cdl(μF·cm−2) n Rp(Ω·cm2) η

40 Blank 0.39 2783.2 0.83 3.20 –

RP −RoP
η¼  100% ð8Þ 5 0.61 1324.4 0.75 14.21 78.74
RP 10 0.61 352.92 0.85 20.37 85.17
20 0.49 526.9 0.81 27.08 88.85
40 0.55 197.4 0.88 30.48 90.09
In Eq. (8), Rp and R0p represent polarization resistance with and with-
60 0.92 90.73 0.86 43.68 93.08
out corrosion inhibitor, respectively. The corresponding impedance 50 Blank 0.57 1038.5 0.77 1.03 –
measurement fitting parameters are listed in the Table 3. The results 5 0.6 934.6 0.76 5.18 80.12
show that impedance measurement is basically consistent with weight 10 0.46 344.9 0.7 5.53 81.37
20 0.56 306.5 0.77 5.78 82.18
40 0.89 182.6 0.8 8.16 87.38
60 0.61 52.91 0.86 14.16 92.73
60 Blank 0.45 2403.4 0.91 0.34 –
5 0.59 836.10 0.71 1.15 70.43
10 0.65 710.49 0.76 1.47 76.87
20 0.59 584.92 0.76 1.7 80.02
40 0.58 316.28 0.76 2.35 85.83
60 0.45 128.21 0.73 5.22 93.49
Blank 0.38 2337.62 0.8 0.06 –
5 0.37 1653.21 0.79 0.25 76.01
80 10 0.37 929.32 0.77 0.28 78.57
20 0.45 444.26 0.72 0.49 87.76
40 0.44 127.25 0.76 0.51 88.24
60 0.34 86.97 0.72 0.9 93.33
Fig. 6. Corresponding equivalent circuit.

6
Z. Chen, A.A. Fadhil, T. Chen et al. Journal of Molecular Liquids 332 (2021) 115852

Fig. 8. ΔGads of NNED in 1 M HCl solution at different temperatures.

Fig. 7. Langmuir adsorption isotherms of NNED on the steel surface in 1 M HCl solution at
different temperatures.

spontaneous [43]. It is generally considered that the adsorption of corro-

increase significantly, which demonstrate that NNED is an excellent cor-
rosion inhibitor.
3.3. Adsorption isotherm
The adsorption of corrosion inhibitor molecules on the surface of
carbon steel is generally considered to be the process of replacing the
adsorbed water molecules [41]. Many adsorption isotherms were veri-
fied. Frumkin,Freundlich,Langmuir,and Temkin adsorption isotherms
were evaluated. The best fitting was obtained by Langmuir adsorption
isotherm. In other words, the adsorption of NNED on the surface of
Q235 steel obeys the Langmuir adsorption isotherm [42]. The Langmuir
adsorption isotherm formula is shown in Eq. (9).
C 1
¼ þC
θ K
Where C is the corrosion inhibitor concentration, θ is the surface cov-
erage, which is replaced by the inhibition efficiency (η), and K is the ad-
sorption equilibrium constant, demonstrating the degree of adsorption.
Fig. 7 shows that the Langmuir adsorption isotherm can be well fitted to
the weight loss results of corrosion inhibitor at different temperatures
with high correlation coefficient (R2 = 0.99). Adsorption equilibrium
constant (K) and adsorption Gibbs free energy (ΔGads) was determined
using the formula:
 
1 ΔGads
K¼ exp −
55:5 RT
Where 55.5 is the molar concentration of water, R represents the
ideal gas constant, T is the absolute temperature, and ΔGads is the ad-
sorption Gibbs free energy. The conresponding adsorption parameters
were shown in Table 4. Obviously ΔGads is a negative value, indicating
that the adsorption of the corrosion inhibitor on the metal surface is
sion inhibitor on the metal surface can be defined as physical or chem-
ical adsorption. When the absolute value of ΔGads is greater than
40 kJ·mol−1, the adsorption mainly due to coordination between inhib-
itor molecules and metal active sites (chemical adsorption),whereas
ΔGads less than 20 kJ·mol−1, the adsorption is mainly caused by electro-
static interaction (physical adsorption) [44]. Take this into account, the
adsorption of NNED estimated as physisorption and chemisorption.
According to the Eq. (11), linear fit was conducted to ΔGads and tem-
perature. Fig. 8 displayed the corresponding results, it's obvious that
that the slope represents the entropy change (ΔSads), while the inter-
cept is on behalf of the enthalpy change (ΔHads). The theory that ad-
sorption is an exothermic process accompanied by negative value of
ΔHads has been widely accepted by many researchers. The negative
value of ΔHads depicted in Table 4 refers to the exothermic nature of
ð9Þ NNED adsorption on Q235 carbon steel surface, on the contrary the pos-
itive value of ΔSads appertains to the increased degree of disorder in the
system, the adsorption of inhibitor molecules is usually accompanied by
the desorption of water molecules so that the metal and solution inter-
faces maintains a balanced state.
ΔGads ¼ ΔHads −TΔSads ð11Þ
3.4. Corrosion kinetic parameters
The influence of temperature on chemical reaction rate is very
significant [45]. Therefore, the relationship between temperature and
ð10Þ
reaction kinetics was systematically studied in present work. The corro-
sion rate and temperature agree with Arrhenius formula (Eq. (12)).
By mathematical processing Eq. (12) can be converted to the linear
form as shown in Eq. (13).
 
