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6CCVD Research

Graphene Oxide Electroreduced onto Boron-Doped Diamond and Electrodecorated with Silver (Ag/GO/BDD) Electrode for Tetracycline Detection in Aqueous Solution

At a Glance

Section titled “At a Glance”
MetadataDetails
Publication Date2021-06-14
JournalNanomaterials
AuthorsSorina Negrea, Lidia Ani Diaconu, Valeria Nicorescu, Sorina Motoc, Corina Orha
InstitutionsGheorghe Asachi Technical University of Iași, Polytechnic University of TimiƟoara
Citations18
AnalysisFull AI Review Included

Executive Summary

Section titled “Executive Summary”

The research details the development and characterization of an ultra-sensitive electrochemical sensor, Ag/GO/BDD, for detecting the emerging pollutant Tetracycline (TC) in aqueous solutions.

  • Material System: The sensor utilizes a commercial Boron-Doped Diamond (BDD) electrode modified with electrochemically reduced Graphene Oxide (GO) and electrodecorated with Silver (Ag) nanoparticles.
  • Performance Benchmark: The Ag/GO/BDD electrode demonstrated superior performance compared to BDD, GO/BDD, and Ag/BDD variants, confirming the synergistic effect of the Ag-GO nanocomposite.
  • Record Sensitivity: Using Square-Wave Voltammetry (SWV) in 0.1 M NaOH, the sensor achieved a high sensitivity of 46.6 ”A·”M-1·cm-2 and a remarkably low Limit of Detection (LOD) of 5 nM (0.005 ”M).
  • Practical Limitation & Solution: The high-sensitivity alkaline procedure is prone to chloride interference, limiting its use in natural water. This was overcome by switching the supporting electrolyte to 0.1 M Na2SO4, which eliminates chloride interference for water monitoring.
  • Alternative Technique: A pseudo-Multiple-Pulsed Amperometry (MPA) technique, operated at two low potential levels (-0.150 V/SCE and +0.300 V/SCE), also yielded excellent results, offering a simpler method with reduced interference risks.
  • Commercial Viability: The procedure is validated for quantitative determination of TC in pharmaceutical formulations (NaOH electrolyte) and practical water monitoring (Na2SO4 electrolyte).

Technical Specifications

Section titled “Technical Specifications”
ParameterValueUnitContext
Best Limit of Detection (LOD)0.005”MSWV, 0.1 M NaOH, SP 5 mV, MA 200 mV
Best Sensitivity46.6”A·”M-1·cm-2SWV, 0.1 M NaOH, SP 5 mV, MA 200 mV
LOD (Water Monitoring)0.155”MSWV, 0.1 M Na2SO4, MA 100 mV, SP 10 mV
Electroactive Surface Area (Ag/GO/BDD)0.045cm2Determined via Randles-Sevcik Equation
Apparent Diffusion Coefficient (Ag/GO/BDD)2.50 x 10-6cm2·s-1Determined via Randles-Sevcik Equation
SWV Modulation Amplitude (MA)200mVOptimized for 0.1 M NaOH detection
SWV Step Potential (SP)5mVOptimized for 0.1 M NaOH detection
SWV Frequency (f)10HzOptimized for detection
GO Electrodeposition Potential-1.50V/SCEChronoamperometry (CA)
GO Electrodeposition Time120sFrom 4 mg/mL GO suspension
Ag Electrodeposition Potential-1.30V/SCEFrom 4 mM AgNO3 solution
Ag Electrodeposition Time5sFor Ag particle decoration
TC Detection Potential (Best SWV)+0.750V/SCEAnodic peak in 0.1 M NaOH
TC Detection Potential (Na2SO4 SWV)+0.670V/SCEAnodic peak in 0.1 M Na2SO4

Key Methodologies

Section titled “Key Methodologies”

The Ag/GO/BDD electrode was fabricated and tested using the following procedures:

  1. BDD Substrate Preparation:
    • Commercial BDD disc electrode (3 mm diameter) was mechanically cleaned using 0.2 ”m alumina powder (Al2O3).
    • Washing was performed using distilled water.
  2. Graphene Oxide (GO) Electroreduction:
    • GO was deposited onto the BDD surface using Chronoamperometry (CA).
    • Deposition parameters: Potential of -1.50 V/SCE for 120 s, using a suspension of 4 mg/mL GO dispersed in water.
  3. Silver (Ag) Electrodecoration:
    • Silver particles (AgPs) were deposited onto the GO/BDD surface via electrodeposition.
    • Deposition parameters: Potential of -1.30 V/SCE for 5 s, using a 4 mM AgNO3 solution.
  4. Electrochemical Stabilization:
    • The working electrode was stabilized using 10 continuous repetitive Cyclic Voltammograms (CV) in 0.1 M NaOH, ranging from -0.50 to +1.00 V/SCE.
  5. Analytical Testing and Optimization:
    • Comparative analysis was performed using CV, Differential-Pulsed Voltammetry (DPV), Square-Wave Voltammetry (SWV), Chronoamperometry (CA), and Multiple-Pulsed Amperometry (MPA).
    • Optimal SWV Conditions (0.1 M NaOH): Step Potential (SP) 5 mV, Modulation Amplitude (MA) 200 mV, and Frequency (f) 10 Hz.
  6. Interference Mitigation:
    • The procedure was tested in 0.1 M Na2SO4 supporting electrolyte to eliminate interference from chloride ions (Cl-), which react with Ag(I) oxide in alkaline media.
  7. Characterization:
    • Morpho-structural analysis was performed using Scanning Electron Microscopy (SEM) coupled with Energy-Dispersive X-Ray analysis (EDX).

Commercial Applications

Section titled “Commercial Applications”

The Ag/GO/BDD sensor technology, leveraging the stability of BDD and the enhanced electrocatalysis of Ag-GO nanocomposites, is highly relevant for several industrial and environmental sectors:

  • Pharmaceutical Quality Control:
    • High-accuracy quantitative determination of TC in pharmaceutical formulations, utilizing the ultra-sensitive 0.1 M NaOH-based SWV procedure (LOD 5 nM).
  • Environmental Water Quality Monitoring:
    • Rapid, on-site detection of Tetracycline (an emerging pollutant) in complex matrices like rivers, groundwaters, and wastewater. The 0.1 M Na2SO4 procedure ensures reliable performance by mitigating chloride interference.
  • Food Safety and Aquaculture:
    • Monitoring antibiotic residues in animal products and aquaculture systems, where TC is widely used for veterinary purposes.
  • Advanced Sensor Development:
    • Integration of the robust BDD platform with nanostructured materials (Ag/GO) for manufacturing stable, reusable, and miniaturized electrochemical sensors suitable for portable field devices.
  • Electrocatalytic Systems:
    • The Ag/GO/BDD architecture provides a model for developing highly efficient electrocatalysts for other redox reactions, benefiting from the high surface area of reduced GO and the catalytic activity of silver.
View Original Abstract

A new electrochemical sensor designed by modifying the commercial boron-doped diamond (BDD) electrode with graphene oxide (GO) reduced electrochemically and further electrodecorated with silver (Ag), named the Ag/GO/BDD electrode, was selected among a series of the BDD, GOelectroreduced onto BDD (GO/BDD) and silver electrodeposited onto BDD (Ag/BDD) electrodes for the detection of tetracycline (TC) in aqueous solution. The best results regarding the sensitivity of 46.6 ”A·”M−1·cm−2 and the lowest limit of detection of 5 nM was achieved using square-wave voltammetry (SWV) operated at the step potential of 5 mV, modulation amplitude of 200 mV and the frequency of 10 Hz in alkaline medium. The application of the alkaline supporting electrolyte-based procedure is limited for water monitoring due to the presence of chloride that interferes with TC detection; however, it can be applied for quantitative determination of pharmaceutical formulations. 0.1 M Na2SO4 supporting electrolyte eliminated chloride interference and can be used for the application of Ag/GO/BDD in practical detection of TC in water.

Tech Support

Section titled “Tech Support”

Original Source

Section titled “Original Source”

References

Section titled “References”
  1. 2017 - A review on the adsorption studies of tetracycline onto various types of adsorbents [Crossref]
  2. 2013 - Tetracycline antibiotics in the environment: A review [Crossref]
  3. 2018 - Electrochemical determination of tetracycline using AuNP-coated molecularly imprinted overoxidized polypyrrole sensing interface [Crossref]
  4. 2018 - Detection and removal of antibiotic tetracycline in water with a highly stable luminescent MOF [Crossref]
  5. 2021 - Occurrence, fate, and risk assessment of typical tetracycline antibiotics in the aquatic environment: A review [Crossref]
  6. 2021 - Electrochemical detection of environmental pollutants based on graphene derivatives: A review [Crossref]
  7. 2018 - Emerging pollutants removal through advanced drinking water treatment: A review on processes and environmental performances assessment [Crossref]
  8. 2016 - A brief review on recent developments of electrochemical sensors in environmental application for PGMs [Crossref]
  9. 2017 - A review on various electrochemical techniques for heavy metal ions detection with different sensing platforms [Crossref]
  10. 2019 - Synthesis, properties, and applications of graphene oxide/reduced graphene oxide and their nanocomposites [Crossref]

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