Electrochemical Exfoliation Method Research Articles

A High-Performance, Low Defected, and Binder-Free Graphene-Based Supercapacitor Obtained via Synergistic Electrochemical Exfoliation and Electrophoretic Deposition Process.

An integrated electrochemical exfoliation and electrophoretic deposition (EPD) method is developed to achieve a high-performance graphene supercapacitor. The electrochemical delamination of graphite sheet has obtained a low-defected few-layer graphene adorned with oxygen-containing functional groups. Then, the EPD process produced a binder-free electrode to alleviate the graphene restacking problem. The electrode prepared using a deposition voltage of 5 V exhibits the highest specific capacitance of 145.95 F/g at 0.5 A/g from three-electrode measurement. Moreover, this EPD-prepared electrode also demonstrates superior electrochemical properties compared to electrodes fabricated using PVDF binder. In the real symmetrical cell, the EPD-prepared electrode also shows excellent performance with a high rate capability of 82.31 % (from 0.5 A/g to 10 A/g), high cycling stability of 95.00 % (at 5 A/g) after 10,000 cycles, and rapid frequency response with short relaxation time ( ) of 9.73 ms. These results indicate that this integration method is beneficial to construct a high performance binder-free supercapacitor electrode consisting of low-defected graphene materials, low electrode resistance, and less agglomeration of graphene sheets by utilizing an environmentally friendly process.

Reduced Graphene Synthesis via Eco-Friendly Electrochemical Exfoliation Method

A novel approach to mass producing graphene without inadvertent damage was needed to meet the increasing demand for the material. Graphite electrochemical exfoliation (EE) is an intriguing method for the large-scale, quick, and easy manufacture of graphene. Using leftover whey as an electrolyte, the EE of commercial graphite was examined in this work. It was shown that a straightforward and affordable exfoliation technique may produce graphene that, in the absence of functionalization or surfactant, forms a stable dispersion in the waste solvent. Because wastewater is acidic, it has been shown that storing it at +4 degrees aids EE. X-ray diffraction (XRD) was used to satisfactorily validate the manufactured graphene's existence. The results point to a low-cost method of producing graphene and graphene oxide.

Morphological and Thermal Characterization of Low-Cost Graphene Produced by Electrochemical Exfoliation Method

The low-cost and mass production of graphene has gained importance in recent years. The electrochemical exfoliation method, one of the graphene production methods, is an efficient technique used to obtain low-cost-effective and large quantities of graphene nanosheets. Exfoliation parameters affect the properties of exfoliated graphene nanosheets. In this study, graphene production is fabricated by the method of exfoliation using electrolyte and voltage parameters. For this, a pen tip was used instead of pure platinum, which is very expensive, at the cathode. The structural research was done by X-ray diffraction spectroscopy (XRD), Raman spectroscopy and Fourier Transform Infrared Spectrometer (F-TIR). Morphological analyses were carried out by Scanning Electron Microscopy (SEM). The number of layers and crystallite of graphene layers were estimated. The obtained results were compared with the results of the other similar studies. Analysis results show that low-cost multilayer graphene can be produced by the electrochemical exfoliation method with the electrical parameters.

Synthesis and Characterization of Graphene Nanoplatelets Fabricated by Electrochemical Exfoliation Method for Conductive Adhesive

Synthesis and Characterization of Graphene Nanoplatelets Fabricated by Electrochemical Exfoliation Method for Conductive Adhesive

Synthesis of Graphene from Pencils Graphite Via Electrochemical Exfoliation Method as a Cu-Foil Coating on the Anode-Free Lithium-Ion Battery

The Anode-free Li-ion Battery (AFLB) is an alternative to a new Li-ion battery model that offers high energy density at the same battery size as conventional models. Uncontrolled dendrite growth inactive the lithium deposition, resulting in decreased specific capacity, shortened lifecycle, and reduced coulombic efficiency. This work reported the utilization of graphene derived from pencil graphite for coating Cu foil as a current collector in AFLBs, to mitigate the formation of lithium dendrites and enhance battery capacity. The graphene-coated Cu foil exhibits a specific capacity of 143 mAh/g, representing a 20 mAh/g increase compared to batteries lacking a graphene coating. The coulombic efficiency of the battery with graphene coating in the charging and discharging process for three cycles is 84.53% in the 1<sup>st</sup> cycle, 101.44% in the 2<sup>nd</sup> cycle, and 98.58% in the 3<sup>rd</sup> cycle.

