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Diethylenetriamine functionalized graphene oxide

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as a novel corrosion inhibitor for mild steel

Cite this: DOI: 10.1039/c8nj04771e
in hydrochloric acid solutions
Nadeem Baig,a D. S. Chauhan, b
Tawfik A. Saleha and M. A. Quraishi *b

Received 19th September 2018,
Accepted 21st December 2018
DOI: 10.1039/c8nj04771e
rsc.li/njc
In the present work diethylenetriamine functionalized graphene oxide (DETA-GO) has been synthesized
and its corrosion inhibition performance was evaluated in 1 M HCl for mild steel. The chemical structure
of the synthesized DETA-GO was analyzed by FTIR and the morphology was studied using SEM, TEM,
and FTIR. The corrosion inhibition behavior was studied using weight loss studies, electrochemical
impedance spectroscopy (EIS) and potentiodynamic polarization. DETA-GO behaved as an efficient
corrosion inhibitor as evident from the results of the electrochemical analysis. Electrochemical studies
showed that the inhibition efficiency of DETA-GO increased with the concentration and reached 92.67%
at a concentration of 25 mg L1. The inhibitor exhibits a mixed type nature with cathodic predominance.
The protective film of the inhibitor over the mild steel surface was examined by SEM and FTIR-ATR
studies. A computational study using DFT further supports the promising corrosion inhibition behavior of
DETA-GO.

1. Introduction large surface area.12–17 The non-polar nature of graphene and

Mild steel is an extensively used structural material due to
its high tensile strength, ductility, malleability, and ease of
availability.1,2 Mineral acids are extensively consumed in many
industrial applications such as acid pickling, oil well acidization,
descaling etc. which lead to considerable corrosion of metallic
structures.1–3 This corrosion damage causes severe economic
loss by plant shutdown, loss of valuable resources, product
contamination, reduction in efficiency, etc.4–6 In order to
counter corrosion, one of the most effective methods is the
use of organic compounds as additives, which are adsorbed
over the metal surface, thereby retarding the corrosion process.
The effectiveness of these corrosion inhibitors is attributable to
their structural characteristics i.e., the presence of phenyl rings,
functional groups, p bonds and heteroatoms such as oxygen,
nitrogen, and sulfur.3,4,6–11 However, a vast majority of such
inhibitors are toxic in nature, which restricts their practical
application due to strict environmental regulations.
Graphene and its derivatives have been conventionally used
as additives in anti-corrosion coatings owing to their hydro-
phobicity, high mechanical strength, chemical resistance, and
a
Department of Chemistry, King Fahd University of Petroleum and Minerals,
Dhahran 31261, Saudi Arabia
b
Center of Research Excellence in Corrosion, Research Institute, King Fahd
University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia.
E-mail: mumtaz.quraishi@kfupm.edu.sa
the absence of any functional groups reduces its solubility in
aqueous media, due to which it can act as an excellent coating
material.18,19 On the other hand, graphene oxide (GO) has
better water dispersibility due to its hydrophilic character,
which is attributed to the oxygen-containing functionalities.
In addition, reactive functionalities such as epoxy, carboxyl,
carbonyl, and hydroxyl groups present over the surface of GO
provide promising prospects for chemical functionalization,
which can improve the solubility in aqueous medium.12,20
Our group has made significant contributions in the appli-
cation of graphene and functionalized graphene oxide.21–23
Previously, diethylenetriamine functionalized graphene oxide
(DETA-GO) has been used as a metal-free catalyst for organic
synthesis and as a sorbent for solid phase extraction.24–27
The three amine groups of DETA impart trifunctional metal-
chelating ability to the GO sheets and the resulting product can
be used as an environmentally benign nanomaterial. Earlier,
we have reported the first application of p-aminophenol and
pyridine functionalized graphene oxide as corrosion inhibitors
for mild steel.28,29 However, the functionalization of GO with
aromatic compounds restricts the solubility of the product in
aqueous medium, which is liable to create a major lacuna for
corrosion inhibition application. In this context, the remark-
able solubility and functional ability of DETA-GO directed our
attention to use this nanomaterial as a corrosion inhibitor.
Accordingly, we herein present the synthesis and characteriza-
tion of DETA-GO and its application as a novel inhibitor against

