Bioinspired Heterocyclic Compounds As Corrosion Inhibitors: A Comprehensive Review

DOI: 10.1002/asia.
202100201 Minireview
Bioinspired Heterocyclic Compounds as Corrosion Inhibitors:

A Comprehensive Review
Lipiar K. M. O. Goni,[a] Mohammad A. Jafar Mazumder,*[a] M. A. Quraishi,*[b] and
Mohammad Mizanur Rahman[b]
Chem Asian J. 2021, 16, 1324 – 1364 1324 © 2021 Wiley-VCH GmbH
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Abstract: Corrosion is a phenomenon that devastatingly limitations, and heterocyclic compounds as potential corro-
affects innovative, industrial, and mechanical applications, sion inhibitors, mainly nitrogen-based compounds (pyridine
especially in the oil and gas industries. The corrosion (1N), pyrimidine (2N), and triazines (3N) fused ring benzimida-
conceivably influences industrial equipment; it deteriorates zole, etc.), and their biological significance has been
the environment and lessens the equipment/infrastructure’s discussed in detail. The mechanism, challenges, and applica-
lifetime. Considering the significant impact of corrosion in tions of heterocyclic compounds as corrosion inhibitors in
our daily lives, this review article aims to briefly discuss the various industrial relevant corrosive environments such as
significance of corrosion and different control methods with acid pickling, descaling operation in the desalination plant,
special attention on corrosion inhibitors. The classification of oil gas industry, etc., have also been highlighted in the
corrosion inhibitors based on types and their advantage/ review.
1. Introduction which, when added in small concentrations to systems, such as

refinery units, cooling systems, chemicals, boiler, oil and gas
The damages done by the corrosion process have become a production units, etc., reduce or impede the reaction of the
persistent and significant global problem.[1] Corrosion has been metal with the media by forming a protective layer on the
defined by the ruinous assault of metal by biological or metal surface.[22] Among various classes of inhibitors, the use of
electrochemical reaction with its environment.[2] It is more organic inhibitors is one of the most cost-effective and eco-
scientifically defined as the simultaneous transfer of mass and friendly approaches.[23] These organic inhibitors produce a
charge across a metal/solution interface.[3] Iron and its alloys uniform film on the metal surface in the wake of getting
have widespread implications as construction materials in adsorbed through electrostatic interaction with the inhibitor
industrial applications, such as chemical industries, power (physical adsorption) or the formation of a coordinate covalent
plants, and petroleum, due to its low cost, easy fabrication, and bond (chemical adsorption).[24] Therefore, organic compounds
mechanical strength. However, their frequent uses bring them containing heteroatoms (N, O, S, and P), or conjugated bonds,
in contact with different corrosive environments, such as acidic or polar functional groups (> C¼O, COOH, OH, CN, NH2,
solutions used for acid cleaning, acid pickling, acid descaling, NO2), or π systems, or aromatic rings, are considered to be
etching, oil well acidification, etc.[4] This acid-driven corrosion or effective CIs.[25–27]
corrosion in other corrosive media instigates the metal‘s anodic Heterocyclic compounds, according to the Encyclopaedia
dissolution to compromise its structure. This occurrence has Britannica, a classical reference book, are “organic compounds
severe impacts on health and human safety, environment, whose molecules contain one or more rings of atoms with at
materials life span, and economy. A saddening and detailed least one atom (the heteroatom) being an element other than
account of how corrosion inflicted damages upon metallic carbon, most frequently oxygen, nitrogen, or sulfur.”[28] There-
structures and killed people on several occasions can be found fore, the lone pair of electrons associated with the heteroatoms
in recently published literature.[5] The corrosion cost for any are readily available to donate to the targeted metal to cause
country has been reported to be in the range of 1–5% of its effective chemical adsorption. Moreover, when the heteroatoms
GNP.[6] According to a study conducted by NACE, the global are present in acid/alkaline media, they may develop a positive/
corrosion cost for the year 2013 was calculated to be US$2.5 negative charge after undergoing protonation/deprotonation.
trillion, which was 3.4% of the worldwide gross domestic In case a positive charge is formed on the heteroatom, an
product (GDP).[7] acceptance of electrons from the metals via back donation can
Several methods, such as corrosion inhibition,[8–11] anodic occur. In contrast, electron donation to the metal surface results
protection,[12] cathodic protection,[13,14] coating,[15,16] alloying,[17,18] from the heteroatom developing a negative charge. Both of
etc., are available to counter the menaces of the corrosion these cases favor effective adsorption.[29] It is noteworthy that
process. However, the use of corrosion inhibitors (CIs) is nitrogen-containing heterocycles behave as better CIs in
prevalent and economical.[19–21] CIs are chemical substances hydrochloric acid, whereas sulfur-containing ones are preferred
for arresting sulfuric acid corrosion.[30] However, heterocycles
containing both sulfur and nitrogen atoms are considered even
[a] L. K. M. O. Goni, Prof. M. A. Jafar Mazumder better.[31]
Department of Chemistry
King Fahd University of Petroleum & Minerals Since heterocycles or heterocyclic compounds are the core
Dhahran 31261 (Saudi Arabia) elements of a wide range of natural products, such as alkaloids,
Tel.: (966)13 860 7836 amino acids, nucleic acids, vitamins, carbohydrates. They are
Fax: (966) 13 860 4277
E-mail: jafar@kfupm.edu.sa considered eco-friendly.[32] These compounds can be easily
[b] Prof. M. A. Quraishi, Dr. M. Mizanur Rahman synthesized from readily and commercially available sources.
Interdisciplinary Research Center for Advanced Materials Besides, they show excellent inhibition efficiency (IE) even when
King Fahd University of Petroleum & Minerals
used in low concentrations.[33] Heterocyclic compounds, there-
Dhahran 31261 (Saudi Arabia)
E-mail: mumtaz.quarishi@kfupm.edu.sa fore, owing to their environmentally friendly nature, cost-
This manuscript is part of a special collection on Chemistry in Saudi Arabia. effectiveness, and super inhibition efficiency a much sought-
Chem Asian J. 2021, 16, 1324 – 1364 www.chemasianj.org 1325 © 2021 Wiley-VCH GmbH
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after combination of features in an inhibitor are an important Herein we report a comprehensive study on some important
and effective class of CIs. However, since the three- or four- five- and six-membered HCIs and their relevant industrial
membered heterocycles are considerably less stable than the applications, preceded by a brief discussion on the types of
five- or six-membered heterocycles due to ring strain, they do corrosion inhibitors and their mechanism of adsorption.
not constitute the most important classes of heterocyclic
corrosion inhibitors (HCIs). Among five-membered heterocycles,
the most important heterocycles contain two or more N atoms 2. Classification of CIs
(imidazoles, pyrazoles, triazoles, tetrazoles, etc.). Some of them
also contain O or S atoms and N atoms, for instance, oxazoles, Various researchers have grouped inhibitors differently. Never-
thiadiazoles, thiazoles, etc. Fused-ring-based heterocycles, such theless, the classification, according to inhibitors’ chemical
as indole, benzotriazole, benzimidazole, benzoxazole, etc., are nature, is probably the most popular organization and are
also very important CIs. The six-membered heterocycles – presented as follows:
owing to the least amount of ring strain present the most
important class of HCIs. Examples include pyridine, triazines,
tetrazines, diazines (pyrazine, pyridazine, and pyrimidine), and 2.1. Inorganic inhibitors
their derivatives. Quinoline derivatives present the most
common fused-ring inhibitors of this system.[29] Literature Inorganic compounds, which act as inhibitors, are referred to as
searches have generated a few reviews on azoles,[34–37] inorganic inhibitors. The addition of electropositive metal salts
pyrimidines,[38,39] pyrazines,[8] benzimidazoles„[40] etc. However, to a destructive medium is probably the most straightforward
to the best of our knowledge, a comprehensive review covering approach to improve metal‘s passivity. Nevertheless, to guaran-
the most important HCIs of various classes is still missing. tee that the defensive metal ion/particle can be released on the
Lipiar K. M. O. Goni received an MS Dr. M. A. Quraishi is a Chair Professor at

degree in Chemistry (Polymer) from the Interdisciplinary Research Center for
King Fahd University of Petroleum & Advanced Materials, King Fahd Univer-
Minerals (KFUPM), Saudi Arabia. Prior sity of Petroleum and Minerals, Saudi
to that, he achieved an MS degree in Arabia. Before joining KFUPM, he was a
Chemistry (Organic) and a B.Sc. (Hons.) Full Professor in Chemistry at the Indian
degree in Chemistry from Jahangirna- Institute of Technology BHU Varanasi.
gar University, Bangladesh, in 2011 and Dr. Quraishi also served as Head of the
2012, respectively. His research interests Chemistry IIT BHU Varanasi. He ob-
include synthetic organic and polymer tained a Ph.D. (Chemistry) in 1986 at
chemistry, corrosion inhibition, and Kurukshetra University and D.Sc. in
water desalination. corrosion inhibition in 2004 from Ali-
garh Muslim University. Dr. Quraishi
Dr. M. A. Jafar Mazumder obtained his has published more than 300 papers (H
Ph.D. in Chemistry from McMaster Uni- index 81 Citations > 20000) in reputed
versity, Canada, in 2009. After postdoc- journals. He is a fellow of the Royal
toral research in Chemical and Biomed- Society of Chemistry, UK. He is an
ical Engineering, he joined as an Editorial Board member of > 12 Interna-
Assistant Professor of Chemistry at King tional Journals and Associate editor
Fahd University of Petroleum and Min- current Material Science Bentham Sci-
erals (KFUPM), Saudi Arabia, in 2012. ence. His current research area is the
Currently, he has been working as an synthesis and applications of green
Associate Professor of Chemistry at corrosion inhibitors.
KFUPM. His research interests include
polymer synthesis and characterization, Mohammad Mizanur Rahman received
corrosion inhibitors, adsorbents materi- his Ph.D. from the Department of
als, hydrogel, water treatment, and Organic Material Science and Engineer-
biomedical engineering. ing, Pusan National University, South
Korea, in 2008. He is currently working
as a Research Scientist-II in Interdiscipli-
nary Research Center for Advanced
Materials at King Fahd University of
Petroleum and Minerals, Saudi Arabia.
His research interests are the concep-
tion, development, and exploitation of
green polymeric materials for their
application in diverse areas of protec-
tion for offshore platforms, pipeline,
ship hull, and concrete structures.
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Table 1. Some triazole- and tetrazole-based HCIs (IEmax: maximum IE MS: mild steel, DE : EHOMO ELUMO ).
Inhibitor with IEmax Metal/Medium DE [DFT] Remarks Ref.
[%] [eV]
Eadsorption ( 4833.478136)
(neutral molecule)
Neutral
[50]
Cobalt/Water molecule
5.421
1,2,4-Triazole TAZ on Co (111) surface in aqueous phase