Synthesis of highly efficient ternary phase graphene/Bi/SnO2 photocatalyst for degradation of organic dye pollutants

In this work, graphene nanosheets (GNs) are prepared from graphite rods obtained from waste dry-cell batteries using the electrochemical exfoliation (ECE) method. Then GNs used as a matrix to modify tin oxide (SnO2) and Bismuth (Bi) nanoparticles to prepare a binary phase SnO2@G and ternary-phase Bi@SnO2@G nanocomposite materials by wet-chemical method and used as a photocatalysts for degradation of organic dye pollutants. XRD diffraction pattern clearly confirmed the presence of tetragonal crystal system of SnO2 which was maintaining its structure in SnO2@G and G/Bi/SnO2. The stretching and bending vibrations of the functional groups were analyzed using FTIR analysis. FESEM images demonstrated the surface morphology and the texture of the as synthesized sample. Raman Spectroscopic investigation was carried out to confirm the in-plane blending of SnO2 and graphene inside the composite matrix. The as-prepared ternary-phase Bi@SnO2@G-based photocatalyst showed high degradation efficiency of 99.6% and 94.5% for direct blue (DB) and methyl blue (MB) dyes, respectively, under visible light irradiation by (i) minimizing the hole and electron recombination, (ii) providing a high surface area, and (iii) reducing the band gap energy. This study provides an effective, low-cost, and smart approach for producing GNs on a wide scale from battery waste along with nanohybrid composites with high photocatalytic efficiency.

Preliminary study of exfoliated graphite (EG) produced by electrochemical exfoliation and EG-TiO2 composite

In this research, Exfoliated Graphite (EG) materials have been synthesized using the electrochemical exfoliation method. The starting materials are graphite sheets, before the exfoliation process, a simple pre-treatment was carried out, by immersing the graphite sheet in a mixture solution of sulfuric acid (H2SO4) and hydrogen peroxide (H2O2) with a ratio of 95:5 to widen the interlayer distance in graphite sheets for the optimum electrochemical exfoliation process. This study used ammonium sulfate solution (NH4)2SO4 as an electrolyte with a concentration 0.25 M. The obtained EG materials are then composited with TiO2 to increase the resulting energy density of the materials. The in-situ sol-gel method was used to synthesize the EG-TiO2 composite assisted by microwave irradiation. The resulting materials were characterized using X-ray diffraction (XRD), Fourier Transform infrared (FTIR), and LCR meter. Based on the XRD results, the EG-TiO2 composite showed an amorphous structure with an average crystallite size of 24.9 - 49.9 nm. It also shows that the XRD pattern of the EG-TiO2 composite has a lower peak intensity than the EG material. The FTIR result shows that the functional group of the rGO-TiO2 composite has a combination of Ti-O-Ti and Ti-O-C vibrations, which indicates the chemical interaction of TiO2 with EGs.

Tuning the carboxyl content of carbon quantum dots by an electrochemical exfoliation method to enhance Fenton-like reactions for contaminants removal in a wide pH range

The complexation of CQDs with Fe(III) through -COO-Fe bond in the CQDs-Fe(III)/H2O2 system can accelerate the Fe(III)/Fe(II) cycle and broaden the pH range for application. However, the yield and carboxyl content of CQDs prepared by conventional electrochemical exfoliation were limited, which hampered the application of CQDs and the enhancement of CQDs Fenton-like process. Hence, in this study, carboxyl-rich and high-yield CQDs were successfully prepared by electrochemical exfoliation of graphite rods in hydrogen peroxide (H2O2) solution. The results suggested that the yield and carboxyl content of the optimal CQDs (CQD@5) were 1.49 and 2.01 times those of CQDs prepared by the conventional electrochemical exfoliation method (CQD@0), respectively. Subsequently, the CQDs were applied in CQDs-Fe(III)/H2O2 systems for phenol degradation. Due to 1.73 times the carboxyl of CQD@ 5 complexing with Fe(III) than that of CQD@ 0, the kinetic constant and removal of the CQD@ 5-Fe(III)/H2O2 system for phenol degradation were 2.36 and 1.44 times those of the CQD@ 0-Fe(III)/H2O2 system at pH= 6, respectively. Under the same condition, Fe(III)/H2O2 and Fe(II)/H2O2 showed negligible degradation performance. Furthermore, the removals of phenol in the CQD@ 5-Fe(III)/H2O2 system were 1.08–7.77 times those of the CQD@ 0-Fe(III)/H2O2 system at pH= 4–8, respectively. Finally, the effect of Fe(III), CQDs, and H2O2 dosages on the phenol degradation, reusability, and universality of CQD@ 5-Fe(III)/H2O2 were investigated individually. In summary, this work provides a new method for tuning the CQDs yield and carboxyl content, which enhances pollutant degradation in CQDs-Fe(III)/H2O2 systems at a wide pH range.