Ea
C R ¼ A exp − ð12Þ
RT

Table 4
Adsorption parameters of NNED at different temperatures in 1 M HCl.

T/K R2 Slope Intercept K ΔGads ΔHads ΔSads

−3 −1 −1
(×10 ) (L·mmol ) (kJ·mol -1)
(kJ·mol ) (J·mol−1·K−1)

313 0.99 1.08 1.06 1.02 −28.47 −11.94 52.98

323 0.99 1.01 1.13 0.89 −29.03
333 0.99 1.04 1.27 0.82 −29.69
353 0.99 0.89 1.47 0.61 −30.59

7
Z. Chen, A.A. Fadhil, T. Chen et al.
Fig. 9. Arrhenius plot of Q235 in 1 M HCl with different concentrations of NNED.
Ea
ln ðC R Þ ¼ ln ðAÞ−
RT
Where CR is the corrosion rate, Ea is the activation energy, R is the gas
constant, T is the absolute temperature, and A is the Arrhenius constant
or frequency factor. Plotting ln (CR) against 1/T and perform linear
fitting, the kinetic parameters of different concentrations of NNED can
be obtained. The fitting results were shown in Fig. 9 and the kinetic pa-
rameters were displayed in Table 5. It's evident that the activation en-
ergy of the reaction had an upward tendency as the concentration of
NNED increased, which indicates that the corrosion process is blocked
after the addition of inhibitor.
3.5. Scanning electron microscopy (SEM)
The treated cylindrical Q235 steel samples with diameter of 1 cm
and height of 0.3 cm (area 0.785 cm2) were soaked in 1 M hydrochloric
acid solution in the absence and presence of 60 ppm NNED for 2 h at
60 °C, respectively. Then the samples were washed with deionized
water, and dried by cold air for later use. Fig. 10 a–f show SEM photo-
graphs of carbon steel under different conditions. It can be seen from
the Fig. 10 that the surface of the uncorroded carbon steel is smooth
and flat, just with a few scratches generated during mechanical
polishing process. The samples in the absence of the inhibitor were
greatly damaged and the surface is uneven and rough. However,
under the same corrosion reaction conditions, after adding 60 ppm of
NNED, the surface of the carbon steel showed only a slight flaky mor-
phology. The above results showed that NNED can inhibit the corrosion
process of carbon steel in hydrochloric acid solution. At the same time, it
can be known that the corrosion type of carbon steel in HCl medium is
homogeneous corrosion.
3.6. Atomic force microscopy (AFM)
AFM is a powerful tool to study the morphology of metal before and
after corrosion. The mainstream corrosion mechanism recognizes that
corrosion inhibitor will adsorb on the metal surface to generate a pro-
tection film [46,47]. Taking this into account, the scanning probe of
atomic force microscopy was applied to quantitatively analyze the ad-
hesion force between the probe tip and the adsorption film, which can
strongly prove the adsorption of corrosion inhibitor on metal surface.
The AFM three-dimensional topography (5 × 5 μm area) of carbon
steel before and after immersion in 1 M HCl at 60 °C for 2 h in the ab-
sence and presence of NNED (60 ppm) were shown in Fig. 11 a–c. It
Journal of Molecular Liquids 332 (2021) 115852
reveals that the surface of the uncorroded steel is very flat and with
an average roughness of 48.63 nm. However, Fig. 11 b shows that the
carbon steel is seriously corroded, with many defects on the surface
and the average roughness reaches 894.71 nm. Fig. 11c reveals the car-
bon steel still corroded after adding NNED with significant reduction in
average roughness. The maximum corrosion depths were 894.71 and
309.3 nm, in absence and presence of NNED, respectively demonstrates
a decreasing in corrosion compared to blank sample.
In the current research, it was found that AFM is mainly used to
study corrosion morphology, which does not take advantage of its pow-
erful function [48,49]. The adhesion force between probe and metal sur-
face was studied to demonstrate the adsorption of inhibitor molecules.
Fig. 12a–b displayed the force curve of carbon steel surface in the ab-
sence and presence of 60 ppm of NNED. Apparently there is no signifi-
cant adhesion characteristic appear on the surface of the blank
sample. After the addition of the corrosion inhibitor, the imidazoline
ring and amine group adsorbed on the metal surface and formed a hy-
drophobic film, when the AFM probe was pulled away from the metal
surface, it showed the characteristics of adhesion due to the hydropho-
bic force, which proves the adsorption process of NNED molecules on
the electrode surface [50]. In order to exclude accidental factors, points
on the surface of two samples were selected randomly for several times
to conduct force curve measurement, and the measurement results and
ð13Þ corresponding parameters are shown in Table 6. It is not difficult to see