(TAZ; 12 mM 84.0%)
(neutral molecule)
Neutral
[51]
MS/1 M HCl molecule
6.52561
5-Decylsulfanyl-1,2,4-triazole TR10 on Fe (110) surface in solution (side view)

(TR10; 10 3 M; 93.0%)
Ebinding (455.087)
(neutral molecule)
Neutral
[52]
MS/1 M HCl molecule
4.039
5-((Thiophen-2-yl)methyleneamino)- TMT on Fe (110) plane in solution

2H-1,2,4-triazole-3-thiol (side view)
(TMT; 5 mmol L 1; 93.0%)
(neutral molecule)
Neutral
[53]
CS/1 M HCl molecule
4.52
5-Hexasulfunyl-1,2,4-triazole HST on Fe (110) surface in solution

(HST; 10 3 M; 98.0%) (side view)
Protonated
6061 Al alloy/ Anodic/mixed [54]
Molecule
0.05 M HCl type inhibition
0.3133
5-[(4-chlorophenoxy)methyl]-4H-1,2,4-triazole-3-thiol
(CMTT; 100 ppm; 95.3%)
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Table 1. continued
[%] [eV]
Ebinding (722)
(neutral molecule)
Neutral
[55]
MS/1 M HCl molecule
4.624
{3-[4-(4-Dimethylamino-phenyl)- DMPTP on Fe (110) surface in solution

[1,2,3]triazol-1-yl]-propyl}-phosphonic (side view)
acid diethyl ester
(DMPTP; 0.001 M; 93.6%)
Neutral
[56]
MS/1 M HCl molecule Adsorption via physisorption on MS
3.31
4-Amino-3-(N-pthallimidomethyl)-1,2,4-triazole-5-thione
(Tz-1; 2.5 × 10 4 M; 95%)
(neutral molecule)
Neutral
[57]
MS/1 M H2SO4 molecule
4.513
Methyl-2-(benzamido)-2-(4-p-tolyl- MBTTA on Fe (110) surface in solution

1H-1,2,3-triazol-1-yl)acetate (top view)
(MBTTA; 0.0005 M; 92.6%)
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Table 1. continued
[%] [eV]
(neutral molecule)
Neutral
[58]
MS/1 M HCl molecule
4.302
(1-(pyridine-4-ylemthyl)-1H-1,2,3-triazole-4-yl)methanol PTM on Fe (100) plane in solution

(PTM; 1 mM; 99.0%) (side view)
Neutral
Adsorption on MS by both [59]
MS/1 M HCl molecule
physi- and chemisorption
5.3787
Ethyl 2-(4-phenyl-1H-1,2,3-triazol-1-yl)acetate
(Tria-CO2Et; 10 3 M; 95.3%)
Neutral
Adsorption on MS by both [59]
MS/1 M HCl molecule
physi- and chemisorption
5.3520
Phenyl-1H-1,2,3-triazol-1-yl)acetohydrazide
(Tria-CONHNH2; 10 3 M; 95.0%)
Ebinding (455.6)
(neutral molecule)
Neutral
Q235 steel/ [60]
molecule
1 M HCl
3.98
1-Phenyl-1H-tetrazole-5-thiol PTZ on Fe (110) plane in solution

(PTZ; 5 mM; 97.1%) (top view)
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Table 1. continued
[%] [eV]
(neutral molecule)
Cathodic
Copper/ [61]
corrosion
1 M CH3COOH
inhibitor
1-Phenyl-1H-tetrazole-5-thiol PMT on Cu (111) surface in solution

(PMT; 5 × 10 4 M; 91.0%) (top view)
(protonated molecule)
3.575
[62]
MS/1 M HCl Protonate
molecule
2-(4,5-dihydro-4-((8-hydroxyquinolin-5- QTB on Fe (110) surface in solution

yl)methyl)tetrazol-1-yl)benzamide (side view)
(QTB; 10 3 M; 89.3%)
Cu Ni (90/10)
alloy/synthetic Mixed Excellent performance even [63]
seawater inhibitor after 30 days of immersion
+ 10 ppm sulfide
5-(3-Aminophenyl)tetrazole
(APT; 6.5 mM; 99.7%)
Protonated
Adsorption on MS surface follows [64]
MS/1 M HCl molecule
Langmuir adsorption isotherm
0.06313
(E)-3-(4-hydroxyphenyl)-2-(1H-tetrazole-5-yl)acrylonitrile
(HTA; 40 mg/L; 98.7%)
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Table 1. continued
[%] [eV]
Ebinding (548.104)
Mixed-type [65]
Cu/0.5 M H2SO4
inhibitor
5-(Benzylthio)-1H-tetrazole BTTAH + on Cu (11) surface

(BTTA; 2 mM; 99.8%) (side view)
metal surface needing protection, the former must have a redox sodium sulfite (Na2SO3), assist by inhibiting corrosion by
potential more positive than the latter and possibly more preventing the oxygen-induced cathodic depolarization.[1]
positive than that required for discharging protons.[41] Depend-
ing on the mode of mechanism, inorganic inhibitors can be
further classified into two categories: 2.2. Organic or film-forming inhibitors
Organic inhibitors, also known as film-forming inhibitors, act by

2.1.1. Anodic or passivating inhibitors forming a uniform film covering the entire metal‘s surface. They
can be classified as anodic, cathodic, or mixed-type. Strong
These inhibitors act by forcing the metallic surface into the interactions, such as π-orbital adsorption, electrostatic adsorp-
passivation range by causing a large anodic shift of the tion, and chemisorption, favor forming this protective film that
corrosion potential.[1] In general, the inhibitors promote the does not let the corrosive species come in contact with the
formation of a cohesive, insoluble film on the metal surface by metal surface.[1,41] The adsorption layer has been reported to be
reacting with the initially formed corrosion product.[42] Oxidizing usually one sub-atomic layer thick and doesn’t enter the more
or non-oxidizing agents might be considered passivating significant part of the actual metal.[43] An efficient organic
inhibitors. Chromates, which are typical oxidizing inhibitors, inhibitor is expected to have polar functional groups and
contain chromate ions reduced to Cr2O3 or Cr(OH)3 on the metal heteroatoms that would establish the adsorption layer and a
(iron or steel) surface to produce chromium and iron blend hydrophobic moiety that would repulse the destructive fluid
oxides. Non-oxidizing passivators, such as phosphates, ben- species from the metal surface. Imidazolines, 1,3-azoles, fatty
zoates, and azelates, first adsorb on the surface and then form a amides, and pyridines are some of the well-known chemical
passive film in the presence of oxygen.[3] Even though families of organic inhibitors.[41]
passivating inhibitors are very effective in reducing the rate of Eco-friendliness, toxicity, cost, and availability are funda-
corrosion, their concentration must not fall below minimum mental criteria that should dictate an inhibitor‘s choice for a
limits, which would cause pitting and accelerate corrosion, particular application.[44] It is well known that inorganic
which is even worse than not using inhibitors at all.[1] inhibitors, for instance, chromates, phosphates, arsenates,
dichromates, etc., are very effective in arresting corrosion. Still,
they are equally harmful as well for the threat they pose to
2.1.2. Cathodic inhibitors health and ecology.[45] Hence, this balance between searching
for effective but benign inhibitors has bothered researchers to
These inhibitors act either by slow down the cathodic response look toward alternatives, such as plant extracts, drugs, amino
itself or specifically encouraging cathodic regions to build the acids, carbohydrates, rare earth elements, etc. Given that
surface impedance and cutoff reducible species’ dissemination heterocyclic compounds constitute many drugs’ building
to these areas. There are three mechanisms that cathodic blocks, several essential/nonessential amino acids, proteins,
inhibitors can show their efficacy through as: (1) cathodic carbohydrates, etc. The phytochemicals found in various plant
precipitates, (2) cathodic poisons, and (3) oxygen scavengers. pieces, like a root, stem, seed, organic product, leaf, bloom, and
Some cathodic inhibitors, such as zinc, calcium, or magnesium so on, are made out of complex heterocycles. They are a
ions, may be precipitated as insoluble oxides on the metal significant class of CIs and are worth special consideration and
surface to form a protective layer. Other cathodic inhibitors, research.[29] However, for the reasons the heterocycles are
such as antimony and arsenic compounds, make molecular abundant in nature, cost-effective, and eco-friendly, they have
hydrogen evolution more difficult. Oxygen scavengers, such as been researched extensively, making their presence in literature
plenty. Consequently, inhibitors that have been published only
Minireview
Table 2. Some imidazole- and pyrazole-based HCIs.