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corrosion of mild steel in 1 M hydrochloric acid solution.
A detailed investigation using electrochemical measurements
and surface analysis is reported in the current study. The
experimental studies were also endorsed by quantum chemical
calculations.
2. Experimental
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2.1 Materials and test solutions
Diethylenetriamine (2,2 0 -diaminodiethylamine), CAS Number
111-40-0 linear formula (NH2CH2CH2)2NH, and molecular
weight 103.17 g mol1 99%, was purchased from Sigma Aldrich.
Other chemicals including potassium persulfate (K2S2O8),
phosphorus pentoxide (P2O5), graphite powder, sulfuric acid
(H2SO4), potassium permanganate, and hydrogen peroxide
were purchased from Sigma Aldrich and used without further
purification.
A mild steel strip having a composition as reported earlier1
and dimensions 8.0 cm  1.0 cm  0.05 cm was used for the
electrochemical corrosion tests. For the weight loss studies, the
mild steel samples were cut into 2.5 cm  2 cm  0.025 cm
pieces. The electrochemical analysis was done by using the
mild steel specimen with the aforementioned dimensions and
1 cm2 unprotected area with the rest being covered by epoxy
resin. Prior to the experiments, SiC paper of different grades in
the range of 600 to 1200 was used to finely polish the surface of
mild steel. Subsequently, the mild steel surface was degreased
with acetone and washed thoroughly with double distilled
water. After performing the cleaning and polishing steps, it
was dried, and stored in a desiccator prior to experimental
evaluation. Analytical grade HCl (Fisher Scientific) was used for
the preparation of the 1 M HCl test solution. The aerated and
unstirred solutions (303  2 K) were used for carrying out the
corrosion testing.
2.2 Synthesis of diethylenetriamine-functionalized graphene
oxide
Graphene oxide was synthesized by Hummer’s method using
graphite powder. 1.2 g of K2S2O8, 1.2 g of P2O5 and 2 g of
natural graphite powder were added into 50 mL H2SO4 in an
ice-water bath, under stirring at 750 rpm. The temperature was
increased to 80 1C, and 412 hours later, the mixture was washed
with distilled water until the pH reached 7 and purified
graphite powder was obtained by centrifugation followed by
drying in a vacuum oven. After that, the dried graphite powder
was added to 30 mL of H2SO4 in a flask under stirring (250 rpm)
in an ice-water bath. KMnO4 (8 g) was slowly added into the
flask and the temperature was increased to 35 1C and stirred at
750 rpm. 2 hours later, 62.5 mL distilled water was added slowly
and the temperature increased very quickly at this time. 1 hour
later, an additional 175 mL of water was added followed by
slowly adding 5 mL of H2O2 (30%) into the solution. The
resulting mixture was filtered and washed with dilute HCl
(1/10 v/v). The obtained sample was collected and dried in a
vacuum freeze drying oven for 48 hours.
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For the synthesis of diethylenetriamine (DETA)-modified
graphene nanosheets, the prepared graphene oxide was treated
with thionyl chloride in anhydrous DMF. The resultant mixture
was ultrasonicated for 1 h. The mixture was refluxed at 70 1C for
a time period of 12 h followed by cooling down to room
temperature. The acylated graphene oxide was separated from
the solution by centrifugation and washed with dry DMF. DETA
was added to the acylated graphene oxide and the mixture was
stirred at 60 1C for 2 days. A schematic representation of the
synthesis process is shown in Scheme 1. The infrared spectrum
of the synthesized DETA-GO was recorded using a Nicolet iS5
FTIR equipped with an iD5 ATR. The surface morphologies
of the graphene oxide and DETA-GO were recorded using a
JSM-6610LV scanning electron microscope from JEOL.
2.3 Corrosion tests
The mild steel samples were weighed followed by immersion in
1 M HCl solution without and with different concentrations
of DETA-GO for 12 h. The samples were taken out followed
by washing with double distilled water and acetone. The
cleaned samples were dried in a moisture-free desiccator and
weighed again.
A Potentiostat/Galvanostat Reference 3000 was used for
performing all the electrochemical experiments. The experimental
data were analyzed and fitted with the help of Gamry Echem
Analyst 6.33 software.1,2 A three-electrode system comprising a
mild steel strip as a working electrode, an Ag/AgCl reference
electrode and a graphite rod as a counter electrode was employed
for taking measurements. Prior to each electrochemical
experiment, the steady state open circuit potential (EOCP) was
determined by immersing the working electrode into the test
solution for 30 min. The EIS experiment was performed in the
frequency range of 100 kHz to 0.01 Hz using the AC 10 mV peak
to peak signal.
The potentiodynamic polarization tests were performed by
scanning the potential at a constant sweep rate of 0.1 mV s1 in
the range of 250 to +250 mV versus EOCP in the absence and
presence of various inhibitor concentrations. The corrosion
current densities (icorr) were derived for the metallic specimen
in uninhibited and inhibited conditions by extrapolating the
obtained Tafel curves.
2.4 Surface studies
The surface morphology of the mild steel samples for visual
inspection was recorded to observe the influence of the protec-
tive inhibitor films on the mild steel sample surface. For this
purpose, the mild steel samples were cleaned comprehensively
and immersed into the acidic medium (1 M HCl) in the absence
and presence of an optimum concentration of DETA-GO. After
immersion for 12 hours, the mild steel samples were removed
from the 1 M HCl solution, washed, dried and SEM images were
recorded with the help of a scanning electron microscope
(JSM-6610LV scanning electron microscope from JEOL). The
ATR technique was used for recording the FTIR spectra of the
mild steel surface to confirm the adsorption and the presence

