Integrated polyaniline with graphene oxide-iron tungsten nitride nanoflakes as ultrasensitive electrochemical sensor for precise detection of 4-nitrophenol within aquatic media
Graphical abstract
Introduction
Nowadays, wide distribution of toxic substrates within the ecosystem and their resulting adverse consequences, raised a global requirement for finding practical approaches for their accurate determination and rapid removal from the nature. Among these toxic pollutants, 4-nitrophenol (4-NP) (i.e., 4-hydroxynitrobenzene or p-nitrophenol) as a highly toxic organic chemical compound with chemical formula of C6H5NO3 found to be highly problematic for life of living species due to its mutagenic, phyto- and cyto-toxic effects which known as a precursor for fabrication of pharmaceutical, dyes, papers, insecticides, herbicides and pesticides [[1], [2], [3]]. 4-NP exist in two polymorphs including alpha and beta, where the alpha type is colorless and stable under sunlight but unstable at room temperature (RT), while the beta form is yellow colored, stable at RT and unstable under sunlight [4].
Human being can be adversely affected by 4-NP through several pathways, including inhalation, ingestion and skin conduct. When this compound polluting the food chain, it could deteriorate the performance of liver and kidney, cause cancer in diverse parts of the body, and negatively affect the function of nervous system [5]. Moreover, 4-NP can lead to inflammation/irritation in eyes repiratory tract and nose. It also interact with the blood and generate methaemoglobin which is responsible for the methaemoglobinemia that lead to cyanosis unconsciousness and confusion [6]. Short term exposure to 4-NP may cause various kinds of health problems among which headaches, nausea, cyanosis and drowsiness can be mentioned [7]. Thus, due to these harmful effects, the U.S Environmental agencies considered the 4-NP as one of the most toxic pollutants for the life of living species and ecosystem, while 20 ppb (i.e., 0.14 μM) considered as the maximum permissible limit of this toxic compound within the aquatic environment [5,8].
So far, various methods have been utilized for precise detection of 4-NP within aqueous media, including UV–vis spectroscopy [9], liquid chromatography [10], fluorescence spectroscopy [11], capillary electrophoresis [12], gas chromatography [13], indirect enzymatic immunosorbent assay [14] and chemiluminescence [15]. Despite the fact that these methods can detect the 4-NP with high accuracy and ideal resolution, however, time consuming approach, expensive equipment, requirement of pretreatment, complicity of the method, tedious procedure, high amount of solvent consumption and restriction of the real-time detection narrowed down the applicability of such approaches and raised the requirement for a rapid, economic, real-time and precise method for detection of 4-NP within aquatic media [2,8].
In this matter, electrochemical-based methods found to be desirable alternative instead of aforementioned protocols due to their superior accuracy, ideal sensitivity, cost affordability, simplicity, real-time viability and rapid measurement/response that can easily identify the analyst within real samples [[16], [17], [18], [19], [20], [21]]. However, development of a highly accurate and sensitive electrochemical sensor with ideal electroanalytical performance is still a required demand [22]. Additionally, the catalytic reduction is a much more supportable method for conversion of 4-NP into 4-aminophenol due to the importance of this compound for fabrication of pigments, pharmaceutical and agrochemicals [23].
In addition, various kinds of nano-based electrocatalysts have been developed for modification of electrodes for precise electrochemical detection of phenol-based compounds, such as carbonaceous materials (e.g., graphene and its by-products including carbon nanotube (CNT) and mesoporous carbon) [[24], [25], [26]], conductive polymers (e.g., polypyrrole and polyaniline) [27,28], metal oxides (e.g., Fe3O4, ZnO and MnO2) [[29], [30], [31]] and noble metals (e.g., Pd, Au and Ag nanoparticles) [7,32,33]. In this matter, carbonaceous materials found to be ideal alternative as support for other metallic or non-metallic materials due to their superior specific surface area, porous structure, hierarchically and multifunctionality that make them fantastic electrocatalysts. Usage of graphene by-products as an active electrode in electrochemical-based sensors/biosensors, could enhance the redox current of the final platform and decrease the final detection limit along with improving the linear detection range. Graphene can considerably improve the current response, while its modification with metallic-complexes can inhibit their aggregation and improve their electrocatalysis performance. Their usage also lead to intense analytical signals owing to their ideal conductivity and high specific surface area [34,35].
Among conductive and electroactive polymers, polyaniline (PANi) considered as ideal candidate for modification of electrodes due to its simple preparation method, high electrical conductivity and ideal stability that make it fantastic alternative for development of precise sensors and electronic devices [36]. In this case, PANi was applied for detection of 4-NP owing to its superior environmental stability, tunable electrical conductivity and facile doping process [37,38]. What is more, doped PANi with practical materials could improve the sensitivity and enhance the dynamic factor of the electrochemical reaction [39], while the modified PANi with metallic complexes showed significantly better sensing, electrical and catalytic responses compared with the pure PANi [40]. Furthermore, integration of PANi with graphene by-products can improve their catalytic performance and modify/control their morphology [41].