Inhibitor with IEmax Metal/ DE [DFT] Remarks Ref.
[%] Medium [eV]
(neutral molecule)
Protonated
[73]
MS/1 M HCl molecule
1.1273
2-(3-Methoxyphenyl)-4,5-diphenyl-1H-imidazole IM-1 on Fe (110) surface in solution

(IM-1; 100 mg/L; 97.5%) (side view)
Neutral
API X65 steel/ Mixed chemi- and physisorption via [74]
molecule
1 M HCl Langmuir adsorption isotherm
5.771
1-Benzylimidazole
(1-B-ImZ; 500 ppm; 82.0%)
Protonated
[75]
MS/1 M HCl molecule
3.8061
3-Methoxy-4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenol P2 + on Fe (110) surface in solution

(P2; 10 3 M; 96.2%) (side view)
(neutral molecule)
Protonated
[76]
MS/0.5 M H2SO4 molecule
4.4423
2-(4-Methoxyphenyl)- 1,4,5-triphenyl-1H-imidazole IM-OCH3 on Fe (110) plane in solution

(IM-OCH3; 10 3 M; 98.9%) (side view)
Minireview
Table 2. continued
[%] Medium [eV]
Protonated
Adsorption on MS surface via [33]
MS/1 M HCl molecule
3.51
4-Methoxy-2-naphthalen-1-yl-4,5-dihydro-1H-imidazole
(IDZ2a; 20 mg/L; 94.1%)
Protonated
J55 steel/ Adsorption via [77]
Molecule
3.5% NaCl Langmuir adsorption isotherm
1.649
2-(4-Methoxyphenyl)-4,5-diphenyl-imidazole
(M-1; 400 mg/L; 93.0%)
Ebinding (70.23)
(neutral molecule)
Neutral
[78]
Cu/0.5 M H2SO4 molecule
3.672
6-Phenyl-2,3,5,6-tetrahydroimidazo[2,1-b][1,3]thiazole LMS on Cu (111) surface in solution

(LMS; 8 mM; 93.0%) (side view)
(neutral molecule)
Neutral
[79]
MS/1 M HCl molecule
3.413
(E)-N‘-(4-Chlorobenzylidene)-2- 4-CP on Fe (110) surface in solution

(3,5-dimethyl-1H-pyrazol-1-yl)- (side view)
acetohydrazide
(4-CP; 10 3 M; 94.0%)
Minireview
Table 2. continued
[%] Medium [eV]
Neutral
Undergoes both chemi- and physisorption [72]
MS/1 M HCl molecule
via Langmuir adsorption isotherm
3.14
(E)-5-(4-(dimethylamino)phenyl)-3-
(4-(dimethylamino)styryl)-
2,3-dihydro-1H-pyrazole-1-carbothioamide
(DDP; 5 × 10 4 M; 96.6%)
(neutral molecule)
Neutral
[80]
MS/1 M HCl molecule
1.944
6’-Amino-3’-methyl-2-oxo-1’-phenyl- SIPP2 on Fe (110) plane in solution

1’H-spiro[indoline-3,4’-pyrano- (side view)
[2,3-c]pyrazole]-5’-carbonitrile
(SIPP2; 200 ppm; 96.9%)
Protonated
[81]
MS/15% HCl molecule
4.241
(E)-5-Amino-3-(methoxyphenyl)-N’- AMPC on Fe (110) plane in solution

(1-(4-methoxyphenyl)ethylidene)- (top view)
1H-pyrazole-4-carbohydrazide
(AMPC; 300 ppm; 98.3%)
Minireview
Table 2. continued
[%] Medium [eV]
(neutral molecule)
Neutral
[82]
MS/1 M HCl molecule
3.69
5-(4-(Dimethylamino)phenyl)- DPC-1 on Fe (110) surface in solution

3-phenyl-4,5-dihydro-1H- (side view)
pyrazole-1-carboxamide
(DPC-1; 4 × 10 4 M; 84.6%)
(neutral molecule)
Neutral
[83]
MS/1 M HCl molecule
0.159
4,4’-((2-hydroxy-4-methoxyphenyl)methylene)- PYR-OHOMe on Fe (110) surface in solution

bis(3-methyl-1-phenyl-1H-pyrazol-5-ol) (side view)
(PYR-OHOMe; 4.58 × 10 4 M; 94.9%)
(neutral molecule)
Neutral
[84]
MS/1 M HCl molecule
3.58
4-((E)-((E)-3-(4-methoxyphenyl)allylidene)amino)- TMCATP on Fe (110) surface in solution

1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one (side view)
(TMCATP; 1.0 mM; 97.0%)
3. Bioinspired heterocyclic compounds as

recently and/or inhibitors that represent the most important corrosion inhibitors
classes of heterocycles only are discussed/tabulated to highlight
their relevance, effectiveness, and broad application in the field
of corrosion inhibition. Biologically active, non-toxic HCIs are known as bioinspired
heterocyclic inhibitors. They are either synthetic or derived from
natural sources. To highlight their salient features reasonably in
a more readable manner, we have discussed them mostly in
table format following a short discussion on their biological
Minireview
Table 3. Some oxazole-based HCIs (SS: stainless steel).

[%] [eV]
Neutral
L316 SS/ Adsorption via Langmuir [86]
molecule
0.5 M H2SO4 adsorption isotherm
4.210
3,3’-(1,4-phenylene)bis-
(2-imino-2,3-dihydrobenzo[d]oxazole-
5,3-diyl)bis(4-ethylbenzenesulfonate)
(1,4-Ph(OX)2(Ts2); 1 × 10 3 M; 80.4%)
Mixed-type Adsorption via Langmuir [87]

MS/1 M HCl
inhibitor adsorption isotherm
2,5-bis(2-pyridyl)-1,3,4-oxadiazoles
(2-POX; 4 × 10 4 M; 99.1%)
Neutral
316 L SS/ Adsorption via Langmuir [88]
molecule
0.6 M H3NSO3 adsorption isotherm
7.159
(E)-2-(2-(pyren-2-yl)vinyl)benzol[d]oxazole
(PBOX; 2 × 10 4 M; 91.0%)
Neutral
Physisorption via Langmuir [89]
MS/0.5 M HCl molecule
adsorption isotherm
7.995829
2-Methyl-2-{4-[5-(6-methylpyridin-
2-yl)-[1,3,4]oxadiazol-2-yl]-phenyl}-
propionitrile
(6-MMOPP; 300 ppm; 89.7%)
Minireview
Table 3. continued
[%] [eV]
Ti-alloy VT-9/ Mixed-type [90]

Adsorption via chemisorption
4 M H2SO4 inhibitor
2-Phenyl-4-[(E)-1-(4-sulfanylanilino)-
methylidene]-1,3-oxazole-5(4H)-one
(L-SH; 30 ppm; 86.0%)
Mixed-type [91]
MS/0.5 M HCl Adsorption via mixed chemi- and physisorption
inhibitor
2-Butyl-hexahydropyrrolo[1,2-b][1,2]oxazole
(BPOX; 5 × 10 3 M; > 95.0%)
Neutral
[92]
MS/1 M HCl molecule Adsorption via Langmuir adsorption isotherm
5.341
4-{[(4-Ethyl-2-phenyl-4,5-dihydro-1,3-oxazol-4-yl)-
methoxy]methyl}benzene-1-sulfonate
(C2; 10 3 M; 94.7%)
Neutral
[93]
MS/1 M HCl molecule Mixed-type inhibitor
10.30
5-((4,5-dihydro-oxazol-2-yl)methyl)quinoline-8-ol
(QDO; 10 3 M; 95.2%)
importance. However, we have emphasized the biologically and (ATT1–ATT6) by the fusion of thiocarbohydrazide and substi-
industrially most important HCIs that were mainly reported in tuted benzoic acid. The authors studied all six inhibitors for
the last five years. their anticorrosion efficiency toward carbon steel (CS) in 0.5 M
HCl using gravimetric weight loss (WL) methods. With WL being
a very reliable and conventional corrosion rate measurement
3.1. Five-membered heterocycles method in practice, an initial study with inhibitor concentration
0.001 M and temperature 30 °C sorted out ATT5 to be the most
3.1.1. Triazoles and tetrazoles as HCIs effective one. Subsequently, ATT5 was investigated further at
different temperatures and concentrations. An IE of 95.8% was
Triazoles and tetrazoles have enormous importance in medici- achieved for the concentration 4 × 10 3 M at 50 °C. This increase
nal chemistry. Both classes show several biological and in IE with increasing temperature was ascribed to the increase
pharmacological activities, including antibacterial, antiviral, in chemisorption of the inhibitor. Tetrazole derivatives, whose
antifungal, anticancer, analgesic, antioxidant, anti-inflammatory, molecules possess many aromatic systems and nitrogen
anti-HIV, etc.[46] Ahmed et al.[4] synthesized six triazole inhibitors heteroatoms, are useful corrosion inhibitors. Deng et al.[47]
Minireview
Table 4. Thiazole and thiadiazole-based HCIs.

[%] Medium [eV]
Protonated
[94]
MS/1 M HCl molecule
1.709
N-(Benzo[d]thiazole-2-ylimino)ethylaniline BTPIA on Fe (110) surface in solution

(BTPIA; 6 mg/L; 91.7%) (side view)
(neutral molecule)
Neutral
[95]
MS/1 M HCl molecule
3.36499
Methyl (E)-2-(((E)-4-chlorobenzylidene)hydrazono)- T3 on Fe (110) surface in solution

5-(4-chlorophenyl)-2,3-dihydrothiazole- (side view)
4-carboxylate
(T3; 5 × 10 4 M; 92.1%)
Neutral
Adsorption via Langmuir [96]
N80/0.5 M HCl molecule
adsorption isotherm
8.443
(S)-6-Phenyl-2,3,5,6-tetrahydroimidazo[2,1-b]thiazole
hydrochloride
(PTTH; 100 ppm; 95.0%)
Neutral
Adsorption via Langmuir [97]
CS/1 M HCl molecule
adsorption isotherm
10.635
3-((4-Amino-2-methylpyrimidin-
5-yl)methyl)-5-(2-hydroxyethyl)-4-
methylthiazol-3-ium chloride
(AMPMHMC; 40 ppm; 91.4%)
Minireview
Table 4. continued
[%] Medium [eV]
Mixed-type [98]
Cu/1 M HCl
inhibitor
4-(2-Aminothiazole-4-yl)phenol ATPH + on Cu (111) surface in solution

(ATP; 2 mM; 90.9%) (side view)
Protonated
[99]
Cu/1 M HCl Molecule
4.33
4-(Pyridin-3-yl)thiazol-2-amine PyTAH + on Cu (111) surface

(PyTA; 1 mM; 94.0%) in solution (side view)
Ebinding (2860.6)
Neutral
MS/0.5 M [100]
molecule
H2SO4
2.869
2-Amino-4-(4-methoxyphenyl)-thiazole MPTH + on Fe (001) surface in

(MPT; 2.5 mM; 95.0%) presence of Cl (top view)
Minireview
Table 4. continued
[%] Medium [eV]
Ebinding (4866.22)
Neutral
MS/0.5 M [101]
molecule
H2SO4
3.055
2-Amino-(4-bromophenyl)-thiazole BPTH + on Fe (001) plane in

(BPT; 1 mM; 95.4%) presence of SO24 (side view)
AA6061 alloy/ Mixed-type Chemisroption via Langmuir [102]