that the adhesion force on the carbon steel surface is almost doubled
after the addition of NNED, which proves that molecules are adsorbed
on the carbon steel surface.
3.7. Quantum chemical calculation
To explore the electron density distribution of NNED and the mech-
anism of corrosion inhibition, quantum chemical calculations using
Gaussian 09 W software was performed. The synthetic corrosion inhib-
itor molecule was in neutral form and was fully optimized by using
B3LYP method at the DFT level with a 6–31G* basis set in the gas
phase [51]. When the molecular optimization is over, several parame-
ters including the energy of the highest occupied molecular orbital
(EHOMO), the lowest unoccupied molecular orbital (ELUMO), and the di-
pole moment (μ) were estimated. Furthermore, other molecular struc-
tural parameters such as energy gap (ΔE), electronegativity (χ), global
hardness (η), ionization potential (I), and electron affinity (A) were cal-
culated according to the following set of equations [52]:
I þ A −ðEHOMO þ ELUMO Þ
X¼ ¼
2 2
I−A −ðEHOMO −ELUMO Þ
η¼ ¼ ð14Þ
2 2
2
X
ω¼
2η
The electron transfers fraction (ΔN) is usually used to judge the cor-
rosion inhibition performance of a corrosion inhibitor. It can quantify
the ability of a corrosion inhibitor molecule to transfer electrons to me-
tallic atoms. Eq. (15) calculates its exact value.
X Fe −X inh
ΔN ¼
ð15Þ
2 ηFe þ ηinh
Where ηinh and ηFe represents the hardness of the corrosion inhibitor
molecular and Fe, among them χinh and ηinh can be obtained with quan-
tum chemical calculation parameters. According to Pearson's electro-
negativity scale, the theoretical value of ηFe is 0 eV and χFe is 7,
respectively [53]. Quantum chemical calculation parameters are closely
related to the inhibition performance of inhibitor molecules. △E is the
index of molecular stability. Fig. 13 shows the optimized structures
and the density distributions of the inhibitor molecular, when △E is
8
Z. Chen, A.A. Fadhil, T. Chen et al.
Table 5
Arrhenius formula fitting parameters and kinetic parameters of corrosion inhibitors with
different concentrations in 1 M HCl solution.
C (ppm) R2 A g·m−2·h−1
Blank 0.98 4.52 × 1012
5 0.99 6.04 × 1012
10 0.99 7.68 × 1012
20 0.98 1.17 × 1013
40 0.99 1.82 × 1012
60 0.96 6.46 × 1013
small, the better stability of the complex formed between the inhibitor
molecular and the metal surface, resulting in better inhibition perfor-
mance [54]. The dipole moment (μ) describes the magnitude of the po-
larity of a molecule, whereas there is no definite conclusion about the
relationship between it and inhibition performance. ΔN is also an im-
portant index, the electron transfer fraction greater than zero, means
that the corrosion inhibitor transfers electrons to the metal. According
to Lukovit's research, if ΔN < 3.6, the inhibition performance increases
with the increase of electron donating ability, ΔN is not actually the
number of electrons transferred from the electron donor to the electron
acceptor, but the electron donating ability [55]. The calculated quantum
chemical parameters are summarized in Table 7. ΔN of the corrosion in-
hibitor synthesized in present work was 0.79, indicating a significant
performance of the inhibitor molecular.
3.8. Molecular dynamics simulation
Molecular dynamics simulation (Materials Studio 8.0, BIOVIA,
San Diego, US) was applied to study the adsorption mechanism
of NNED corrosion inhibitor on mental surface at the molecular
level. Fe (110) crystal plane was selected in a rectangular box
(22.34 Å × 22.34 Å × 68.23 Å) for simulating computation. The sim-
ulation system consists of a three-layer structure, the first layer is the
Fe (1,1,0) surface with a size of 2.866 × 2.866 × 7.764 nm, and the
second layer is an amorphous structure composed of single inhibitor
molecule and 500 H2O molecules, the third layer contains 500 “fro-
zen” water molecules [56]. The established model is shown in
Fig. 14. All the simulations were performed at 333 K, with a time
step of 1 fs, and simulation time of 200 ps (NVT ensemble). When
the temperature and potential energy of the system remain stable,
the simulation process reaches equilibrium. The adsorption of
NNED molecule on the metal surface after molecular dynamics sim-
ulation is shown in Fig. 15, as can be seen that the furan and imidaz-
ole rings in the molecule are adsorbed horizontally on the metal
surface, and the alkyl chain is in the water phase. In order to quantify
the adsorption capacity of the molecule, the adsorption energy is cal-
culated with Eq. (16) [56].