Modification of Electrochemical Exfoliation of Graphene Oxide with Dopamine and Tannic to Enhance Anticorrosion Performance of Epoxy Coatings

Graphene oxide (EGO) was prepared via an electrochemical exfoliation method and modified with dopamine and tannic acid, and it was then incorporated into epoxy resins to enhance their barrier, self-healing and anticorrosion performances. The morphologies, structures and compositions of the HGO (GO prepared via Hummers’ method), EGO and MGO (modified EGO) were characterized via SEM, TEM, AFM, Raman spectroscopy and XPS. The protective performances of the epoxy varnish coatings, EGO/epoxy coatings and MGO/epoxy coatings with different contents of MGO were evaluated via EIS measurements, and the role played by MGO on the coating defects was determined via LEIS and salt spray tests on the scratched coatings in a 3.5% NaCl solution. The results show that the dopamine and tannic were successfully grafted onto the EGO surface via π–π interactions and chemical bonding, and that the dispersibility of the MGO in the epoxy resins was facilitated. The epoxy coatings with a 0.1% addition of MGO possessed the best anticorrosion properties (|Z|0.01Hz > 1010 Ω cm2 after 70 days immersion in 3.5% NaCl solution) in comparison to the other coatings due to the “labyrinth effect” formed by the uniformly dispersed MGO. Meanwhile, the grafted tannic acid was released at the coating defects and provided inhibition functionalities for the substrate. As a result, the corrosion of the carbon steel was significantly decreased. This work provides a new perspective on the efficient modification of electrochemically exfoliated GO epoxy coatings for metals by combining the advantages of dopamine and corrosion inhibitors.

Effect of electric potential on the structure and yield of graphene oxide using electrochemical exfoliation method

Optimization of the electrochemical exfoliation of graphene oxide synthesis was investigated in this report using varying potentials. Graphite from waste lithium-ion batteries was used as the electrodes for the DC (direct current) electrochemical set-up. Electric potentials of 7.5 V, 12 V, and 15 V were applied for 225 minutes using 0.2M H2SO4 as the electrolyte. The characterization of the produced graphene oxide was done using Raman spectroscopy, high-resolution scanning electron microscopy (HRSEM), and energy dispersive x-ray spectroscopy (EDS) attached to the scanning electron microscope (SEM). The results obtained showed that both the rate of graphene oxide yield and the C/O ratio increased correspondingly with the increase in electric potential. However, the structure of graphene oxide produced at 7.5 V was of superior quality compared to others produced at higher potentials with regards to the crystallite lattice characteristics such as defects, lateral dimensions, thickness, and the number of graphene layers. Consequently, tailor-made graphene oxide properties (and yield) for target applications may be achieved using the electrochemical exfoliation method via the choice of the electric potential.

Electrochemical Exfoliation of Graphene Oxide: Unveiling Structural Properties and Electrochemical Performance.

An electrochemical exfoliation method for the production of graphene oxide and its characterization by electrochemical techniques are presented here. Graphite rods are used as working electrode in a three-electrode electrochemical cell, and electro-exfoliation is achieved by applying anodic polarization in a sulfuric acid solution. The electrochemical process involved two steps characterized by an intercalation at lower potential and an exfoliation at higher potential. The electrochemical behavior of the produced GO is studied through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). X ray Photoelectronic Spectroscopy (XPS), Raman spectroscopy, Transmission Electron Microscopy (TEM), and Atomic Force Microscopy (AFM) are employed to characterize the structural and chemical properties of the exfoliated GO. The results demonstrate that the electrochemical exfoliation method yields GO materials with varying degrees of oxidation, defect density, and crystallite size, depending on the applied potential and acid concentration. The graphene oxide samples exhibited distinct electrochemical properties, including charge transfer resistance, interfacial capacitance, and relaxation times for the charge transfer, as revealed by CV and EIS measurements with a specifically selected redox probe. The comprehensive characterization performed provides valuable insights into the structure-property relationships of the GO materials synthesized through electrochemical exfoliation of graphite.