0.5 M HCl inhibitor adsorption isotherm
2-Amino-4-methyl-1,3-thiazole-5-carboxylate
(EMTC; 100 ppm; 92.7%)
IE decreases
Adsorption on MS [103]
MS/1 M HCl with increasing
via physisorption
temp.
2-Amino-5-(4-nitrophenyl)-1,3,4-thiadiazole
(ANTD; 5 × 10 1 M; 82.0%)
Protonated
[104]
MS/1 M HCl molecule
3.885
2-Amino-5-(2-methoxyphenyl)-1,3,5-thiadiazole 5-AMTH + on Fe (110) surface in solution (side

(5-AMT; 5 × 10 4 M; 98.0%) view)
Minireview
Table 4. continued
[%] Medium [eV]
(neutral molecule)
Neutral
[105]
MS/1 M HCl molecule
1.741
N,N’-(1,4-phenylenebis(methanylylidene))bis- PMTTA on Fe (110) surface

(5-methylthio)-1,3,4-thiadiazol-2-amine) in solution (side view)
(PMTTA; 125 ppm; 92.7%)
Mixed-type
inhibitor with Adsorption on MS via [106]
MS/1 M HCl
cathodic mainly physisorption
predominance
5-Amino-1,3-thiadiazole-2-thiol
(5-ATT; 2 mM; 92.0%)
DMTD prevents
Film formed for immersion at
Bronze/ oxide formation [107]
10 mM DMTD is highly stable
30 g/L NaCl at high concentra-
even at high anodic overvoltage
tion
2,5-Dimercapto-1,3,4-thiadiazole
(DMTD; 10 mM; 99.0%)
Neutral
Adsorption on MS via [108]
MS/1 M HCl molecule
6.798
(4-Dimethylamino-benzylidene)-
[1,3,4]thiadiazol-2-yl-amine
(DBTA; 0.500 M; 91.0%)
Minireview
Table 4. continued
[%] Medium [eV]
(neutral molecule)
MS/
CO2-saturated Neutral
[109]
oilfield molecule
formation 3.657
water
5,5’-Disulfanediylbis-1,3,4-thiadiazol-2-amine DSTA on Fe (110) surface in solution

(DSTA; 0.025 mM; 99.4%) (side view)
reported that most of the tetrazole derivatives that have been increased with NTBC concentration. Some additional recently
reported in the literature so far contain only one tetrazole ring. reported triazole- and tetrazole-based HCIs have been listed in
The authors evaluated nitrotetrazolium blue chloride (NTBC), a Table 1. Eadsorption or Ebinding reported throughout the review is in
tetrazole compound containing two tetrazole rings, for its kJ/mol unless otherwise stated.
inhibition effect on cold-rolled steel (CRS) in 0.5 M H2SO4. NTBC
with two tetrazole rings (eight N heteroatoms), six O atoms in
NO2 and OCH3 groups, π electrons, aromatic systems, the 3.1.2. Imidazoles and pyrazoles as HCIs
possibility, and being protonated in acid solution, and a
prominent molecular structure was anticipated to exert good IE. Srivastava et al.[66] synthesized three amino acid-based imidazo-
WL study at 25 °C showed that the IE increased with increasing lium zwitterions (AIZ-1, AIZ-2, and AIZ-3) by condensing glyoxal,
concentrations of NTBC, with > 90% IE being achieved for only formaldehyde, and amino acids. The naturally occurring,
0.04 mM, whereas the highest IE (95.7%) was performed in biodegradable amino acids are good corrosion inhibitors. They
0.1 mM, meaning that NTBC is an excellent inhibitor for CRS in show a broad range of biological and pharmaceutical
0.5 M H2SO4. NTBC was found to obey Langmuir adsorption activities,[67–70] synthesized zwitterions contain one imidazole
�
isotherm. Gibbs free energy of adsorption (DGads ) value of ring, and two carboxylate groups make them excellent CIs. An
40.97 kJ/mol indicated that the adsorption process was initial WL study conducted at different temperatures (308–
spontaneous and chemisorption. Potendiodynamic polarization 338 K) in 1 M HCl revealed that AIZ-1, AIZ-2, and AIZ-3 had
(PDP) study showed that the value of corrosion current (Icorr ) shown maximum IEs of 90.0, 93.5, and 96.1%, respectively, for
kept decreasing with increasing concentrations of NTBC, with the temperature 308 K at 0.55 mM concentration. The higher IEs
no consistent shifts in corrosion potential (Ecorr ) and no of AIZ-2 and AIZ-3 were attributed to methyl and benzyl
significant changes in anodic ba and cathodic bc values, mean- substituents’ presence in them, respectively. The poor inhibition
ing that the inhibitor was covering more surface upon more performance at elevated temperatures was ascribed to AIZ
addition but not altering the reaction mechanism. Nyquist molecules’ desorption from the MS surface. Activation energies
diagrams, obtained from electrochemical impedance spectro- ðEa Þ were found to be 81.33, 89.43 and 101.64 kJ/mol for AIZ-1,
scopy (EIS) investigation, having similar shapes all through the AIZ-2 and AIZ-3, respectively. The increasing values of Ea within
tested concentrations further proved that practically no sight of AIZ molecules are credited to increasing energy barrier
corrosion mechanism happens because of inhibitor. In any case, for the mild steel disintegration in the corrosive media. Both
the impedance spectra had a huge capacitive circle at high PDP and EIS study revealed the IE order of the AIZ inhibitors to
frequencies followed by a little inductive one at low-frequency be AIZ-1 < AIZ-2 < AIZ-3, confirming the findings of the WL
values. The high-frequency capacitive loop is associated with study. Shifts in the Ecorr values obtained from PDP study
the charge transfer of the corrosion process and double-layer disclosed that AIZ-1 acted as cathodic inhibitor for the Ecorr
manners. However, the low-frequency inductive loop was value moved in the cathodic or more negative direction by
assumed to have been caused by the relaxation process more than 85 mV, whereas AIZ-2 and AIZ-3 played roles as
obtained by adsorption species like FeSO4[48] or inhibitor species mixed inhibitors. Increase in Rct (charge transfer resistance)
on the electrode surface.[49] Alternatively, it may have been values due to increase in the thickness of the electrical double
caused by the re-dissolution of the passivated surface at low layer and decrease in double layer capacitance (C dl ) values due
frequencies.[49] Nevertheless, the capacitive loop diameter in an to the displacement of pre-adsorbed water molecules with
inhibitor‘s presence is bigger than that in the absence of an increasing inhibitor concentrations were observed.
inhibitor, meaning that the inhibited substrate‘s impedance
Minireview
Table 5. Fused-ring heterocycle-based compounds as HCIs.

[%] Medium [eV]
Neutral Mixed physi- and

[126]
Cu/0.5 M H2SO4 molecule chemisorption via Langmuir
0.129 adsorption isotherm
3,3’-((4-methylthio)phenyl)methylene)-
bis(1H-indole)
(TPBI; 12 mM; 98.7%)
Protonated
C38 steel/ Physical adsorption via [114]
molecule
1 M HCl Langmuir adsorption isotherm
4.06
1-Methyl-9H-pyridol[3,4-b]indole
[harmane; 1.2 mM; 93.0%)
22
Eadsorption ( 4.96 × 10 )
(neutral molecule)
Neutral
MS Q235/ [127]
molecule
0.1 M H2SO4
5.182
Indole Ind on Fe (110) surface in gaseous phase

3
(Ind; 8 × 10 M; 97.1%) (side view)
Mixed-type Adsorption via Langmuir [128]

MS/1 M H3PO4
inhibitor adsorption isotherm
5-Chloro-1-(2-dimethylamino)ethyl)-
indoline-2,3-dione
(Indo 1; 10 3 M; 91.0%)
Minireview
Table 5. continued
[%] Medium [eV]
(neutral molecule)
Neutral
[110]
Cu/1 M HCl molecule
2.6800
3-(phenyl(piperidin-1-yl)methyl)-1H-indole AAI-3 on Fe (110) surface in solution

(AAI-3; 0.862 mM; 96.9%) (side view)
Mixed-type Adsorption on MS surface [129]

MS/1 M HCl
inhibitor via physisorption
1-Allyl-5-chloro-indoline-2,3-dione
(TZACI; 10 3 M; 96.0%)
Mixed-type Physisorption via [130]

MS/0.5 M H2SO4
inhibition Langmuir adsorption isotherm
Benzotriazole
(BTA; 0.01 M; 80%)
Mixed-type Adsorption on Cu surface via [131]

Cu/0.1 M HCl
inhibition Langmuir adsorption isotherm
Benzotriazole
(BTA; 0.02 M; 99%)
Low CS/
Mixed-type Addition of 5 mM KI to 100 ppm [132]
1 M HCl +
inhibition MHB increases the IE to 85%
3.5 wt% NaCl
5-Methyl-1H-benzotriazole
(MHB; 100 ppm; 80%)
Minireview
Table 5. continued
[%] Medium [eV]
(neutral molecule)
Neutral
Cobalt/ [50]
molecule
Water
3.797
Benzotriazole BTA on Co (111) surface in solution

(BTA; 9 mM; 88.6%) (side view)
Cathodic Adsorption was spontaneous and [133]

Al/0.1 M HCl
inhibitor followed Temkin adsorption isotherm
5-Methyl benzoxazole-2-tione
(CH3-BOZ; 10 3 M; 73.7%)
(neutral molecule)
Neutral
[134]
3.10
2-(2-Chlorophenyl)-1H-benzimidazole CPBI on Cu (111) surface in solution

(CPBI; 5 mmol/L; 92.3%) (side view)
(neutral molecule)
Protonated
[135]
MS/1 M HCl molecule
2.817
1,4-Bis(2-(4-chlorophenyl)-1H- (IM Cl) + on Fe (110) surface in solution

benzo[d]imidazole-1-yl)butane (side view)
(IM Cl; 5 × 10 < M- > 3M; 93.0%)
Minireview
Table 5. continued
[%] Medium [eV]
Low CS/ Mixed-type Adsorption on CS via [136]

dil. H2SO4 inhibitor Langmuir adsorption
Methyl-5-benzoyl-2-benzimidazole carbamate
(MBZ; 1 g/L; 96.6%)
Protonated
Bronze/ Adsorption via Langmuir [137]
molecule
30 g/L NaCl adsorption isotherm
5.47
Decyl-2-[(5-methylisoxazol-2-yl)methyl]benzimidazole
(DIB; 10 3 M; 98.1%)
(neutral molecule)
Neutral
[138]
MS/1 M HCl molecule
4.682
2-(2-(4-Chlorophenyl)-1H)benzo[d]imidazole-1-yl)- CBIN-2 on Fe (110) surface in solution