Eads ¼ ENNEDþsurface − ENNED þ Esurface
Where ENNED+surface represents the total energy of Fe and NNED
molecules, ENNED the energy of NNED molecule, and Esurface the en-
ergy of Fe surface. The adsorption energies were − 103.09 kcal/mol
and − 6.5 kcal/mol for NNED and water, respectively. It can be
seen that adsorption energy of water was much smaller than the
NNED molecules. It can be speculated that the inhibitor molecules
Journal of Molecular Liquids 332 (2021) 115852
can spontaneously replace water molecules adsorbed on the metal
surface to protect the metal.
Ea kJ/mol 3.9. Inhibition mechanism
67.23
73.48 The previous AFM force curves, quantum chemical calculation
75.44 and molecular dynamics simulation proved that NNED adsorbed on
76.83
the exposed metal surface to form a protective film. Thermodynamic
78.24
82.36 parameter results further manifest that adsorption is classified as
physical and chemical adsorption. According to adsorption model
based on molecular dynamics simulation, the possible corrosion in-
hibition mechanism was predicated and the schematic diagram
was shown in Fig. 15. It includes the corrosion inhibitor molecules
replace the water molecules adsorbed on the metal surface. This pro-
cess can be expressed simply by Eq. (17).
NNEDsol þ nH2 Oads ! NNEDads þ nH2 Osol ð17Þ
Where n is the number of water molecules. On account of the
rapid anodic reaction in the aggressive solution, there is an excess
of Fe2+ in the solution, therefore the following adsorption process
is also possible.
Fes ! Fe2þ
aq þ 2e ð18Þ
2þ
Fe2þ
aq þ NNEDads ! ½Fe−NNEDads ð19Þ
It is worth emphasizing that process (19) only occurs when large
amounts of NNED molecules are added. [Fe-NNED)]2+ (ads) complex can
stabilize Fe2+ from being oxidized to Fe 3+ which can accelerate
metal degradation, this partly accounts for the degradation rate of
metals decreases significantly with the increase of inhibitor concen-
tration. Electrostatic attraction is the main reason for the formation
of protective film, NNED molecule contains elements such as oxygen
and nitrogen as well as unsaturated bonds. Unsaturated bonds or
heteroatoms in the molecule provides active adsorption centers
that adsorbed on the metal surface, giving the compound high corro-
sion inhibition performance.
3.10. Comparison of inhibition efficiency with recent corrosion inhibitors
The study of the inhibition performance of different types of organic
corrosion inhibitors in acidic solution was conducted by many re-
searchers [57–61]. Some of them were illustrated in Table 8 for compar-
ison with the present research work. As shown in Table 8, NNED was
more efficient at lower concentrations and higher temperature than
the other inhibitors.
4. Conclusion
ð16Þ
The present work is an important attempt to introduce biomass
platform molecules into the synthesis of NNED corrosion inhibitors.
The inhibitive capacity was investigated by the implementation of
electrochemical measurement and weight loss methods. The result
revealed that NNED presents excellent inhibition performance for
Q235 mild steel in 1 M HCl aggressive solutions although the concen-
tration is 5 mg/L, the inhibition efficiency reaches up to 90%. More-
over, the thermodynamic parameters indicate that the adsorption
9
Z. Chen, A.A. Fadhil, T. Chen et al. Journal of Molecular Liquids 332 (2021) 115852

Fig. 10. SEM topography of Q235 carbon steel. a-b SEM topography of uncorroded Q235 carbon steel, c-d SEM topography of Q235 carbon steel immersed in 1.0 M HCl. e-f SEM topography
of Q235 carbon steel in presence of 60 ppm inhibitor in 1.0 M HCl.