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Scheme 1 Synthesis of DETA-GO.
of DETA-GO on the metal surface. The infrared spectra were
recorded using a Nicolet iS5 FTIR equipped with an iD5 ATR.
2.5 Computational studies
Density Functional Theory (DFT) was applied for theoretical
calculations30 using the Becke three-parameter hybrid
functional and the Lee–Yang–Parr correlation functional
(B3LYP).31,32 The Gaussian 09 software for Windows (Revision
D.01) was used with the 6-31G(d,p) basis set for all the
calculations.33 Different quantum chemical parameters were
assessed, which include absolute electronegativity (w), energy
gap (DE), softness (s), dipole moment (m), global hardness (Z),
the energy of the lowest unoccupied molecular orbitals (ELUMO),
and the energy of the highest (EHOMO) occupied molecular
orbitals.
3. Results and discussion
3.1 Synthesis and characterization of DETA-GO
The FTIR spectra of GO and DETA-GO were recorded to observe
their characteristic functionalities. The C–O stretching peaks of
the alkoxy, epoxy and carboxylic acid functional groups were
observed at 1115, 1228 and 1333 cm1, respectively. The band
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that appeared at 1716 might be assigned to the carbonyl group.
The sharp absorbance band at 1625 cm1 is attributed to the
aromatic –CQC–. The absorption bands at 2849 and 2917 cm1
were assigned to the –C–H vibrations. The band that appeared
at 3416 cm1 was due to the hydroxyl group stretching
vibrations. The characteristic FTIR peaks of GO demonstrate
the successful synthesis of the nanomaterial (Fig. 1a). The
spectrum of DETA-GO reveals the successful functionalization
of GO. Although the structure of GO contains a number of
functionalities, DETA can only react with certain groups such
as acyl chloride transformed from the carboxylic acid group.
Therefore, the characteristic FTIR peaks of GO can still be
visualized in the spectrum of DETA-GO. A broad band appears
in the range of 2884 to 3708 cm1, which is attributable to the
amide linkage. The CQO peak of GO is also shifted in position
and now a major peak at 1635 cm1 can be observed. The
characteristic N–H stretching and the peak at 1716 cm1 are also
an indication of the possible formation of the amide linkage.
A new absorption band appeared at 600 cm1 in the spectrum of
DETA-GO, which was absent in the FTIR spectrum of GO. It can be
assigned to the N–H out of plan bending vibrations.
The morphological properties of the synthesized graphene
oxide and the amine functionalized graphene oxide were
studied using scanning electron and transmission electron
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Fig. 1 FTIR spectra of (a) graphene oxide and (b) diethylenetriamine

functionalized graphene oxide.

microscopy (Fig. 2). The SEM image shows the wrinkled shape
formation of graphene oxide sheets. The TEM image of GO
indicates the formation of very thin layers of graphene. The
TEM image of DETA-GO shows the graphene layer grafted with
the branches of diethylenetriamine.

3.2 Corrosion inhibition studies

3.2.1 Weight loss measurements. The weight loss method
is a reliable technique to optimize the effect of inhibitor
concentration on corrosion inhibition efficiency.2,10 The corro-
sion inhibition efficiency of the studied inhibitor was investi-
gated for MS in 1 M HCl using different concentrations of
DETA-GO from 5 mg L1 to 50 mg L1. The corrosion rate CR
(mg cm2 h1) was calculated as follows:7,10
W Fig. 2 (A) SEM image of GO, (B) TEM image of GO and (C) TEM image of
CR ¼ (1) DETA-GO.
At
where, W is the average weight loss value of the mild steel
samples, A is the total area and t is the immersion time (12 h). Table 1 Weight loss parameters obtained for mild steel in 1 M HCl in the
The corrosion inhibition efficiency (Z%), which is defined as absence and presence of different concentrations of DETA-GO
the relative decrease in the corrosion rate in the presence of an
Inhibitor conc. CR Surface
inhibitor, was calculated using the following relationship:7,10 (mg L1) (mg cm2 h1) coverage (y) Z%
CR  CRi Blank — 12.26 — —
Z% ¼  100 (2) DETA-GO 5 2.53 0.7936 79.36
CR
10 1.87 0.8467 84.67
where, CR and CRi are the average weight loss values obtained in 15 1.36 0.8884 88.84
25 0.80 0.9344 93.44
the absence and in the presence of an inhibitor. DETA-GO 50 0.74 0.9393 93.93
inhibits corrosion by increasing the surface coverage of mild
steel, which improves the corrosion inhibition efficiency. The
surface coverage (y) was computed as given below:7,10 listed in Table 1, which shows that, upon addition of different
CR  CRi concentrations of DETA-GO, there is an increase in the inhibi-
y¼ (3) tion efficiency and a corresponding decrease in the corrosion
CR
rate. The inhibition efficiency increased with an increase in the
The results obtained from the weight loss measurements, concentration of DETA-GO and reached 93.44%. This suggests
such as corrosion rate and corrosion inhibition efficiency, are that the increase in the concentration of DETA-GO caused an