N-(3,5-dimethylphenyl)acetamide (side view)
(CBIN-2; 10 3 M; 95.0%)
API 5 L X42 steel/ Mixed-type Adsorption on API 5 L X42 surface via [139]
3.5 wt.% NaCl inhibitor chemical and physical adsorption
2-Mercaptobenzothiazole (MBT)
and sodium phosphate dibasic dehydrate
(1 : 1 molar ratio; 90.0%)
Pyrazole derivatives are very well known and widely concentration 5 × 10 4 M. This level of efficiency for a low
researched because of their many important chemical and concentration of 0.5 mM suggests that DDP is a promising
biological properties.[71] These compounds are considered to inhibitor for MS in 1 M HCl acidic medium. However, a WL study
have low toxicity and high solubility in acidic solutions; hence at different temperatures indicated that the IE increased with
showed good corrosion arrestors in acidic media. increasing concentration but decreased with increasing temper-
Boudjellal et al.[72] synthesized carbothioamide (DDP) based ature, ascribed to the desorption of inhibitor molecules from
corrosion inhibitors using chalcone derivative and thiosemicar- the MS surface at elevated temperatures. At the temperatures
bazide in ethanolic sodium hydroxide solution and studied its IE mentioned above, the thermodynamic parameters study re-
toward MS in 1 M HCl solution. The compound containing vealed that the inhibitor followed Langmuir adsorption iso-
�
nitrogen heteroatoms and additional sulfur, nitrogen atoms, therm at all studied temperatures. DGads values for those
amino group, and benzene ring moiety was expected to impart temperatures were all found to be above 40 kJ/mol, suggest-
good IE. A WL study at 30 °C disclosed that the IE kept ing that the adsorption was spontaneous and chemisorption.
increasing with increasing concentration of DDP inhibitor. PDP study revealed that increasing the concentration of DDP
However, a maximum IE of 96.1% was achieved for the inhibitor significantly lowered the corrosion current density and
Minireview
Table 6.
Pyridine-based HCIs.
[%] [eV]
(neutral molecule)
Neutral
[141]
MS/0.1 M HClO4 molecule
3.4850
2-Amino-5-chloropyridine ACP on Fe (110) surface in solution

(ACP; 0.05 M; 68.4%) (top view)
(neutral molecule)
Protonated
[142]
MS/1 M HCl molecule
4.157
6-Bromo-2-(4-methoxyphenyl)-3-nonyl-3H- PIP on Fe (110) surface in solution

imidazo[4,5-b]pyridine (side view)
(PIP; 10 4 M; 92.0%)
Mixed-type Spontaneous chemisorption [143]

Cu/3 wt% NaCl
inhibition on Cu surface
Pyridine
(Pyr; 5% v/v; 97.0%)
(neutral molecule)
Neutral
[144]
MS/1 M HCl molecule
3,278
1,4,7-Tris[hydrogen(6-methylpyridin-2-yl)phosphonate]- TPP on Fe (110) surface in solution

1,4,7-triazacyclononane (side view)
(TPP; 0.075 mM; 90.0%)
Minireview
Table 6. continued
[%] [eV]
(neutral molecule)
Neutral
[145]
MS/1 M HCl molecule
4.53
2,4-Diamino-7-hydroxy-5-(phenylthiol)-5H- DHPC-3 on Fe (110) surface in solution

chromeno[2,3-b]pyridine-3-carbonitrile (side view)
(DHPC-3; 12.70 × 10 5 M; 97.9%)
corrosion rate, with a maximum IE of 95.5% being achieved for of the WL and PDP study. It was seen that the diameters of the
the concentration 5 × 10 4 M. Shifts in Ecorr , ba , and bc values semicircles for both inhibitors kept increasing with increasing
indicated that the inhibitor played role as mixed type with inhibitor concentrations, and this trend was more pronounced
predominant anodic activity. EIS measurements study further at higher inhibitor concentrations. Linear polarization resistance
corroborated the findings of the WL and PDP study, with (LPR) study also showed that the polarization resistance
increasing inhibitor concentration showing the increasing increased with increasing inhibitor concentrations and IE values
diameter of the semicircles and phase angle values. Some more were comparable with those of EIS. Overall, all IEs obtained
HCIs representing the classes of imidazoles and pyrazoles are from every test method seemed to agree with each other. Both
listed in Table 2. of these inhibitors were found to follow Langmuir adsorption
�
isotherm. DGads values for 2 A5MT and 2MT were found to be
37.99 and 36.59 kJ/mol, respectively, meaning that the
3.1.3. Oxazoles as HCIs inhibition processes were spontaneous and took place through
physisorption and chemisorption, with chemisorption being the
Oxazole is an unsaturated 5-membered ring containing one predominant one. Table 4 outlines more thiazole and thiadia-
oxygen atom at position 1 and nitrogen at position 3 zole-based compounds as HCIs for different corrosive environ-
segregated by carbon in between. Oxazoles and their deriva- ments.
tives play an important role in medicinal chemistry, serving as a
component of aleglitazar (antidiabetic), mubritinib (tyrosine
kinase inhibitor), ditazole (platelet aggregation inhibitor), and 3.1.5. Fused-ring heterocycles (indole, benzotriazole,
oxaprozin (COX-2 inhibitor).[85] Some recently reported oxazole- benzoxazole, and benzimidazole) as HCIs
based HCIs have been mentioned in Table 3.
Verma et al.[110] synthesized three amino alkylated indoles (AAIs)
as AAI-1, AAI-2, and AAI-3 from aldehyde, secondary amines,
3.1.4. Thiazole and thiadiazoles as HCIs and indole using L-proline as a catalyst in solvent-free condition
at room temperature. As the synthetic procedures did not
Döner et al.[31] studied the inhibition effect of 2-amino-5- involve any solvent and L-proline is straightforwardly detached
mercapto-1,3,4-thiadiazole (2 A5MT) and 2-mercaptothiazoline from common organic sources with no unsafe chemicals or
(2MT) on MS corrosion in 1 M H2SO4. These compounds solvents,[111] the essential principles of green chemistry were
containing nitrogen and sulfur in their structures are usually upheld. As indole and its derivatives are already appeared to be
deemed better CIs than those with only one of these an excellent metallic corrosion inhibitor in different electrolytic
heteroatoms. WL study for 24 h immersion at 25 °C showed that media,[112–115] the authors wanted to investigate the effect of
maximum IE of 98.6 and 97.2% were achieved for 2 A5MT and open- and closed-chain amino groups and the ring size of
2MT, respectively, for the concentration 10 mM. PDP study amino groups on the inhibition performance of indole on MS in
showed that the IE increased and corrosion current density 1 M HCl solution. WL experiments revealed that AAI-1, AAI-2,
decreased with increasing inhibitors’ concentrations, with no and AAI-3 had shown IEs of 94.3, 96.1, and 96.9%, respectively,
significant change in the corrosion potential value than that of for the concentration of 0.862 mM after 3 h of immersion in 1 M
the blank solution, meaning that both inhibitors act as mixed- HCl. The IEs of AAIs in the order AAI-1 < AAI-2 < AAI-3 were
type inhibitors. EIS investigation also corroborated the findings ascribed to the increased efficiency imparted by secondary
Minireview
Table 7. Triazine and tetrazine-based HCIs (AA: Aluminum Alloy).

[%] Medium [eV]
(neutral molecule)
Neutral
Cu/3.5 wt.% [148]
molecule
NaCl
0.19914
2-(Dibutylamino)-4,6-Dimercapto-1,3,5-Triazine MSDS on Cu (111) surface in solution

(MSDS; 2 mM; 97.9%) (side view)
22
Eadsorption ( 4.96 × 10 )
(neutral molecule)
Neutral
Medium [149]
molecule
CS/1 M HCl
2.829
6-((1,3,4-thiadiazol-2-yl)thio)-N2-(3-(dimethylamino)propyl)-N4-octyl- Ind on Fe (110) surface in gaseous phase

1,3,5,-trizine-2,4-diamine (side view)
(S3; 1 mM; 99.2%)
(neutral molecule)
Protonated
[150]
MS/1 M HCl molecule
3.724
1,3-Bis-(5,6-diphenyl-1,2,4-triazin-3-yl)thiourea BTT on Fe (110) surface in solution

(BTT; 200 ppm; 98.5%) (side view)
Mixed-
N80 Steel/ Chemisorption via Langmuir [151]
type
15% H2SO4 adsorption isotherm
inhibition
1,3,5-Tris-(4-methoxyphenyl)-1,3,5-triazine
(TZ-3; 800 mg/L 93.2%)
Minireview
Table 7. continued
[%] Medium [eV]
Mixed-
Spontaneous, exothermic adsorption [152]
CS/2% NH4Cl type
via Langmuir adsorption isotherm
inhibition
5-(2-Hydroxyethyl)-1,3,5-triazine-2-thione
(HOTAT; 0.12 mM; 82%)
Cathodic-
2024-T3 AA/ Both triazine ring and carboxyl group [153]
type
1 M HCl play important role in adsorption
inhibitor
Triazine-Methionine
(TRME; 50 mg/L; 97.0%)
Mixed-
SUS304 SS/ Combined chemi- and physisorption [154]
type
0.1 M HCl via Langmuir adsorption isotherm
inhibitor
6-Dibutylamino-1,3,5-triazine-2,4-dithiolmonosodium
(DBN; 0.25 mM; 99.8%)
Cathodic-
Brass/ Physical adsorption via [155]
type
0.5 M NaCl Langmuir adsorption isotherm
inhibitor
6-Dibutylamino-1,3,5-triazine-2,4-dithiolmonosodium
(DBN; 1.2 mM; 98.0%)
Minireview
Table 7. continued
[%] Medium [eV]
Mixed- Inhibition increased with increasing