Herein, well-exfoliated GO nanoflakes were decorated with interconnected, porous, highly dense and sensitive pathway of iron tungsten nitride and thence the protonated polymeric structure of PANi was reinforced/modified with different weight percentages of iron tungsten nitride toward improving its sensitivity for accurate detection of 4-NP within aquatic media. Thereafter, the electrode was modified using as prepared nanocomposite consisted of polyaniline-GO‑iron tungsten nitride and then applied for accurate detection of 4-NP in the aqueous samples through a real-time and repeatable approach. Outcome of performed evaluations exhibited the superior sensitivity and very low detection limit of the developed sensor till the nano molar level.
Section snippets
Characterization of developed nanomaterials
In this part, developed nanomaterials were subjected to diverse analyses to confirm their successful synthesis and modification. In Fig. 1 (a), outcome of XRD analysis for developed GO nanoflakes can be seen. As shown, GO nanoflakes exhibited 2θ peak of about 23.06 that attributed to the (002) plane of heterocyclic graphene. Likewise, Fig. 1 (b) illustrated the outcome of micro Raman spectroscopy for graphene nanoflakes that showed well-resolved D, G and D + G bands at 1366.25, 1627.42 and
Conclusions
The uprising level of 4-NP consumption in diverse industries and its careless disposal in the ecosystem highlighted an urgent requirement for developing an accurate method for its determination and removal from the aquatic ecosystem. Herein, we addressed this requirement through reinforcement of PANi with interconnected, porous and highly sensitive hybrid GO-ITN nanoflakes toward real-time and accurate detection of 4-NP within aqueous media. In this matter, the surface of GCE electrode was
Acknowledgement
Full details of experimental section including used chemical reagents, procedures, characterization techniques and details of electrochemical setup can be seen within the supporting information.
Declaration of Competing Interest
None.
References (83)
- et al.
Synthesis of silver nanoparticles decorated on core-shell structured tannic acid-coated iron oxide nanospheres for excellent electrochemical detection and efficient catalytic reduction of hazardous 4-nitrophenol
Compos. Part B
(2019) - et al.
Amperometric microbial biosensor for p-nitrophenol using Moraxella sp.-modified carbon paste electrode
Biosensors Bioelectronics
(2005) - et al.
Controlled synthesis of reduced graphene oxide supported silver nanoparticles for selective and sensitive electrochemical detection of 4-nitrophenol
Electrochim. Acta
(2016) - et al.
An electrochemical sensor based on polyelectrolyte-functionalized graphene for detection of 4-nitrophenol
J. Electroanal. Chem.
(2014) - et al.
Oxidized multiwalled carbon nanotubes as a novel solid-phase microextraction fiber for determination of phenols in aqueous samples
J. Chromatogr. A
(2007) - et al.
Highly selective detection of p-nitrophenol using fluorescence assay based on boron, nitrogen co-doped carbon dots
Talanta
(2018) - et al.
The separation and determination of nitrophenol isomers by high-performance capillary zone electrophoresis
Talanta
(2004) - et al.
Application of a quick, easy, cheap, effective, rugged and safe-based method for the simultaneous extraction of chlorophenols, alkylphenols, nitrophenols and cresols in agricultural soils, analyzed by using gas chromatography–triple quadrupole-mass spectrometry/mass spectrometry
J. Chromatogr. A
(2010) - et al.
Development and optimization of an indirect enzyme-linked immunosorbent assay for 4-nitrophenol. Application to the analysis of certified water samples
Anal. chimica Acta
(1999) - et al.
Electrochemical sensors based on platinum electrodes modified with hybrid inorganic–organic coatings for determination of 4-nitrophenol and dopamine
Electrochim. Acta
(2009)
Electrochemical sensor for detection of p-nitrophenol based on nanoporous gold
Electrochem. Commun.
A graphene oxide-based electrochemical sensor for sensitive determination of 4-nitrophenol
J. Hazard. Mater.
Catalytic reduction of 4-nitrophenol over Ni-Pd nanodimers supported on nitrogen-doped reduced graphene oxide
J. Hazard. Mater.
Polyelectrolyte-free layer by layer self-assembled multilayer films of cationic phthalocyanine cobalt (II) and carbon nanotube for the efficient detection of 4-nitrophenol
Sensors Actuators B Chem.
Simultaneous voltammetric determination of nitrophenol isomers at ordered mesoporous carbon modified electrode
Electrochim. Acta
pH robust electrochemical detection of 4-nitrophenol on a reduced graphene oxide modified glassy carbon electrode
J. Electroanal. Chem.
AgNWs-PANI nanocomposite based electrochemical sensor for detection of 4-nitrophenol
Sensors Actuators B Chem.