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increase in the extent of adsorption and surface coverage due to
the availability of a greater number of inhibitor molecules,
which leads to an increase in the inhibition efficiency.
3.2.2 Electrochemical impedance spectroscopy. EIS is a
useful tool to understand the kinetics and mechanism of
electrochemical processes taking place on a metal/solution
interface.10,34,35 In the present work, EIS was employed to study
the adsorption of DETA-GO and the capacitive behavior of the
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mild steel electrode in the presence of different concentrations
of the studied inhibitor. Different EIS parameters were calcu-
lated by applying the equivalent circuit shown in Fig. 3(a) and
are listed in Table 1. The obtained impedance data for con-
centrations ranging from 5 mg L1 to 50 mg L1 in the form of
Nyquist plots are shown in Fig. 3(b). It can be observed that in
the studied frequency range, the obtained Nyquist curves show
a single capacitive loop characteristic of one time constant.
The Nyquist loops are in the form of depressed semicircles
having their centers lying below the real axis, indicating that
the corrosion is mainly being controlled by the charge transfer
process. The deviation observed from the ideal capacitive
behavior might be attributed to the rough surface, frequency
dispersion, relaxation, and porosity in mass transfer effects.2
Therefore, in order to accurately model the electrode/solution
interface, in the present study, the constant phase element
(CPE) was used to replace the classical double layer capacitor,
which signifies a frequency distributed double layer capacitance
Fig. 3 (a) Equivalent circuit model used to fit the EIS data (b) Nyquist plots
recorded for mild steel corrosion in 1 M HCl in the absence (inset) and in
the presence of different concentrations of DETA-GO.
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with a phase shift (n). The impedance of the CPE (ZCPE) is
given by:7,10
ZCPE = Yo1( jo)n (4)
where Yo is a proportionality coefficient, o is the angular
frequency given by o = 2pfmax (rad s1) at which the imaginary
component of impedance Zim is maximum, and n is an expo-
nent related to the phase shift. From an inspection of the
results, it can be observed that in the presence of DETA-GO, the
diameter of the Nyquist semicircle is larger than that observed
in the absence of DETA-GO. On the real axis, the difference in
the real impedance between the lowest and highest frequencies
is conventionally described as charge transfer resistance (Rct).
There are additional contributions to the real resistance arising
from the corrosion process, which cannot be neglected.
Therefore, in the present study, the term polarization resistance
(Rp) is used to represent the collection of resistance compo-
nents on the mild steel electrode undergoing uniform corro-
sion in an aggressive solution of 1 M HCl.2,10,34 Herein, Rp is the
sum of the charge transfer resistance (Rct), the diffuse layer
resistance (Rd), the film resistance (Rf), and the resistance
contribution from all other accumulations (Ra). The observed
elongations in the low-frequency regions of the Nyquist loops
can be attributed to the adsorbed inhibitor species.36
It can be observed from Fig. 3 that the values of Rp show
an increase upon addition of increasing concentrations of
DETA-GO, suggesting the establishment of a protective inhibitor
film over the surface of mild steel, which forms a barrier against
the charge transfer process.
The adsorption of DETA-GO on the corroding surface of
mild steel blocks the active sites that are prone to corrosion,
which can be correlated with the corrosion inhibition behavior.
The inhibition efficiency can be evaluated from the polarization
resistance (Rp) as given below:7,10
RpðinhÞ  Rp
Z% ¼  100 (5)
RpðinhÞ
where Rp, and Rp(inh) are the polarization resistance values
determined in the presence and absence of inhibitors in 1 M
HCl. The value of the parameter ‘n’ can be taken as a gauge for
surface homogeneity. A lower n value is related to a higher
surface roughness (e.g. that of a metal sample undergoing
corrosion) while an increase in the n value can be correlated
with a more homogenous surface. An observation of the data in
Table 1 indicates that compared to the blank sample, the values
of n are higher in the case of DETA-GO. This suggests an
improvement in the surface smoothness of the mild steel
sample in the presence of an inhibitor, which is attributable
to the formation of a protective film of DETA-GO.
The Cdl is the double layer capacitance, which can be
calculated using the following equation:37
Cdl = Yo(omax)n1 (6)
The dielectric constant of organic inhibitor molecules is
significantly lower than that of water. The Cdl can be related to
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the thickness of the protective layer formed by the inhibitor Table 2 Electrochemical impedance parameters determined in the
molecules dorg using the following equation: absence and presence of different concentrations of DETA-GO