[156]
MS/1 M HCl type concentration of HT3 but decreased
inhibitor with increasing temp.
6-(4-Hydroxyphenyl)-3-mercapto-7,8-dihydro-
[1,2,4]triazol[4,3-b][1,2,4,5]tetrazine
(HT3; 0.5 mM; 74.0%)
Mixed-
M/0.5 M Chemisorption via Langmuir [157]
type
H2SO4 adsorption isotherm
inhibitor
3,6-Bis(2-methoxyphenyl)-1,2-dihydro-1,2,4,5-tetrazine
(2-MDHT; 100 mg/L; 99.3%)
amine structures in the order opened-chain < pyrrolidine < 2107 and 10508. The Re incentive at 200 rpm shows fluid
piperidine, respectively. Therefore, it was decided that closed- framework progress from laminar to violent stream, while the Re
chain and big-sized ring structures are a better replacement for incentive at 1000 rpm demonstrates fluid under real
opened-chain and small-sized ring structures. The formers turbulence.[125] EIS measurements for the concentrations 300,
would cover a larger portion of the MS surface area and provide 600, and 1200 ppm for BHB and BMB inhibitors under both
better protection. The underlying reason for the observed laminar and turbulent flow conditions showed that the semi-
increased inhibition performance due to the introduction of the circles’ diameter kept increasing with increasing concentration.
ring and increasing the length of hydrophobic carbon/alkyl BMB showed better IE, which could be due to the methyl group
chain was ascribed to the way that the repulsion between the that donates electrons to the benzene ring through inductive
non-polar hydrophobic chain and the polar water stage con- effect. However, the diameter of the semicircles and the values
strained the AAIs to get adsorbed onto MS surface, with polar of total impedance decreased under turbulent flow conditions,
part orienting toward the surface and hydrophobic region meaning that the transfer of corrosive agents to the active sites
toward the solution driving the corrosive species away.[116–118] on the MS surface and desorption of inhibitors from the MS
Benzimidazole derivatives – a class of nitrogen-based fused-ring surface increases under such condition. Nevertheless, BMB still
heterocycles – have been known to act as excellent acid CIs, as played a role as better CI. BHB’s IE under laminar (200 ppm) and
they offer high IEs and less toxicity.[119] Onyeachu et al.[120] turbulent flow (1000 rpm) conditions were recorded to be 64.5
studied the IE of two benzimidazole derivatives: BHB and BMB and 81.6% for the concentration 1200 ppm, respectively, where-
for X60 steel in 1 M HCl solution. The authors’ previous study as, BMB were found to be 70.8 and 86.0%, respectively. X-ray
with these inhibitors for MS in 0.5 M HCl under static conditions photoelectron spectroscopy (XPS) analysis corroborated this
appeared to be a useful corrosion inhibitor.[121] However, in the finding by showing that the steel surface inhibited by BMB
current investigation, the authors wanted to investigate these showed lower intensity of H2O(ads), Cl , Fe and Fe2O3 peaks. Both
inhibitors’ efficacy under hydrodynamic (or flow) conditions. As PDP and LPR measurements further supported the findings of
hydrodynamic conditions reflect the actual industrial acid the EIS study, with PDP study showing that the inhibitors acting
cleaning scenario, studies under these conditions would high- as mixed type inhibitors. IEs found from three different electro-
light inhibitors’ performance while being used industrially. An chemical methods were in good agreement. More of fused-ring
inhibitor can impart excellent IE under static conditions; heterocycles as HCIs are tabulated in Table 5.
however, hydrodynamic factors such as mass transport and wall
shear stress could dramatically change its efficiency.[122–124] In
this regard, the authors employed the rotating cylinder 3.2. Six-membered heterocycles
electrode (RCE) technique to investigate the IE of BHB and BMB
under laminar and turbulent flow conditions. The electro- 3.2.1. Pyridines as HCIs
chemical measurements performed at room temperature under
atmospheric conditions using different rotation speeds (200 Pyridine and its derivatives have engrossed much consideration
and 1000 rpm) were equivalent to Reynolds number (Re) of in recent years due to their superb corrosion inhibition
Minireview
Table 8. Diazine-based compounds as HCIs.

[%] [eV]
Neutral Physisorption dominated

[174]
MS/1 M HCl molecule mixed-adsorption via
4.00 Langmuir adsorption isotherm
(E)-N-{(Thiophene-2-yl)methylene}-
pyrazine-2-carboxamide
(HL; 100 ppm; 94.6%)
Neutral
Chemisorption via Langmuir [175]
MS/0.5 M H2SO4 molecule
adsorption isotherm
9.35
2,5-Dimethylpyrazine
(2,5-DMP; 10 2 M; 97.1%)
(neutral molecule)
Neutral
[176]
Fe/3.5% NaCl molecule
7.878
4-(6-Phenyl-pyridazin-3-ylsulafnyl)- PPS B on Fe (111) surface in solution

butyric acid ethyl ester (top view)
(PPS B; 400 ppm; 93.0%)
Neutral Mixed-type inhibitor;

[177]
MS/1 M HCl molecule adsorption on MS via
5.6455 Langmuir adsorption isotherm
1-((3,6-Di(pyridine-2-yl)pyridazine-4-yl)methyl)-
indoline-2,3-dione
(FM1; 10 3 M; 92.0%)
Mixed-type Physicochemical adsorption via [178]

CS/1 M HCl
inhibitor Langmuir adsorption isotherm
(6-Phenyl-pyridazin-3-ylsulfanyl)-acetic acid
(2,4-dihydroxy-benzylidene)-hydrazine
(PABH; 200 ppm; 93.0%)
Minireview
Table 8. continued
[%] [eV]
(neutral molecule)
Protonated
N80 Steel/ [179]
molecule
15% HCl
1.323
5-Styryl-2,7-dithioxo-2,3,5,6,78-hexahydropyrimido- PP-1 on Fe (110) surface in solution

[4,5-d]pyrimidin-4(1H)-one (top view and side view)
(PP-1; 250 mg/L; 89.1%)
Neutral
Adsorption on MS via [180]
MS/1 M HCl molecule
3.51
6-Phenyl-2H-pyridazine-3-thione
(PPYS; 0.5 mM; 98.0%)
(neutral molecule)
Neutral
[181]
MS/1 M HCl molecule
4.92
2-(6-Chloropyridazin-3-yl)-2-phenylacetone CPA on Fe (110) surface in solution

(CPA; 500 ppm; 95.8%) (side view)
Neutral Mixed-type inhibitor;

[182]
MS/1 M H2SO4 molecule Physisorption via Langmuir
4.15 adsorption isotherm
Acenaptho[1,2-b]pyrazine
(AP; 10 mM; 88.6%
Minireview
Table 8. continued
[%] [eV]
Ebinding (834.645)
(neutral molecule)
N80 Steel/ Mixed-type [166]

15% HCl inhibitor
8,8-Dimethyl-5-p-tolyl-8,9-dihydro-1H-chromeno CP-1 on Fe (110) surface in solution

(;)pyridmidine-2,4,6(3H,5H,7H)-trione (top view and side view)
(CP-1; 200 mg/L; 97.0%)
Ebinding (982.813232)
(neutral molecule)
Neutral
[67]
MS/1 M HCl molecule
4.241
5-(4-hydroxyphenyl)-10-((3R,5S,6R)-2,4,5- CARB-4 on Fe (110) surface in solution

trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-3-yl)- (top view)
9,10-dihydropyrido[2,3-d:6,5-d]dipyrimidine-
2,4,6,8(1H,3H,5H,7H)-tetraone
(CARB-4; 7.41 × 10 5 M; 96.8%)
Minireview
Table 8. continued
[%] [eV]
(neutral molecule)
Neutral
[183]
3.489
4-Mercaptopyrazolo-pyrimidine MPP on Cu (111) surface in solution

(MPP; 4 mM; 99.0%) (top view)
performance.[30,89,140] Meng et al.[140] synthesized two novel development.[146] Tetrazines, because of being both biologically
pyridine Schiff base derivatives, 3-PCPTC and 4-PCPTC, and important and building blocks in synthetic transformation, are
studied their anticorrosion properties for MS in 1 M HCl. A WL equally important.[147] Even though there are many reports on
study in the temperature range 30–50 °C showed that the IE of triazines as HCIs, surprisingly, reports on tetrazines as HCIs are
the inhibitors increased with increasing concentration, with scarce. Since these compounds contain multiple nitrogen atoms
maximum IE being imparted at the concentration of 1 mM for in their structures, they deserve much more attention as an
both inhibitors at 50 °C. However, the IE of the inhibitors was important CI. We have highlighted some of these compounds
found to follow the order: 3-PCPTC (97%) > 4-PCPTC (95%). as HCIs for different corrosive media in Table 7.
Sudheer and Quraishi[30] synthesized three pyridine derivatives:
ADTP I, ADTP II, and ADTP III. The compounds, ADTPs, were
tested for their IE for MS in 1 M HCl. An initial WL study revealed 3.2.3. Diazines (pyrazine, pyridazine, and pyrimidine) as HCIs
the order of the maximum IEs of the studied compounds to be
ADTP I (97.6%) > ADTP II (96.1%) > ADTP III (94.7%) at 308 K for The Well treatment methodology in oil and gas industries
the concentration 1.22 mmol/L above which adding more involves weak or strong acid to restore old wells and eliminate
inhibitor did not show any significant impact. The reason scales. During this activity, corrosive is added to broaden
behind ADTP I showing the best performance among three existing tracks, open new wells, and eliminate scales.[158] Pipes
ADTPs was attributed to the compound possessing an electron- and other metallic structures, however, are exposed to this
donating methoxy group ( OCH3) that helped increase the acidization process and are severely corroded. The corrosive
electron density in the compound through the + I effect. The choice for these treatments relies upon the wellbore HCl, H2SO4,
thermodynamic study showed that the adsorption of ADTPs CH3COOH, and HF are some of the commonly used acids, while
onto MS surface followed Langmuir adsorption isotherm and HCl is preferred to others to the salt‘s solubility produced from
�
DGads values in the range 28.6 to 38.9 kJ/mol proved that it in water. The concentration of the acids used in the process
the adsorption process involved complex interactions as a result ranges from 15 to 28%, leading to severe corrosion only
of both physisorption and chemisorption. Some additional controllable by using an appropriate inhibitor.[159] Pyrazine is a
pyridine-based compounds as HCIs have been discussed in very important heterocyclic molecule that is being exploited for
Table 6. its diverse applications. A pyrazine and its derivatives have
applications in ligands,[160] pharmaceuticals,[161] flavoring in
food,[162] fragrances,[163] anti-tuberculosis and antidiabetic
3.2.2. Triazines and tetrazines as HCIs drugs,[164] and light-emitting diodes.[165] The planarity of the
pyrazine molecules and the availability of π-electrons and N
Triazine scaffold – owing to its possession of an extensive range atoms in its structure make them very efficient inhibitors. They
of biological activities – holds a prominent position as a have applications in food flavoring and pharmaceuticals; as
particular class among all heterocycles. It shows anti-mycobac- already mentioned, they are environmentally friendly and cost-
terial, anti-inflammatory, anti-cancer, anti-viral, etc., activities effective. Obot et al. synthesized three pyrazine molecules as
that make it a very attractive scaffold in drug designing and Pyrazine C, Pyrazine E, and Pyrazine H. They tested them for
Minireview
Table 9. Macrocyclic and six-membered fused-ring heterocycles as HCIs.