Highly selective and sensitive simple sensor based on electrochemically treated nano polypyrrole-sodium dodecyl sulphate film for the detection of Para-nitrophenol
Anal. Chim. Acta
A sensor for detection of 4-nitrophenol based on a glassy carbon electrode modified with a reduced graphene oxide/Fe3O4 nanoparticle composite
Int. J. Electrochem. Sci.
Facile synthesis of α-MnO2 nanorod/graphene nanocomposite paper electrodes using a 3D precursor for supercapacitors and sensing platform to detect 4-nitrophenol
Electrochim. Acta
Nitrogen-doped carbon spheres surface modified with in situ synthesized Au nanoparticles as electrochemical selective sensor for simultaneous detection of trace nitrophenol and dihydroxybenzene isomers
Sensors Actuators B Chem.
Pd nanospheres decorated reduced graphene oxide with multi-functions: highly efficient catalytic reduction and ultrasensitive sensing of hazardous 4-nitrophenol pollutant
J. Hazard. Mater.
Fabrication of graphene–gold nanocomposites by electrochemical co-reduction and their electrocatalytic activity toward 4-nitrophenol oxidation
J. Electroanal. Chem.
Polyaniline/silver nanocomposites: dielectric properties and ethanol vapour sensitivity
Sensors Actuators B Chem.
Polyanilines modified electrodes to be assayed as halides sensors
Int. J. Electrochem. Sci.
Graphene–polyaniline composite film modified electrode for voltammetric determination of 4-aminophenol
Sensors Actuators B Chem.
Synthesis and characterization of tungsten trioxide powders prepared from tungstic acids
Mater. Res. Bull.
Infrared and Raman study of WO3 tungsten trioxides and WO3, xH2O tungsten trioxide tydrates
J. Solid State Chem.
Thermodecomposition synthesis of WO3/H2WO4 heterostructures with enhanced visible light photocatalytic properties
Appl. Catal. B Environ.
Microspherical polyaniline/graphene nanocomposites for high performance supercapacitors
J. Power Sources
Preparation and characterization of polyaniline nanoparticles synthesized from DBSA micellar solution
Synth. Met.
Synthesis and characterization of nanocomposites consisting of polyaniline, chitosan and tin dioxide
Mater. Chem. Phys.
Synthesis of microspherical polyaniline/graphene composites and their application in supercapacitors
Electrochim. Acta
Synthesis of polyaniline/graphene/MoS2 nanocomposite for high performance supercapacitor electrode
Polymer
Synthesis of CeO2–ZnO nanoellipsoids as potential scaffold for the efficient detection of 4-nitrophenol
Sensors Actuators B Chem.
Investigation of photoelectrocatalytic activity of Cu2O nanoparticles for p-nitrophenol using rotating ring-disk electrode and application for electrocatalytic determination
Electrochim. Acta
Determination of 4-nitrophenol in water by use of a screen-printed carbon electrode modified with chitosan-crafted ZnO nanoneedles
J. Colloid Interface Sci.
Bimetallic metal–organic framework derived FeOx/TiO2 embedded in mesoporous carbon nanocomposite for the sensitive electrochemical detection of 4-nitrophenol
Sensors Actuators B Chem.
Highly sensitive p-nitrophenol determination employing a new sensor based on N-methylphenazonium methyl sulfate and graphene: analysis in natural and treated waters
Sensors Actuators B: Chemical
Simple and sensitive detection of 4-nitrophenol in real water samples using gold nanoparticles modified pretreated graphite pencil electrode
J. Electroanal. Chem.
Electrochemical synthesis of nanostructured copper-curcumin complex and its electrocatalytic application towards reduction of 4-nitrophenol
Sensors Actuators B Chem.
Cited by (49)
Cubic engineering approached a novel needle-structured cobalt-doped zinc oxide interconnected with carbon nanofiber as a composite for the determination of toxic 4-nitrophenol in environmental water samples
2024, Colloids and Surfaces A: Physicochemical and Engineering AspectsGraphene-based nanomaterials for the electrochemical sensing of nitroaromatic compounds
2024, Comprehensive Analytical ChemistryCamellia oleifera derived carbon dots modified TiO<inf>2</inf> as sensor for the rapid detection of 4-nitrophenol in wastewater
2023, International Journal of Electrochemical ScienceAnticancer, antimicrobial and biomedical features of polyoxometalate as advanced materials: A review study
2022, Inorganic Chemistry CommunicationsCitation Excerpt :Thanks to the antiviral and bacterial activity, the suppression and regulation of the translation/transcription processes of viral attachment to the host cell were revealed. Tumour activity also showed apoptosis and cellular partial oxidation [1,134–138]. Examples of the application of POMs in antiviral and antibacterial activity are listed in Table 2.