Synthesis and characterization of graphene via electrochemical exfoliation technique and study its electrochemical properties

In this study, we present a one-pot approach for the large-scale synthesis of multilayer to few-layer graphene nanosheets in an aqueous medium that is cost-effective, environmentally friendly, high-yielding, and simple. This electrochemical exfoliation method produces low defect and high yield graphene nanosheet products and is more efficient than chemical exfoliation methods. Two highly oriented pyrolytic graphite plates (HOPG) are utilized as the anode and cathode in this method, which also incorporates two electrode geometry configurations. XRD, HRTEM, AFM, XPS, and Raman spectroscopy are used to describe graphene nano-sheets. Raman characterization supports graphene’s inherent qualities. By using cyclic voltammetry, the electrochemical performance of the produced nano-sheets is evaluated.

Passively Q-Switched Thulium-Holmium Doped Fibre Laser with Electrochemical Exfoliation Graphene in Chitin Based Passive Saturable Absorber

Recent years saw low-dimensional carbon nanostructures like graphene as excellent saturable absorber (SA) for its unique electric and optical properties. Graphene exhibits ultrafast recovery times and high damage thresholds and can be manufactured by relatively simple methods. In this work, Graphene was synthesized using the electrochemical exfoliation (ECE) method. Chitin biopolymer was used to develop graphene-based SA as a more environmentally friendly alternative to conventional synthetic polymers. The fabricated passive SA was then integrated into Thulium-Holmium-doped fibre laser (THDFL) in ring cavity for pulsed laser generation via Q-switching. The optical and physical properties of the graphene-based SA were characterized using Raman spectroscopy, field emission scanning electron microscopy (FESEM) and energy-dispersive x-ray spectroscopy (EDS). Q-switched pulse was successfully demonstrated using the fabricated graphene SAs. ECE graphene-chitin SA generated a Q-switched pulse region at 2 micro-metre with the repetition rate and shortest pulse width of 67.78 kHZ and 10.03 micro-second, respectively. The signal-to-noise ratio (SNR) values obtained was 40 dB indicating high stability of the pulse laser-generated. This study demonstrated the potential of graphene embedded in chitin biopolymer as a sustainable and environmentally friendly SA for a wide range of applications, particularly for pulsed fibre lasers.

Preparation of Antioxidative MXene by Deep Eutectic Solvent-Assisted Electrochemical Ultrasonic Composite Exfoliation and Its Application in Flexible Solid-State Supercapacitors

In this work, we achieved a novel preparation of Ti3C2 MXene (MXene–DES) with few layers and a high degree of hydroxylation by a deep eutectic solvent (DES)-assisted electrochemical ultrasonic composite exfoliation method which is easy to scale up. The electrochemical process used a mixture of low-cost DES (choline chloride–urea) and water as the electrolyte, in which DES acts as a triple role of intercalation, interlayer expansion, and anti-oxidation. DES attached to the surface and interlayer of layered Ti3C2 formed an antioxidative protective cover, resulting in the layered Ti3C2 being grafted with hydroxyl functional groups instead of forming TiO2 in water during the entire exfoliation process. The prepared MXene–DES exhibits fewer layers, larger interlayer spacing, higher degree of hydroxylation, and stronger oxidation resistance than the MXene prepared by traditional ultrasound in a nitrogen atmosphere (MXene–N2). The symmetric flexible solid-state supercapacitor based on an activated carbon electrode and the composite gel polymer electrolyte composed of MXene–DES, DES, and polyvinyl alcohol exhibits good mechanical properties, a wide voltage window of 2.3 V, and a high specific capacitance of 133.7 F·g–1 (0.1 A·g–1). Our strategy paved a simple, low-cost, and relatively environmentally friendly way to the scalable preparation and application of antioxidative high-quality MXene.