e0 er Inhibitor
Cdl ¼ (7) conc. R Yo  1016 Cdl
dorg
(mg L1) Rs (O) (O cm2) n (O1 sn cm2) (mF cm2) Z%
where, e0 and er denote the vacuum and the relative dielectric Blank — 1.120 7.74 0.84 330.11 111.18 —
constant, respectively. The decrease in the Cdl can be observed DETA- 5 1.071 44.31 0.87 120.82 55.77 82.53
GO 10 0.783 59.38 0.88 99.79 52.56 86.63
due to a decrease in the local dielectric constant or an increase 15 0.868 81.34 0.88 74.46 38.68 89.58
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in the electrical double layer thickness. The higher values of Cdl
in the presence of an inhibitor compared to that obtained for
the blank mild steel indicate the adsorption of the DETA-GO
molecules at the electrode/solution interface.38,39 This suggests
that the inhibitor molecules gradually replace the pre-adsorbed
water molecules and form a protective film over the metal
surface, which causes a decrease in the surface area available
for corrosion.
3.2.3 Potentiodynamic polarization. The potentiodynamic
polarization curves of mild steel obtained without and with
different concentrations of DETA-GO are displayed in Fig. 4.
The corrosion current density (icorr) and the potential (Ecorr)
were evaluated by extrapolating the cathodic and anodic
branches of the Tafel plots. The electrochemical parameters
such as inhibition efficiency (Z%), icorr, anodic and cathodic
Tafel slopes (ba and bc) and corrosion potential (Ecorr) are
described in Table 2. The inhibition efficiency was measured as
follows,3,10
icorr  icorrðinhÞ
Z% ¼  100
icorr
where, icorr and icorr(inh) denote the corrosion current densities
in the absence and the presence of an inhibitor, respectively.
The parallel lines in the cathodic branch indicate that the
hydrogen evolution process was actually activation controlled
and the introduction of DETA-GO does not affect the mecha-
nism of the reduction process.40 From Table 2 and Fig. 4, it can
be observed that the corrosion current densities for the Fe
25 0.899 99.34 0.89 80.74 47.22 92.67
50 0.864 115.5 0.87 94.55 47.68 94.52
dissolution as well as the hydrogen evolution reactions show a
decreasing trend with the addition of DETA-GO, signifying the
suppression of both the anodic and cathodic processes.10
The observed decrease in the icorr values in the presence of
DETA-GO implies that the mild steel surface is protected from
the aggressive acid attack due to the formation of a protective
film formed by the inhibitor molecules. It can also be observed
that there is a shift in the Ecorr values towards the negative
direction, which describes the cathodic predominance of
the inhibitory behavior. However, this shift is only slight,
indicating a mixed type behavior of inhibition rather than a
pure cathodic type inhibitor action.7,10,35
3.3 Surface analysis
The SEM images of the uninhibited and inhibited metallic
(8) specimens after an immersion time of 12 h are shown in Fig. 5.
The SEM images depict strong corrosive damage to the mild
steel surface after immersion in 1 M HCl in the absence of
DETA-GO. On the other hand, in the presence of DETA-GO,
a significantly smooth morphology of the mild steel surface can
be observed. This suggests the adsorption of DETA-GO and its
protective action on the metal surface.
The adsorption of DETA-GO on the mild steel surface was
also studied by FTIR-ATR spectroscopy. Fig. 6(c) shows the
FTIR-ATR spectra of the mild steel surface following immersion
in 1 M HCl in the absence (a) and in the presence of (b) DETA-GO.
The FTIR spectrum of the synthesized DETA-GO is already
discussed in Section 3.1. The FTIR-ATR spectrum of the mild
steel surface in the presence of DETA-GO shows representative
peaks of the inhibitor (Fig. 6). However, these peaks do not appear
in the spectrum of the blank sample, which indicates the absorp-
tion of DETA-GO.

3.4 Computational study

Fig. 4 Potentiodynamic polarization curves for mild steel in 1 M HCl
containing different concentrations of DETA-GO.
3.4.1 Frontier molecular orbitals. The HOMO and LUMO
of organic molecules play a key role in the understanding of
their corrosion inhibition behavior. The HOMO density distri-
bution is related to the tendency to donate electrons while the
LUMO distribution signifies the tendency to accept electrons.
In general, the heteroatoms, the p bonds, the phenyl rings, and
the different functional groups contribute towards the HOMO
and LUMO regions and thereby act as the active sites available
for adsorption. In the present study, we have made a comparison
of the quantum chemical parameters of GO, DETA, and DETA-GO

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Fig. 5 SEM images of mild steel in the absence (a) and the presence (b) of 25 mg L1 of DETA-GO.
Fig. 6 FTIR-ATR spectra of mild steel and mild steel with adsorbed
DETA-GO.
to determine the influence of the organic functionalization of GO
on corrosion inhibition. To model a considerably large structure
of GO considering the computational restrictions, in the present
work, we have chosen six graphene rings. Fig. 7 shows the
optimized structures of GO, DETA, and DETA-GO, where blue
color denotes nitrogen, grey indicates carbon, red represents
oxygen and white means hydrogen. The optimized structure of
GO, as expected, shows a highly planar arrangement of rings. The
DETA molecule is also planar and shows a typical zig-zag arrange-
ment of the carbon chain. DETA-GO also shows a largely planar
structure with branches formed from the amide linkage between
Fig. 7 Optimized molecular structures of DETA, GO and DETA-GO.
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the amine groups of DETA and the –COCl groups of acylated GO
as shown in Scheme 1 above.
3.4.2 Quantum chemical parameters. The DFT study of the
corrosion inhibitors provided the information of the frontier
molecular orbital (FMO) energies. DFT analysis can furnish an
estimation of the chemical reactivity, which is useful for an
assessment of the adsorption behavior. On the basis of FMO
theory, the HOMO and LUMO regions of chemically reacting
species represent the major sites for electron exchange. A high
EHOMO value of an inhibitor indicates a higher tendency to
donate electrons to the metal while a low ELUMO value is correlated
with a tendency to accept electrons. Hence, inhibitor molecules
with a higher EHOMO and lower ELUMO are likely to depict an ease
of adsorption on the surface of a metal, which can facilitate its
better inhibitor action.10,41 The HOMO and LUMO distributions
of DETA, GO and DETA-GO are shown in Fig. 8. The HOMO
region of GO is widely distributed on the phenyl rings and on the
epoxy groups. The HOMO of DETA is distributed along the chain
with the amine groups being the major contributors. The HOMO
region of DETA-GO is mainly centered on the GO structure.
A similar trend is observed in the LUMO density distributions,
where the LUMO in DETA is distributed across the chain and the
LUMO regions of GO and DETA-GO are distributed on the phenyl
rings and the epoxide groups.
The ionization potential (I) and electron affinity (A) can be
correlated with the frontier molecular orbital energies as follows:
EHOMO = I (9)
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Fig. 8 (a) LUMO and (b) HOMO density distributions of DETA, GO and DETA-GO.

