Chapter Four · failure evidence
What Cyclic Voltammetry (CV) got wrong, from 28 dissertations
Across the records, cyclic voltammetry frequently encounters severe measurement challenges caused by background currents, solvent window limits, and high scan rate distortions. Researchers also encounter difficulties when overlapping processes, complex electrolyte matrices, and unmodeled reaction kinetics prevent the accurate extraction of thermodynamic and kinetic parameters. These records come from PhD theses at 16 institutions, 2021 to 2026. Each links to its thesis. They were extracted by language models reading the full text, so treat each as a lead to read, not a verdict.
Parasitic electrolyte reactions and capacitive currents mask Faradaic signals
Target electrochemical signals are frequently masked when background currents from the electrolyte or electrode dominate the measurement. Sub-picoampere Faradaic currents and low surface concentrations are easily obscured by capacitive charging, solvent reactions, or spurious gas evolution.
Tried and failed
cyclic voltammetry applied to organic ligand redox characterization. Outcome: no signal. Reason: redox currents were undetectable due to overlapping background processes
Synthesis and characterisation of conductive metal-organic framework materials · Oxford
Tried and failed
cyclic voltammetry applied to atomically thin 2D heterostructures. Outcome: no signal. Reason: Sub-picoampere electrochemical currents were dominated and obscured by parasitic electrolyte background reactions
The Physics of High-Temperature Superconducting Cuprates in van der Waals Heterostructures · Harvard
Considered and rejected
Considered and rejected: Rejected cyclic voltammetry (CV) and linear sweep voltammetry (LSV) for electrode current-potential characterization due to large capacitive currents; multistep chronoamperometry was selected instead.
Considered and rejected
Considered and rejected: Rejected cyclic voltammetry for monitoring intercalation because sub-picoampere currents were swamped by parasitic electrolyte reactions, choosing in-situ Hall potentiometry instead
The Physics of High-Temperature Superconducting Cuprates in van der Waals Heterostructures · Harvard
Tried and failed
cyclic voltammetry applied to surface ligand desorption on nanocrystals. Outcome: no signal. Reason: low sensitivity and low surface ligand concentration obscured desorption signals
Tried and failed
in situ liquid-cell cyclic voltammetry applied to uncleaned nanoparticle-modified microelectrodes. Outcome: no signal. Reason: surface contamination caused spurious gas evolution obscuring characteristic electrochemical redox peaks
In situ electron microscopy of nanomaterials dynamics in heterogeneous phase environments · MIT
High scan rates cause ohmic drop distortions and instrument overload
Operating at elevated scan rates introduces severe peak broadening, uncompensated resistance drop, and significant capacitive currents. These kinetic and experimental limitations produce switching artifacts, degrade measurement stability, and can overload the data acquisition hardware.
Tried and failed
physics-informed Bayesian model hypothesis testing applied to electrochemical cyclic voltammetry classification. Outcome: did not generalise. Reason: kinetic limitations, uncompensated resistance drop, and unmodeled capacitive charging currents at faster scan rates
Voltammetric Methods Augmented with Physical Models and Statistical Inference · MIT
Considered and rejected
Considered and rejected: Rejected cyclic voltammetry (20 mV/s) for liquid cell degradation studies because high scan rate causes mass transport limitations and peak broadening, failing to match galvanostatic battery degradation
Towards reproducible lithium-ion battery cycling using liquid-phase transmission electron microscopy · EPFL
Tried and failed
Fast scan cyclic voltammetry at high potentials applied to analyte detection in HEPES buffer. Reason: Buffer introduced a large negative switching peak artifact when scanning up to high anodic potential.
Electroanalytical engineering strategies for monitoring molecules in neuroscience · Imperial
Tried and failed
carbon nanotube modification of carbon paste electrodes applied to fast-scan cyclic voltammetry sensing. Outcome: unstable. Reason: excessive noise and uncontrollable sensitivity overloaded the data acquisition system
Novel engineering and characterization of sensing materials and fluidic devices for neuroscience · Imperial
Considered and rejected
Considered and rejected: Rejected extracting ET rate constants at high overpotentials via fast-scan cyclic voltammetry (Laviron method) due to uncorrectable iR drop distortion and potential SAM oxidative desorption.