[%] [eV]
Neutral
Adsorption on MS [184]
MS/2.0 M H3PO4 molecule
surface via chemisorption
2.358
5-((2-(4-nitrophenyl)-1H-benzo[d]imidazol-
1-yl)methyl)quinolin-8-ol
(Q-NO2; 10 3 M; 86.0%)
Eadsorption ( 3.01 eV)

(neutral molecule)
Mixed-type [185]
MS/1.0 M H2SO4
inhibitor
2,3-di(furan-2-yl)quinoxaline Optimized parallel adsorption configuration

(FQ; 10 mM; 97.6%) of FQ on Fe (100) surface
(neutral molecule)
Neutral
[186]
MS/1 M HCl molecule
2.974
4-(1-((4-hydroxynaphthalen-1-yl)methyl)- QN1 on Fe (110) surface in solution

5-methyl-1H-benzo[d]imidazol-2-yl)benzoic acid (side view)
(QN1; 1.0 mM; 97.7%)
Minireview
Table 9. continued
[%] [eV]
Mixed-type Adsorption on J55 steel surface through [187]

J55 steel/3.5% NaCl
inhibitor both chemi- and physisorption
4,4’,4’’,4’’’-(porphyrin-5,10,15,20-
tetrayl)tetrakis(benzoic acid)
(PF-2; 400 ppm; 93.0% )
Neutral
Adsorption through both [188]
N80 steel/3.5% NaCl molecule
chemi- and physisorption
3.07
1,2,4,7,9,10-
hexaazacyclo-pentadeca-10,15-
dien-3,5,6,8-tetraone
(HPT; 200 ppm; 95.0%)
Mixed-type Both physical and chemical (comprehensive) [189]

J55 steel/3.5 wt.% NaCl
inhibitor adsorption on a J55 steel surface
1,2,4,7,9,10-
hexaazacyclo-pentadeca-10,15-
dien-3,5,6,8-tetraone
(HPT; 400 ppm; 93.0%)
(neutral molecule)
Mixed-type [190]
J55 steel/3.5 wt.% NaCl
inhibitor
1-phenyl-1,2-dihydronaphtho[1,2-e]- PNO on Fe (110) surface in solution

[1,3]oxazin-3-one (side view)
(PNO; 500 ppm; 90.4%)
Minireview
Table 9. continued
[%] [eV]
Electron donation of O and N atoms

Hot dip galvanized steel (HDG)/ Mixed-type [191]
from 8-HQ onto the anodic sites
50 mM NaCl solution inhibitor
of HDG forms a protective layer
8-Hydroxyquinoline
(8-HQ; 0.5 g/L; 97.8%)
Cathodic Adsorption on MS surface through both [192]

MS/1 M HCl
inhibitor chemical and physical adsorption
2-amino-4-(4-(dimethylamino)phenyl)-7-hydroxy-
1,4-dihydroquinoline-3-carbonitrile
(Q-4; 150 ppm; 98.1%)
their IEs on X60 steel in 15% HCl, simulating oil well acidizing conditions, and the test results from different methods were in
conditions.[159] The increase in the radii of the capacitive arcs in good agreement.
Nyquist plots obtained from EIS measurements for solutions Very recently, Singh et al.[166] synthesized two bioinspired
with 0.2 wt% inhibitors at 25 °C was a clear indication of and environmentally benign chromeno pyrimidine (CPs) deriva-
inhibition. However, it was inhibitor pyrazine E that contains tives using a typical green methodology. The CP molecules,
one extra N atom that helped it adsorb strongly onto the steel namely CP-1 and CP-2, were tested as potential CI for N80 steel
surface showed the best IE (54.9%) among all three pyrazine in 15% HCl solution. CPs exhibit a wide range of biological
derivatives. PDP study also showed that pyrazine E was the properties, such as antitumor,[167] anti-anaphylactic,[168]
best-performing inhibitor with IE 61.9%, as it reduced the Icorr anticoagulant,[169] antimicrobial,[170] diuretic,[171] and
[172]
value more than others. All of the studied inhibitors were spasmolytic activities. These corrosion inhibitors were re-
evaluated as a mixed type, but pyrazine E was found to be ported to be in the green CI category.[173] Additionally, since
predominantly cathodic with constant Ecorr . The findings of the CPs’ molecular framework contains pyrimidine and pyran rings
PDP study were further corroborated by the results obtained in the single-molecule, heteroatoms like N and O, and π-
from LPR measurements, as it was pyrazine E that increased the electrons, they can adsorb very well onto the metal surface. An
Rp value from its blank solution (57.9 Ω cm 2) to the maximum initial WL study at 35 °C for N80 steel immersed in the corrosive
value of 138.6 Ω cm 2; hence showed the best IE (58.2%). After solution for 6 h indicated that CP-1, owing to the presence of
conducting the electrochemical tests at a constant concentra- an electron-donating CH3 group, performed as a better
tion of 0.2 wt%, the authors further exploited the WL technique corrosion inhibitor than CP-2, with CP-1 and CP-2 showing 97%
to realize the concentration and temperature effect on the and 94% IE, respectively at 200 mg/L. Because any further
inhibitor‘s inhibition performances. The IE values were ranked increase in the concentration did not significantly improve the
as pyrazine E > pyrazine C > pyrazine H at both 60 °C and 90 °C, IE, 200 mg/L was fixed as the optimum concentration. While the
with the best efficiency achieved at 90 °C and 1% concentration, service life of N80 steel without adding any inhibitors was
which has been ascribed to the development of the desorption- found to be 0.12 yrs only in the corrosive solution, its service
adsorption equilibrium of the inhibitors towards adsorption and lifetime increased to 4.08 yrs and 2.04 yrs in presence of CP-1
thermally initiated chemisorption and the formation of stronger and CP-2 inhibitors, respectively at 200 mg/L. Adsorption
bonds at higher inhibitor concentration and elevated temper- isotherm study revealed the values of adsorption equilibrium
�
ature. Overall, the inhibitors performed very well in highly acidic constant (K ads ) and DGads for CP-1 to be 90.9 × 103 M 1 and
Minireview
Table 10. Some industrially useful HCIs.

Inhibitor with IEmax Metal/ Concentration [IEmax] Applications Ref.
[%] Medium
Marine corrosion [148]

Cu/3.5% NaCl 2 mM (97.9%)
environment
2-(Dibutylamino)-4,6-dimercapto-1,3,5-triazine
(MSDS)
Oil well acidization/

N80 steel/ [151]
800 mg/L (93.2%) rejuvenation in
15% HCl
oil industries
1,3,5-Tris(4-methoxyphenyl)-1,3,5-triazine
(TZ-3)
Pipelines in deep
J55 steel/ and ultra-deep [77]
400 mg/L (93.0%)
3.5% NaCl saturated with CO2 wells in oil and
gas industries
2-(4-Methoxyphenyl)-4,5-diphenyl-imidazole
(M1)
Cleaning of demisters,
heat exchangers,
316 L SS/ 4 [88]
2 × 10 M (91.0%) and cooling waters
NH2SO3
systems in
desalination plants
(E)-2-(2-(Pyren-2-yl)vinyl)benzo[d]oxazole
(PBOX)
Minireview
Table 10. continued

Inhibitor with IEmax Metal/ Concentration [IEmax] Applications Ref.
[%] Medium
Industrial acid pickling/ [80]