ELUMO = A (10) given in Table 4. It can be observed from the data that DETA-GO
possesses the highest level of EHOMO, which indicates its higher
The absolute electronegativity and the global hardness can inclination to donate electrons to mild steel. Although the
be expressed as follows: lowest value of ELUMO is shown by GO, a negative value of the
1 same in the case of DETA-GO suggests that it does show a good
w ¼ ðI þ AÞ (11)
2 tendency of electron acceptance. Further, the lowest value of
DE in the case of DETA-GO shows its better reactive tendency.
1 This is again reflected in terms of the considerably low value of
Z ¼ ðI  AÞ (12)
2 Z and the highest value of s.
where w represents the absolute electronegativity and Z denotes Parr et al. prefaced the global electrophilicity index (o),
the global hardness. A greater value of the molecular orbital which can be expressed as:43,44
energy gap (DE) is attributable to a stable molecular structure,
w2
which also shows a larger Z value.10,30,42 The difference between o¼ (14)
4Z
the electronegativity of two molecules acts as the driving force
for a reaction to proceed whereas a higher value of the hardness The reciprocal of electrophilicity is nucleophilicity (e).
indicates the difficulty in electron transfer. The inverse of Accordingly, a higher value of o indicates the tendency to
hardness is the global softness s which can be given as: accept electrons whereas a higher e value of an inhibitor
1 molecule indicates a greater capability to donate electrons.
s¼ (13)
Z Hence, a good nucleophile can be recognized by its high e and
lowo. It is also clear from Table 3 that DETA-GO shows the lowest
A higher value of softness indicates a higher reactivity of a o and therefore the highest e value, which shows that compared
molecule. Different reactivity indices were evaluated and are to the parent molecules, it possesses a better capability of electron
donation.
Table 3 Potentiodynamic polarization data for mild steel in the absence According to Pearson et al., the fraction of electrons trans-
and presence of different concentrations of DETA-GO ferred to the metal surface from the inhibitor molecules can be

Inhibitor Ecorr
conc. (mV vs. ba bc icorr Table 4 Calculated quantum chemical parameters
(mg L1) Ag/AgCl) (mV dec1) (mV dec1) (mA cm2) Z%
Blank 494 77.9 110.5 931 — Component EHOMO ELUMO DE w Z s o e DN
DHA 5 527 62.2 132.6 174 81.31 DETA 4.9155 2.1908 7.1063 1.36 3.55 0.28 0.13 7.66 0.49
10 530 66.8 124.8 131 85.93 GO 4.9089 3.4387 1.4702 4.17 0.74 1.36 5.92 0.17 0.44
15 531 64.6 118.1 103 88.94 DETA-GO 3.6833 2.3473 1.3361 3.02 0.67 1.50 3.40 0.29 1.35
25 533 57.7 121.1 76 91.84
50 534 61.8 117.5 70 92.48 All energy values are in eV; s is in eV1

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Table 5 Comparative chart listing the performance of different corrosion inhibitors

Inhibitor Medium of testing Metal surface Optimum concentration (mg L1) Z% Ref.
Expired drug tramadol 1 M HCl Mild steel 100 97.1 2
Pyridine derivatives 1 M HCl Mild steel 400 97.0 3
Chitosan–PEG 1 M HCl Mild steel 200 89.4 7
Chitosan–thiosemicarbazide 1 M HCl Mild steel 200 88.6 10
Chitosan–thiocarbohydrazide 1 M HCl Mild steel 200 90.4 10
Oligomeric aniline 1 M HCl Low carbon steel 200 96.1 34
DETA-GO 1 M HCl Mild steel 25 92.7 Present work
Published on 21 December 2018. Downloaded by University of Winnipeg on 1/20/2019 10:03:29 PM.