10
Z. Chen, A.A. Fadhil, T. Chen et al. Journal of Molecular Liquids 332 (2021) 115852

Fig. 11. AFM 3D topography of carbon steel under different experimental conditions, (a) before corrosion, (b) corrosion in 1 M HCl without NNED, (c) corrosion in 1 M HCl in the presence
of (60 ppm) NNED.

of NNED onto metallic surface is in accordance with Langmuir ad- Table 6

sorption isotherm. The fabrication of adsorption film involving The force curves measured under blank and the presence of NNED (60 ppm), four random
points are selected for measurement under each condition.
both physisorption attributed to electrostatic interaction and chem-
isorption ascribed to covalent bonds, but the latter plays leading sample adhesion force(nN) average value standard deviation
role. Furthermore, potentiodynamic polarization measurements blank 3.4 3.0 0.4
reveals that NNED serves as a mixed-type inhibitor and primarily 2.9
inhibits the electrochemical reaction of metal dissolution in the 3.0
2.9
anode region. SEM and AFM are combined to observe the morphol-
60 ppm 6.2 6.2 0.2
ogy of mild steel in the absence and presence of NNED inhibitor, in 6.1
addition, the adhesion force of metal surface increases significantly 6.4
after the addition of inhibitor, which strongly demonstrates the fab- 6.2
rication of NNED film onto metal surface. Eventually, the low ΔE and
high ΔN derived from quantum chemical computation represents

Fig. 12. Force curves measured under different conditions, (a) in the absence of NNED, (b) in the presence of NNED (60 ppm).

11
Z. Chen, A.A. Fadhil, T. Chen et al. Journal of Molecular Liquids 332 (2021) 115852

Fig. 13. Quantum computational chemistry, a optimized molecular structure and electron density distribution, b the highest occupied molecular orbital (HOMO) density, c the lowest
unoccupied molecular orbital (LUMO) density.

the strong adsorption as well as electrostatic interaction between

Table 7 the inhibitor molecule and metal surface. Molecular dynamics simu-
Calculated quantum chemical parameters. lations reveal the horizontal adsorption orientation of NNED onto
EHOMO(eV) ELUMO(eV) ΔE(eV) μ(debye) η (eV) χ (eV) ω ΔN metal surface to facilitate the donation and reception of electron,
thus more excellent inhibitive performance.
−5.55 −0.52 5.03 3.42 2.52 3.04 15 0.79

Fig. 14. (a) Three-layer model established by Material Studio (after optimization). Equilibrium adsorption configurations simulated for NNED on Fe (1 1 0) surface in aqueous solution: side
view (b) and top view (c).

Fig. 15. Schematic diagram of NNED inhibition mechanism.

Z. Chen, A.A. Fadhil, T. Chen et al.
Table 8
Comparison of NNED inhibition efficiency with some literature values for steel in 1 M HCl at moderate temperature (around 30 °C).
No Inhibitor
1 5- octylsulfanyl-1,2,4-triazole
2 (Z)-2-hydroxy-N′-(2-hydroxy-1,2-diphenylethylidene) benzohydrazide
3 (3ar,6ar)-3a,6a-di-p-tolyltetrahydroimidazo[4,5-d]imidazole-2,5(1h,3h)-dithione
4 5-(azidomethyl)-7-(piperidin-1-ylmethyl)quinolin-8-ol
5 4,4′-oxybis(N,N-bis(oxiran-2-ylmethyl)aniline)
Author statement
Zhan Chen and Ahmed A. Fadhil: Conceptualization; Data curation.
Tianqi Chen: Funding acquisition; Investigation. Anees A. Khadom;
Investigation; Methodology; Project administration; Writing - review
& editing; Resources. Chaoyang Fu: Software; Supervision; Validation;
Visualization. Noor A. Fadhil: original draft.
Declaration of Competing Interest
None.
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