Few layers graphene-based electrocatalysts for ORR synthesized by electrochemical exfoliation methods

Graphene-based materials were synthesized by electrochemical exfoliation method (cathodic method) starting from a graphite sheet. In the established methodology, an initial immersion in H2SO4 was applied, followed by cathodic expansion in potassium sulphate, where the effect of the applied voltage was studied. Finally, by ultrasound treatment, the exfoliation was achieved to produce a dispersion of few layer graphene material. Once the optimum procedure was established, Pt nanoparticles were incorporated using H2PtCl6.6H2O. This incorporation was studied at each stage of the graphene-based material synthesis to determine which was the most adequate to obtain the highest Pt dispersion and the best distribution of the Pt nanoparticles. In this sense, the incorporation of Pt in the graphene-based material colloidal dispersion by stirring for 3 h and sonication for 1 h, results in Pt nanoparticles with an average size of around 1 nm with an excellent distribution in the carbon material. The performance of this catalyst was compared with the commercial Pt/C electrocatalyst, showing a great oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) activity, exceeding it by far when comparing the mass-specific activity (A gPt−1) In addition, it presents excellent stability and selectivity toward the 4-electron pathway in ORR, which is the most energy-efficient, and using half of the platinum loading compared to the commercial material.

Room-temperature defect-controlled fabrication of graphene via sustainable electrochemical exfoliation: An ultra-performance supercapacitor

Electrochemical Double-Layer Capacitors (EDLCs) afford low specific capacitance when graphene structure has high degree of graphitization and defect. In this study, a novel, facile and economical electrochemical exfoliation method is used for the straightforward fabrication of graphene from graphite electrode under ambient conditions. Successful fabrication of graphene structures is verified via X-ray diffraction (XRD), Raman and FT-IR spectroscopy. The morphology of the prepared samples is studied using Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The electrochemical performances of the as-prepared graphene show excellent specific capacitance (210 F/g) for the sample synthesized in the lowest electrolyte concentration being several times higher than that of the initial graphite electrode (~26 F/g). The optimal electrode displays significant capacitive retention (~96 %) and notable coulombic efficiency after 10,000 cycles galvanostatic charge/discharge at current density of 10 A/g. The prepared graphene structure with this novel method exhibits remarkable EDLC performances compared to other graphene-based supercapacitors cited in the literature. Owing to their sustainable quality and considerable quantity, these performant supercapacitor electrodes should be beneficial from an industrial vantage point.

Incorporation of graphene oxide/titanium dioxide with different polymer materials and its effects on methylene blue dye rejection and antifouling ability.

Exposure of synthetic dye, such as methylene blue (MB), in water bodies led to a serious threat to living things because they are toxic and non-degradable. Amongst the introduced dye removal methods, membrane separation process can be considered a powerful technique for treating dye contamination. However, this method commonly suffered from drawbacks, such as short membrane lifetime, low permeability and selectivity. To overcome these issues, graphene oxide (GO) and titanium dioxide (TiO2) were used as additives to fabricate polyethersulfone (PES)- and polyvinylidene fluoride (PVDF)-based hybrid membranes via non-solvent-induced phase separation method. Prior to membrane fabrication, GO was synthesised via electrochemical exfoliation method assisted by customised triple-tail surfactant. The potential of PES- and PVDF-based hybrid membranes for wastewater treatment has been discussed widely. However, direct comparison between these two polymeric membranes is not critically discussed for MB dye separation application yet. Therefore, this study is aimed at evaluating the performance of different types of polymers (e.g. PES and PVDF) in terms of membrane morphology, properties, dye rejection and antifouling ability. Results showed that the incorporation of GO and TiO2 alters the morphology of the fabricated membranes and affects dye rejection further, as well as their antifouling performance. In contrast with pristine membrane, PES-GO/TiO2 and PVDF-GO/TiO2 possessed high hydrophilicity, as indicated by their low contact angle (67.38° and 62.12°, respectively). Based on this study, PVDF-GO/TiO2 showed higher porosity value (94.88%), permeability (87.32 L/m2hMPa) and MB rejection rate (92.63%), as well as flux recovery ratio value of > 100% as compared with others. Overall, the incorporation of GO and TiO2 with PVDF polymer are proven to be effective hybrid materials of membrane fabrication for dye rejection application in the near future. The polymer material's intrinsic properties can affect the attributes of the fabricated membrane.