assessed as:30,41,45,46 corrosion by adsorption on the mild steel surface as evident

wmetal  winh
DN ¼
2ðZmetal þ Zinh Þ
where, winh and wmetal indicate the absolute electronegativity
values for the inhibitor and the metal, respectively, whereas Zinh
and Zmetal denote the respective values of the hardness. The
important point to note about the DN value is that it does not
represent the exact number of electrons transferred. The DN
value is an estimate of the electron donating ability. For the
calculation of DN, a theoretical value of 7 eV for the wFe of the
bulk metal and a global hardness ZFe = 0 are used considering
I = A for the bulk metal. A modification of the above relation-
ship has been shown by Kokalj, which suggests that instead of
wFe, the work function fFe is a more suitable parameter for this
calculation. Thus, using wFe with fFe and taking ZFe = 0, eqn (12)
becomes:47,48
fFe  winh
DN ¼
2Zinh
The DFT obtained f values of 4.82, 3.88 and 3.91 correspond
to the Fe(110), Fe(111) and Fe(100) surfaces, respectively.
Herein the Fe(110) surface is chosen considering its higher
packed surface and stabilization energy. From Table 3, it can be
observed that the value of DN is the highest for DETA-GO, which
further emphasizes its better tendency to transfer electrons to the
surface of mild steel (Table 4).
A comparison of the corrosion inhibition performance of
DETA-GO with those of earlier reported corrosion inhibitors is
shown in Table 5. The experimental results obtained in the
present study and the comparative chart show that DETA-GO is
a novel and potent corrosion inhibitor.
4. Conclusions
In the present investigation, graphene oxide (GO) was chemi-
cally modified using diethylenetriamine (DETA) following a
facile method. The structure of the obtained DETA-GO was
characterized using FTIR and TEM. The synthesized nano-
material was investigated as a novel inhibitor against corrosion
of mild steel in 1 M HCl by an electrochemical study and
surface analysis. The studied nanomaterial behaved as an
effective corrosion inhibitor, and the inhibition performance
increased with an increase in the concentration, leading to a
maximum efficiency of 92.67% at a concentration of 25 mg L1.
The results of the EIS study indicate that DETA-GO inhibits the
from the observed increase in the polarization resistance.
(15) Potentiodynamic polarization data suggest that DETA-GO acts
as a mixed type inhibitor with cathodic predominance. The
surface analysis using SEM shows the formation of a protective
film of DETA-GO over the mild steel surface, which separates
the metal from the corrosive environment. This observation
was corroborated by the results of FTIR-ATR. The quantum
chemical parameters also suggested the better capability of
electron donation of DETA-GO compared to that of GO and
DETA alone.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
(16)
Nadeem Baig and Dheeraj Singh Chauhan are thankful for the
Post-Doctoral Research fellowships provided by King Fahd
University of Petroleum and Minerals, Saudi Arabia.
References
1 C. Verma, L. O. Olasunkanmi, E. E. Ebenso, M. A. Quraishi
and I. B. Obot, J. Phys. Chem. C, 2016, 120, 11598–11611.
2 P. Singh, E. E. Ebenso, L. O. Olasunkanmi, I. Obot and
M. Quraishi, J. Phys. Chem. C, 2016, 120, 3408–3419.
3 K. Ansari and M. Quraishi, J. Ind. Eng. Chem., 2014, 20,
2819–2829.
4 A. Dandia, S. Gupta, P. Singh and M. Quraishi, ACS Sustainable
Chem. Eng., 2013, 1, 1303–1310.
5 K. Ansari, M. Quraishi and A. Singh, Corros. Sci., 2014, 79,
5–15.
6 C. Verma, D. Chauhan and M. Quraishi, J. Mater. Environ.
Sci., 2017, 8, 4040–4051.
7 V. Srivastava, D. S. Chauhan, P. G. Joshi, V. Maruthapandian,
A. A. Sorour and M. A. Quraishi, ChemistrySelect, 2018, 3,
1990–1998.
8 M. Quraishi Sudheer, Corros. Sci., 2013, 70, 161–169.
9 D. K. Yadav, B. Maiti and M. Quraishi, Corros. Sci., 2010, 52,
3586–3598.
10 D. S. Chauhan, K. Ansari, A. Sorour, M. Quraishi, H. Lgaz
and R. Salghi, Int. J. Biol. Macromol., 2017, 107, 1047–1057.
11 M. Quraishi Sudheer, RSC Adv., 2015, 5, 41923–41933.

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019 New J. Chem.