Target redox couples fall outside the accessible solvent potential window
Molecules often fail to exhibit detectable redox waves because their formal potentials lie outside the accessible potential window of the electrolyte. Extending the potential sweep window cannot resolve features when high electron affinities or solvent breakdown limits prevent redox cycling.
Tried and failed
solution cyclic voltammetry applied to free organic capping ligands. Outcome: no signal. Reason: ligands exhibited no redox activity or formal electroreduction across the tested potential window
Tried and failed
electrochemical reduction characterization via cyclic voltammetry applied to uranyl Schiff base coordination complexes. Outcome: no signal. Reason: redox couples fell outside the electrochemical solvent potential window
Synthesis and Characterization of Acyclic Schiff Bases and Redox Active Chelation of Actinides · Texas Tech
Considered and rejected
Considered and rejected: Rejected cyclic voltammetry (CV) for HOMO determination in Chapter II because many BBOs did not exhibit a redox cycle within the solvent window, using UPS instead.
Tried and failed
widening cyclic voltammetry potential sweep window applied to single-peak iron macrocycle electrocatalysts. Outcome: no signal. Reason: extended potential ranges did not reveal hidden redox desorption features for single-peak complexes
Oxygen reduction on iron macrocycles kinetics study and engineering of the electrochemical interface · Imperial
Tried and failed
electrochemical cyclic voltammetry in aqueous electrolyte applied to conjugated copolymer with high electron affinity. Outcome: no signal. Reason: electron affinity was too high to permit redox response in aqueous solution
Design, Synthesis, and Characterization of Electron Transporting DPP-based Copolymers for Application in Organic Electronics · Georgia Tech
Complex matrices and overlapping reactions distort target redox peaks
Complex electrolyte environments and multi-component systems introduce interfering peaks that obscure the primary analyte response. Contact with polar solvents, cell culture media, or concurrent processes such as bulk oxygen intercalation alters energy levels and distorts electrochemical signatures.
Considered and rejected
Considered and rejected: Rejected cyclic voltammetry (CV) for measuring dye frontier orbitals because polar electrolyte solvents altered energy levels upon contact with thin films
Bridging the gap between stability and performance of next-generation light-converting materials · ResearchWorks
Considered and rejected
Considered and rejected: Rejected measuring catalyst cyclic voltammetry redox potentials due to excessive unknown peaks from oxidized catalyst forms and ligands.
Anti- Bacterial Properties Of Bisphenolic Honokiol Derivatives · Penn
Considered and rejected
Considered and rejected: Rejected using fast cyclic voltammetry for quantifying intrinsic OER activity on oxygen-deficient perovskites because currents from bulk electrochemical oxygen intercalation overestimate catalytic activity; used steady-state galvanostatic measurements instead.
Activity and Stability Design Principles of Transition Metal Compounds for Decarbonization · MIT
Tried and failed
Fast scan cyclic voltammetry at microelectrodes applied to analyte detection in cell culture media. Outcome: no signal. Reason: Complex media components caused severe peak broadening, positive potential shifts, and attenuated oxidative current.
Electroanalytical engineering strategies for monitoring molecules in neuroscience · Imperial
Quantitative parameter extraction fails due to insufficient precision and coupled kinetics
Researchers struggle to extract reliable standard potentials and transfer coefficients due to limited overpotential ranges and experimental precision. Poorly defined onset potentials and unknown coupled background reaction mechanisms further hinder accurate kinetic modeling.
Tried and failed
direct cyclic voltammetry on sensing electrode applied to standard reduction potential determination. Outcome: data insufficient. Reason: could not acquire standard potential with sufficient precision under experimental conditions
Tried and failed
variable scan rate cyclic voltammetry trumpet plots applied to interfacial electron transfer kinetic parameter extraction. Outcome: data insufficient. Reason: limited overpotential perturbation ranges prevented reliable extraction of transfer coefficients
Considered and rejected
Considered and rejected: Rejected onset potentials in voltammetry for calculating standard electrochemical potentials because onset potentials are poorly defined and sensitive to temperature and ohmic currents.