Minireview on Cathodic and Anodic Exfoliation for Recycling Spent Zinc–Carbon Batteries To Prepare Graphene Material: Advances and Outlook of Interesting Strategies

The recycling of spent batteries has always been a daunting and difficult task throughout the long history of battery development. Zinc–carbon batteries, one of history’s most popular batteries, still widely used today, have become a serious environmental problem. Although zinc–carbon batteries are the first primary batteries that belong to non-rechargeable cells, they are still widely used as a result of their low cost and ease of product. Currently, thousands of tons of zinc–carbon batteries are released into the environment each year, requiring advanced recycling methods. Among various strategies that have been developed, electrochemistry is one of the interesting methods, with the advantages of being cheap and fast and able to synthesize a new material, graphene, a material that changes the technology game. Graphene derived from carbon rods in spent zinc–carbon batteries has been successfully synthesized by a short-time, simple instrumentation of electrochemical exfoliation under direct current supply, which demonstrates a low-cost and environmental strategy for mass production of graphene material from electronic device waste. This review provides a great overview aiming to introduce the electrochemical exfoliation method to recycle spent zinc–carbon batteries to synthesize graphene materials, which contributes to battery recycling technology as an alternative strategy.

Electrolyte effect in electrochemical exfoliation of graphite

Exfoliated graphene has been successfully synthesized using electrochemical exfoliation method followed by sonication of the graphite rod. Ammonium sulfate, sodium sulfate, ammonium oxalate, hydrogen peroxide, and ammonium persulfate were used as electrolytes. The effect of sonication time was studied for several products. The exfoliated graphene (EG) was characterized using XRD, Raman, FTIR, SEM-EDS, TEM and electrical conductivity measurement. The exfoliation using ammonium sulfate-ammonium persulfate as the electrolyte gives the highest mass-product, with a yield of almost 70%. Adding peroxide to the electrolyte reduces the mass of the exfoliated product. In addition, different sonication times results in different phenomena of particle size changes. The XRD data show that the EG has 2θ = 26.4° which is lower than its origin graphite. Raman data confirm that the EG has been obtained with the FWHM (G) value of 45–70 cm−1, and the resulting EG is a multilayer (2D peak). The O–H and C–C aromatic group has been assigned from FTIR spectrum. From SEM and TEM images, it was understood that the morphology of material is wrinkled, crumpled, and has a transparent zone, while from EDS data, it is found that the O/C value is in the range of 0.15–0.35. The electrical conductivity of EG reaches 52 S/cm.

Effect of current flow applied for graphene synthesis and its application for the detection of ciprofloxacin in fish, urine and drugs

The electrochemical exfoliation method adopted in this study presents the quality variations of the graphene oxide (GO) produced under applied currents flow (Alternating current (AC) and Direct current (DC)). The obtained GOs were reduced by a fast, efficient, and environmentally-friendly electrochemical method using CV without the addition of chemical agents. Subsequently, the r-GOs obtained were used as carbon paste electrode (CPE) modifiers (r-GOAC-CPE and r-GODC-CPE) for the determination of Ciprofloxacin (Cipro) traces in fish tissues, urine and drug samples. The prepared electrodes were characterized by X-ray diffraction (XRD) and thermogravimetric and differential thermal analysis (DTA-TGA). Comparison of the electrochemical performances of each preparation (r-GOAC-CPE and r-GOAC-CPE) has been performed using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Under the optimal experimental parameters, the electro-oxidation peak signal was linearly related to Cipro concentration in the range from 1.0 × 10−7 to 5.0 × 10−5 mol/L for r-GOAC-CPE and from 3.0 × 10−7 to 5.0 × 10−5 mol/L for r-GODC-CPE. The developed sensors enabled to achieve a detection limit (DL) of 4.08 × 10−9 mol/L and a quantification limit (QL) of 13.36 × 10−9 mol/L for r-GOAC-CPE and 17.74 × 10−9 mol/L and 59.13 × 10−9 mol/L for r-GODC-CPE. The prepared sensors were successfully applied for Cipro recognition in fish tissues, urine and drug samples.