Paper
12 W. Gao, Graphene oxide, Springer, 2015, pp. 61–95.
13 X. Li, W. Cai, J. An, S. Kim, J. Nah, D. Yang, R. Piner,
A. Velamakanni, I. Jung and E. Tutuc, Science, 2009, 324,
1312–1314.
14 S. Stankovich, D. A. Dikin, G. H. Dommett, K. M. Kohlhaas,
E. J. Zimney, E. A. Stach, R. D. Piner, S. T. Nguyen and
R. S. Ruoff, Nature, 2006, 442, 282.
15 Y. Zhu, S. Murali, W. Cai, X. Li, J. W. Suk, J. R. Potts and
Published on 21 December 2018. Downloaded by University of Winnipeg on 1/20/2019 10:03:29 PM.
R. S. Ruoff, Adv. Mater., 2010, 22, 3906–3924.
16 D. Li, M. B. Müller, S. Gilje, R. B. Kaner and G. G. Wallace,
Nat. Nanotechnol., 2008, 3, 101.
17 N. Baig and A.-N. Kawde, RSC Adv., 2016, 6, 80756–80765.
18 R. S. Raman, P. C. Banerjee, D. E. Lobo, H. Gullapalli,
M. Sumandasa, A. Kumar, L. Choudhary, R. Tkacz, P. M.
Ajayan and M. Majumder, Carbon, 2012, 50, 4040–4045.
19 D. Prasai, J. C. Tuberquia, R. R. Harl, G. K. Jennings and
K. I. Bolotin, ACS Nano, 2012, 6, 1102–1108.
20 S. Stankovich, D. A. Dikin, R. D. Piner, K. A. Kohlhaas,
A. Kleinhammes, Y. Jia, Y. Wu, S. T. Nguyen and R. S. Ruoff,
Carbon, 2007, 45, 1558–1565.
21 T. A. Saleh and V. K. Gupta, Nanomaterial and polymer
membranes: synthesis, characterization, and applications,
Elsevier, 2016.
22 A. M. Alansi, M. Al-Qunaibit, I. O. Alade, T. F. Qahtan and
T. A. Saleh, J. Mol. Liq., 2018, 253, 297–304.
23 A. Mostafa, A. El-Dissouky, A. Fawzy, A. Farghaly, P. Peu,
P. Dabert, S. Le Roux and A. Tawfik, Bioresour. Technol.,
2016, 216, 520–528.
24 A. Yang, J. Li, C. Zhang, W. Zhang and N. Ma, Appl. Surf. Sci.,
2015, 346, 443–450.
25 H. Lu, H. Zhang, J. Wang, J. Zhou and Y. Zhou, RSC Adv.,
2014, 4, 47297–47303.
26 M.-L. Ye and Y. Zhu, Int. J. Mol. Sci., 2017, 18, 2333.
27 E. Aliyari, M. Alvand and F. Shemirani, Anal. Methods, 2015,
7, 7582–7589.
28 R. K. Gupta, M. Malviya, C. Verma and M. Quraishi, Mater.
Chem. Phys., 2017, 198, 360–373.
New J. Chem. This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
View Article Online
NJC
29 R. K. Gupta, M. Malviya, C. Verma, N. K. Gupta and
M. Quraishi, RSC Adv., 2017, 7, 39063–39074.
30 P. Geerlings, F. De Proft and W. Langenaeker, Chem. Rev.,
2003, 103, 1793–1874.
31 A. D. Becke, J. Chem. Phys., 1993, 98, 5648–5652.
32 C. Lee, W. Yang and R. G. Parr, Phys. Rev. B: Condens. Matter
Mater. Phys., 1988, 37, 785.
33 M. Frisch, G. Trucks, H. B. Schlegel, G. Scuseria, M. Robb,
J. Cheeseman, G. Scalmani, V. Barone, B. Mennucci and
G. Petersson, Gaussian 09, Revision A.02, Wallingford, CT,
2009, vol. 200.
34 D. K. Yadav, D. Chauhan, I. Ahamad and M. Quraishi, RSC Adv.,
2013, 3, 632–646.
35 P. Singh, D. S. Chauhan, K. Srivastava, V. Srivastava and
M. Quraishi, Int. J. Ind. Chem., 2017, 1–10.
36 M. Özcan, I. Dehri and M. Erbil, Appl. Surf. Sci., 2004, 236,
155–164.
37 R. Baboian, Corrosion tests and standards: application and
interpretation, ASTM international, 2005.
38 M. ElBelghiti, Y. Karzazi, A. Dafali, B. Hammouti, F. Bentiss,
I. Obot, I. Bahadur and E. Ebenso, J. Mol. Liq., 2016, 218,
281–293.
39 F. Bentiss, M. Lebrini and M. Lagrenée, Corros. Sci., 2005,
47, 2915–2931.
40 D. K. Yadav, M. Quraishi and B. Maiti, Corros. Sci., 2012, 55,
254–266.
41 I. Obot, D. Macdonald and Z. Gasem, Corros. Sci., 2015, 99,
1–30.
42 R. G. Pearson, Acc. Chem. Res., 1993, 26, 250–255.
43 R. G. Parr, L. v. Szentpaly and S. Liu, J. Am. Chem. Soc., 1999,
121, 1922–1924.
44 A. Kokalj and N. Kovačević, Chem. Phys. Lett., 2011, 507,
181–184.
45 V. Sastri and J. Perumareddi, Corrosion, 1997, 53, 617–622.
46 R. G. Pearson, Proc. Natl. Acad. Sci. U. S. A., 1986, 83, 8440–8441.
47 A. Kokalj, Electrochim. Acta, 2010, 56, 745–755.
48 A. Kokalj, Chem. Phys., 2012, 393, 1–12.