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Designs and Materials of Electrodes for Electrochemical Sensors

MetadataDetails
Publication Date2025-08-11
JournalChemElectroChem
AuthorsPierre J. Obeid, Nouha Sari‐Chmayssem, Paolo Yammine, Doris Homsi, Hanna El‐Nakat
InstitutionsUniversity of Balamand, Lebanese University
Citations1
AnalysisFull AI Review Included

This review provides a critical engineering analysis of electrode designs and materials essential for developing high-performance electrochemical sensors and biosensors.

  • Design Focus: Emphasizes miniaturized platforms, particularly Screen-Printed Electrodes (SPEs), which integrate all three electrodes (Working, Counter, Reference) onto a single chip for portability and cost-effectiveness.
  • Electrode Sizing Requirement: Mandates that the Counter Electrode (CE) surface area must be at least three times greater than the Working Electrode (WE) area (ACE/AWE > 3) to ensure stable potential control and minimize ohmic drop.
  • Boron-Doped Diamond (BDD): Identified as a superior primary sensing material due to its exceptionally wide potential window (up to 3 V in aqueous solution) and ultra-low background current (nA cm-2 range), offering high resistance to fouling.
  • Carbon Nanomaterials (CNTs/Graphene): Crucial for enhancing electron transfer kinetics (Vert fast for CNTs) and increasing electroactive surface area, enabling detection limits typically in the nM to pM range for high-sensitivity applications.
  • Conductive Polymers (CPs): Materials like PEDOT: PSS are highlighted for their high electrical conductivity (up to 1000s S cm-1 when doped) and water processability, making them ideal for functionalizing WEs in biocompatible biosensors.
  • Modifying Nanoparticles: Metal (Au, Pt, Pd, Ni) and Metal Oxide (MOXNPs) nanoparticles are used primarily as catalytic components to accelerate redox reactions, improve selectivity, and facilitate detection of electrochemically inactive species at lower potentials.
  • Application Relevance: The material selection directly supports the development of next-generation devices for rapid diagnostics, environmental monitoring, and flexible/wearable sensing platforms.
ParameterValueUnitContext
BDD Potential Window~-1.5 to ≈+2.5Vvs. Ag/AgCl, Very wide in aqueous solution
BDD Capacitive CurrentFewnA cm-2Ultra-low background current density
Conventional Material Capacitive Current (e.g., Pt)Tens to hundreds”A cm-2Comparison to BDD
Glassy Carbon (GC) Potential Window1.5 to 2VTypical range
GC Electrical Conductivity101 to 104S m-1Range for GCEs
Carbon Fiber (CF) Diameter5 to 10”mTypical fiber size
CNT Current Density CapacityUp to 1010A cm-2Extremely high capacity
PEDOT: PSS Conductivity (Enhanced)10 to 1000sS cm-1Enhanced by polar solvent doping
WE/CE Area Ratio (Minimum)>3RatioRequired for stable potential control
WE-RE Separation (Recommended)1 to 3mmTo minimize ohmic drop
WE Surface Area (Kinetic Studies)10-4 to 10-6cm2Corresponding to microelectrodes (tens of ”m diameter)
WE Surface Area (Electroanalytical)0.01 to 0.1cm2Corresponding to small disk electrodes (≈1-4 mm diameter)
PtNP/AuNP Detection LimitsnM to pMConcentrationHigh sensitivity for biosensors
PPy/PANI Thermal StabilityModerateTemperatureLimited under high temperatures
PEDOT/PEDOT: PSS Thermal StabilityHigh stable up to 200°CGood stability range
  1. Screen-Printing Technology: Utilized for mass production of cost-effective, disposable SPEs. Inks typically consist of carbon (for WE/CE) and Ag/AgCl (for RE), deposited onto ceramic or flexible substrates (PET, Kapton).
  2. Chemical Vapor Deposition (CVD): The dominant method for synthesizing high-quality Boron-Doped Diamond (BDD) electrodes, typically using Microwave Plasma-Assisted CVD (MPCVD) at high temperatures (>400 °C).
  3. Electrochemical Pretreatment (BDD): Anodic or cathodic preconditioning is applied to BDD surfaces to tune the termination:
    • Cathodic: Results in hydrogen-terminated surfaces (hydrophobic, enhanced electron transfer).
    • Anodic: Results in oxygen-terminated surfaces (hydrophilic, slower electron transfer).
  4. Electrodeposition and Polymerization: Used to integrate modifying materials onto the WE surface. This includes direct deposition of metal nanoparticles (Au, Pt, Ni) and electrochemical polymerization of conductive polymers (PANI, PPy, PEDOT) to form thin, conductive films.
  5. Additive Manufacturing (3D/Inkjet Printing): Enables rapid, customizable fabrication of electrodes with specific geometries and controlled porosity, facilitating integration into complex microfluidic or wearable systems.
  6. Spin Coating: Used specifically for aqueous dispersions of PEDOT: PSS, where the blend is coated onto a substrate at speeds between 1000 to 5000 rpm to control film thickness and uniformity.
Industry SectorSpecific Application/Target AnalyteKey Materials
Medical & Clinical DiagnosticsGlucose, H2O2, Lactic Acid, Uric Acid, Dopamine detection; Immunosensors; DNA sensors.PtNPs, AuNPs, PdNPs, Enzyme-modified CNTs/Graphene, PEDOT: PSS, Prussian Blue (PB) mediator.
Environmental MonitoringHeavy metals (Pb, Cd, Hg), Pesticides (organophosphorus), Nitrates, Organic pollutants.BDD (for degradation/sensing), AgNPs, MOXNPs (SnO2, ZnO), Graphite/PGEs.
Food Safety & Quality ControlDetection of contaminants (e.g., Salmonella, metronidazole); Monitoring purine metabolites; Lactic acid in fermented products.Pt/PdNP composites, Enzyme-modified PGEs, Biochar-based sensors.
Wearable & Flexible ElectronicsReal-time monitoring of sweat cortisol, strain sensing, integrated biosensors for health monitoring.Graphene, PEDOT: PSS, Recycled Carbon Fibers (CFs), SPEs on flexible substrates (PET, Kapton).
Microfluidics & Lab-on-a-ChipMultiparametric detection (pH, lactate, H2O2, NO) under flow conditions; Organ-on-a-chip integration.Miniaturized SPEs, PEDOT: PSS, PB ink printing, Glass/Silicon/Ceramic substrates.
Wastewater TreatmentDegradation of organic micropollutants via electrogenerated hydroxyl radicals.Boron-Doped Diamond (BDD) electrodes.
View Original Abstract

Electrode material selection and structural designs of electrochemical chips are fundamental parameters in the field of electrochemical sensing. These parameters directly affect sensor conductivity, selectivity, stability, surface area, and overall performance. This article summarizes the most common electrode architectures and commercially available materials currently used in the development of electrochemical sensors, including carbon‐based materials (e.g., boron‐doped diamond, graphite, graphene, glassy carbon, carbon nanotubes, and carbon fibers), metal‐based materials and alloys (e.g., gold, platinum, silver, nickel, and metal oxides), conductive polymers (e.g., polyaniline, polypyrrole, and poly(3,4‐ethylenedioxythiophene)), and redox dyes and mediators (Prussian blue, Meldola blue, etc.). It highlights the advantages of each category and identifies suitable electrode materials for specific target analytes. Finally, this review aims to guide readers in selecting appropriate electrode materials and designs tailored to a specific application.