MS/1 M HCl 200 ppm (96.9%)
cleaning/descaling
6’-Amino-3’-methyl-2-oxo-1’-phenyl-1’H-
spiro[indoline-3,4’-pyrano[2,3-c]pyrazole]-
5’-carbonitrile
(SIPP-2)
Seawater piping,
condensers in ships,
Cu Ni (90/10) alloy/ [63]
6.5 mM (99.7%) heat exchangers,
synthetic seawater + 10 ppm sulphide
ship hulls,
and power plants
5-(3-Aminophenyl)tetrazole
(APT)
Aerospace, aviation,
AA6061 alloy/ [102]
100 ppm (92.7%) automotive, and
0.5 M HCl
construction sectors
Ethyl-2-Amino-4-methyl-1,3-thiazole-5-carboxylate
(EMTC)
Chemical mechanical
polishing in the [194]
Cobalt (Co) 12 mM (81.8%)
preparation of
integrated circuits
1,2,4-Triazole
(TAZ)
39.5 kJ/mol, respectively, whereas, that of CP-2 to be 58.5 × respectively, whereas, that of CP-2 were found to be 93.1% and
103 M 1 and 38.4 kJ/mol, respectively, indicating that both 92.0%, respectively, at 200 mg/L, indicating that results
inhibitors underwent strong adsorption onto N80 steel surface obtained from all corrosion measurement techniques were in
and the mechanism of adsorption was combined process of good agreement. The shifts in Ecorr , ba and bc values of CP-
physisorption and chemisorption. The Ea values for the blank added solutions with respect to those of blank solution
solution, CP-1 and CP-2 inhibitors added solution were indicated that both inhibitors acted as mixed-type. Atomic force
computed to be 4.083, 12.27 and 11.28 kJ/mol, respectively, microscopy (AFM) and XPS study further showed that the
indicating that the activation energy for the metal dissolution inhibitors were adsorbed onto N80 steel surface to reduce
increased in the inhibitors added solution hence increased metal dissolution. MD simulation study showed that CP-1 has
protection in their presence. The IE of CP-1 obtained from EIS flat orientation on top of the metal specimen, whereas, in CP-2
and PDP measurements were found to be 96.4% and 93.0%, phenyl ring is perpendicular to the surface, thereby reducing
Minireview
the IE of CP-2. Furthermore, the calculated binding energy of However, chemisorption would probably be the most dominant
CP-1 and CP-2 were found to be 834.6 kJ/mol and 814.8 kJ/mol, adsorption mechanism for HCIs. In chemisorption or chemical
respectively, indicating that CP-1 had higher adsorption capa- adsorption, lone pair of electrons from the metal atoms (n to d)
bility. Some more diazine-based HCIs have been discussed in or π-electrons from the aromatic systems or conjugated bonds
the following Table 8. (π to d) can donate to the empty d-orbitals of Fe in the metal
substrate. On the contrary, sometimes, electrons from the filled
d-orbitals of Fe can also contribute to the π antibonding
3.2.4. Other six-membered fused-ring and macrocyclic orbitals (d to π*) of the aromatic system to cause adsorption via
heterocyclic compounds as HCIs retro donation. These different forms of adsorptions that HCIs
could keep the metal surface highly protected from the attack
Quinoline derivatives have been reported to be acting as of any aggressive corrosive species present in the electrolyte
excellent CIs owing to the planarity they possess and hence media. The hydrocarbon tail, or the hydrophobic portion of any
protect the surface of metals from aggressive electrolytic corrosion inhibitor, is mainly responsible for driving away from
species.[184] Additionally, they are essential components of anti- the water molecules from the metal substrates’ surface for
malarial drugs and have significant pharmacological activities. better protection.
Quinoxaline, containing a pyrazine cycle annulated with the
benzene ring, is another important class of fused ring hetero-
cycles. Quinoxaline derivatives are not only good HCIs but also 5. Industrial applications of HCIs
possess significant anti-tuberculotic, anti-mycobacterial, anti-
cancer, and anti-trichomonas activities.[185] Macrocycle ligands The phenomenon of corrosion is liable for scores of losses in
and metal complexes, a rather less explored but effective CI the industrial scope. Several potential disasters – economic
class, deserve more attention because of the excellent losses, casualties, and environmental side effects – can be
protection they can provide to metal surfaces in aggressive avoided following an appropriate corrosion control method.[42]
corrosive media. In this section of the review, we have tabulated Inhibitors have great appeal in the industries because of their
some recent and high efficiency macrocyclic and six-membered excellent anticorrosive nature. However, they leave harmful
fused-ring heterocycles as HCIs in Table 9. effects on the environment, leaving us with no choice but
finding eco-friendly corrosion inhibitors. Environmentally be-
nign inhibitors have pronounced industrial implications as
4. General Mechanism of Corrosion inhibition inhibitors in oil and gas industries, coal-water slurries, cooling
water systems, reinforcing steel in concrete, coatings, etc.[193]
Heterocyclic compounds, owing to their possession of different HCIs – being both eco-friendly and excellent CIs – have found
heteroatoms (O, N, S, P, etc.) and additional conjugated bonds, implications in several industrial applications as well. Some of
π systems, and aromatic rings, adsorb very well on the surface them, with their industrial scopes, have been mentioned in
of the steel substrates.[25] Figure 1 shows the general mecha- Table 10.
nism of adsorption for a triazine-based HCI. When the inhibitor
is in an acid medium, there is always a chance that it can get
protonated and undergo adsorption via electrostatic interac- 6. Conclusions
tion, also known as physical adsorption or physisorption.[29]
This review article has discussed and tabulated an enormous
pool of HCIs representing different classes from five- and six-
membered heterocycles. Corrosion study is a multidisciplinary
approach combining many areas of science and engineering. It
is impossible to stop corrosion from happening; however, it can
be prevented from causing the losses it incurs largely by an
intelligent corrosion tackling approach. Of all the available
corrosion prevention methods, corrosion inhibition has been
dubbed as a great approach in both efficacy and economy.
However, a CI being an excellent performer only in terms of IE
is no longer desirable. Therefore, the modern approach is to
find and exploit the ones that are efficient, cheap, and non-
toxic – equally. HCIs, as we have highlighted rather excessively,
are environmentally benign, with their IEs being top-notch as
well. Their structures carry multiple numbers of heteroatoms, π-
bonds, lone pair of electrons, etc., that help them adsorb very
well onto different metal surfaces. As a consequence, they have
Figure 1. Different adsorption routes for protonated 2-(Dibutylamino)-4,6- implications in industrial setup enormously. To highlight that
dimercapto-1,3,5-triazine on a steel surface in an acid medium. feature, we showed earlier in Table 10 how they are being used
Minireview
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[20] A. Miralrio, A. E. Vázquez, Processes 2020, 8, DOI 10.3390/PR8080942.
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Bioinspired Heterocyclic Compounds As Corrosion Inhibitors: A Comprehensive Review

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Bioinspired Heterocyclic Compounds As Corrosion Inhibitors: A Comprehensive Review

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DOI: 10.1002/asia.

Bioinspired Heterocyclic Compounds as Corrosion Inhibitors:

1. Introduction which, when added in small concentrations to systems, such as

Lipiar K. M. O. Goni received an MS Dr. M. A. Quraishi is a Chair Professor at

1,2,4-Triazole TAZ on Co (111) surface in aqueous phase

5-Decylsulfanyl-1,2,4-triazole TR10 on Fe (110) surface in solution (side view)

5-((Thiophen-2-yl)methyleneamino)- TMT on Fe (110) plane in solution

5-Hexasulfunyl-1,2,4-triazole HST on Fe (110) surface in solution

{3-[4-(4-Dimethylamino-phenyl)- DMPTP on Fe (110) surface in solution

Methyl-2-(benzamido)-2-(4-p-tolyl- MBTTA on Fe (110) surface in solution

(1-(pyridine-4-ylemthyl)-1H-1,2,3-triazole-4-yl)methanol PTM on Fe (100) plane in solution

1-Phenyl-1H-tetrazole-5-thiol PTZ on Fe (110) plane in solution

1-Phenyl-1H-tetrazole-5-thiol PMT on Cu (111) surface in solution

2-(4,5-dihydro-4-((8-hydroxyquinolin-5- QTB on Fe (110) surface in solution

5-(Benzylthio)-1H-tetrazole BTTAH + on Cu (11) surface

Organic inhibitors, also known as film-forming inhibitors, act by

Table 2. Some imidazole- and pyrazole-based HCIs.

2-(3-Methoxyphenyl)-4,5-diphenyl-1H-imidazole IM-1 on Fe (110) surface in solution

3-Methoxy-4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenol P2 + on Fe (110) surface in solution

2-(4-Methoxyphenyl)- 1,4,5-triphenyl-1H-imidazole IM-OCH3 on Fe (110) plane in solution

6-Phenyl-2,3,5,6-tetrahydroimidazo[2,1-b][1,3]thiazole LMS on Cu (111) surface in solution

(E)-N‘-(4-Chlorobenzylidene)-2- 4-CP on Fe (110) surface in solution

6’-Amino-3’-methyl-2-oxo-1’-phenyl- SIPP2 on Fe (110) plane in solution

(E)-5-Amino-3-(methoxyphenyl)-N’- AMPC on Fe (110) plane in solution

5-(4-(Dimethylamino)phenyl)- DPC-1 on Fe (110) surface in solution

4,4’-((2-hydroxy-4-methoxyphenyl)methylene)- PYR-OHOMe on Fe (110) surface in solution

4-((E)-((E)-3-(4-methoxyphenyl)allylidene)amino)- TMCATP on Fe (110) surface in solution

3. Bioinspired heterocyclic compounds as

Table 3. Some oxazole-based HCIs (SS: stainless steel).

Mixed-type Adsorption via Langmuir [87]

Ti-alloy VT-9/ Mixed-type [90]

Table 4. Thiazole and thiadiazole-based HCIs.

N-(Benzo[d]thiazole-2-ylimino)ethylaniline BTPIA on Fe (110) surface in solution

Methyl (E)-2-(((E)-4-chlorobenzylidene)hydrazono)- T3 on Fe (110) surface in solution

4-(2-Aminothiazole-4-yl)phenol ATPH + on Cu (111) surface in solution

4-(Pyridin-3-yl)thiazol-2-amine PyTAH + on Cu (111) surface

2-Amino-4-(4-methoxyphenyl)-thiazole MPTH + on Fe (001) surface in

2-Amino-(4-bromophenyl)-thiazole BPTH + on Fe (001) plane in

AA6061 alloy/ Mixed-type Chemisroption via Langmuir [102]

2-Amino-5-(2-methoxyphenyl)-1,3,5-thiadiazole 5-AMTH + on Fe (110) surface in solution (side

N,N’-(1,4-phenylenebis(methanylylidene))bis- PMTTA on Fe (110) surface

5,5’-Disulfanediylbis-1,3,4-thiadiazol-2-amine DSTA on Fe (110) surface in solution

Table 5. Fused-ring heterocycle-based compounds as HCIs.

Neutral Mixed physi- and

Indole Ind on Fe (110) surface in gaseous phase

Mixed-type Adsorption via Langmuir [128]

3-(phenyl(piperidin-1-yl)methyl)-1H-indole AAI-3 on Fe (110) surface in solution

Mixed-type Adsorption on MS surface [129]

Mixed-type Physisorption via [130]

Mixed-type Adsorption on Cu surface via [131]

Benzotriazole BTA on Co (111) surface in solution

Cathodic Adsorption was spontaneous and [133]

2-(2-Chlorophenyl)-1H-benzimidazole CPBI on Cu (111) surface in solution

1,4-Bis(2-(4-chlorophenyl)-1H- (IM Cl) + on Fe (110) surface in solution

Low CS/ Mixed-type Adsorption on CS via [136]

2-(2-(4-Chlorophenyl)-1H)benzo[d]imidazole-1-yl)- CBIN-2 on Fe (110) surface in solution

2-Amino-5-chloropyridine ACP on Fe (110) surface in solution

6-Bromo-2-(4-methoxyphenyl)-3-nonyl-3H- PIP on Fe (110) surface in solution

Mixed-type Spontaneous chemisorption [143]

1,4,7-Tris[hydrogen(6-methylpyridin-2-yl)phosphonate]- TPP on Fe (110) surface in solution

2,4-Diamino-7-hydroxy-5-(phenylthiol)-5H- DHPC-3 on Fe (110) surface in solution

Table 7. Triazine and tetrazine-based HCIs (AA: Aluminum Alloy).

2-(Dibutylamino)-4,6-Dimercapto-1,3,5-Triazine MSDS on Cu (111) surface in solution