Considered and rejected
Considered and rejected: Rejected full cyclic voltammetric wave analysis (peak potential/current) for extracting acetic acid dissociation parameters in favor of steady-state limiting current analysis at a microelectrode to avoid requiring unknown hydrogen evolution reaction kinetics/mechanisms on Pt electrodes.
Computational electrochemistry · Oxford
Left open by the authors
Problems the authors named and did not get to.
Left open
Test pCOOH-DPPTz-BTh films via cyclic voltammetry in aqueous electrolyte to assess electrochemical stability and measure OECT device performance. Blocker: Requires synthesized polymer samples and physical wet lab electrochemical/transistor testing apparatus.
Design, Synthesis, and Characterization of Electron Transporting DPP-based Copolymers for Application in Organic Electronics · Georgia Tech
Left open
Resolve the discrepancy in current peak magnitudes between cyclic voltammetry and differential pulse voltammetry measurements during oligomer degradation. Blocker: Requires wet lab electrochemical experiments (CV and DPV) and physical samples undergoing oligomer degradation.
Thin-film transistor : characterization, scaling studies, and applications in electrochemical charge sensing · UT Austin
Left open
Elucidate mechanistic pathways and obtain cyclic voltammetry profiles for direct and NaCl-mediated electrochemical oxidations of amines. Blocker: Requires wet-lab electrochemical equipment and cyclic voltammetry experiments
An Electrochemical Oxidation Prins-type Cyclisation Sequence for the Synthesis of Substituted N-Heterocycles and Copper-Catalyzed Conjugate Addition Towards Hydnocarpic Acid Synthe · Research Repository UCD
Left open
Investigate low-potential current density increases observed during cyclic voltammetry of P(EO-MO) electrolytes with LiTFSI. Blocker: Requires a wet lab with polymer synthesis capabilities and electrochemical cyclic voltammetry equipment.
Developing Dynamic Plastics for Improved Sustainability and Energy Storage Technologies · Cornell
Left open
Perform cyclic voltammetry on 5,6,9,10-tetramethoxy-2-methylphenanthro[9,10-b]thiophene to determine the mechanism of the second oxidative annulation. Blocker: Requires wet lab electrochemistry equipment and synthesized chemical intermediate (5,6,9,10-tetramethoxy-2-methylphenanthro[9,10-b]thiophene).
Left open
Identify and test negative electrolytes with redox potentials between -0.3 V and -0.6 V for acidic Fe-QA redox flow batteries. Blocker: Requires wet chemistry lab, chemical synthesis, and electrochemical full-cell testing hardware
Development of Iron Complex-based Aqueous Redox Flow Batteries for Large-scale Energy Storage · Harvard
Left open
Characterize square wave voltammetry on bipolar electrodes to background-subtract capacitive charging current. Blocker: Requires a physical electrochemical wet lab and bipolar electrode apparatus
Left open
Develop deconvolution or Fickian diffusion models to separate overlapping secondary insulin and serotonin oxidation peaks from fast-scan cyclic voltammograms. Blocker: Requires experimental FSCV voltammogram datasets from bevelled carbon fiber microelectrodes or wet lab electrochemistry equipment.
Electroanalytical engineering strategies for monitoring molecules in neuroscience · Imperial
Left open
Develop statistical variance models for voltammetric current measurements incorporating baseline drift and capacitive effects. Blocker: Requires experimental voltammetry data with known ground-truth noise profiles or a wet lab to collect calibration datasets
Voltammetric Methods Augmented with Physical Models and Statistical Inference · MIT
Left open
Apply Partial Least Squares deconvolution to resolve overlapping DPASV voltammograms and copper interference on gold screen-printed electrodes. Blocker: Requires experimental stripping voltammetry dataset with complex overlapping peaks and copper interference on Au SPEs.
Electrochemical method for the rapid in situ screening of heavy metals in soil and water samples · Cranfield
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