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Cited by 14Electrochemical Analysis and ApplicationsElectrodeposition and Electroless CoatingsElectrocatalysts for Energy Conversion

Copper deposition on metallic and non‐metallic single particles via impact electrochemistry

Open access
Oladeji, Abiola V., Courtney, James M., Rees, Neil V.·2022·Electrochimica Acta
DOI 10.1016/j.electacta.2022.139838
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Abstract

This study demonstrates the possibility of depositing metals onto low-metal content particles via impact electrochemistry, a technique used to measure transient current signals (electrochemical impacts) produced from the collision between particles moving under Brownian motion and a potentiostated interface (Rees, 2014; Markham et al., 2020; Zhang and Zhou, 2020). The deposition of copper onto the surface of fly-ash cenospheres via electrochemical impacts is reported, along with its deposition onto silver and gold nanoparticles. A comparison with linear sweep voltammetry confirmed that impact signals correlated with deposition potentials (bulk and underpotential deposition). Reductive impact events were observed at potentials negative of −0.3 V (for Ag) and −0.1 V (for Au) (vs. MSE), with evidence for a change in coverage of deposition from ca. 103% at −0.1 V to 261% at −0.8 V vs. MSE for Au. Cenospheres were shown to be sufficiently electrochemically active to facilitate copper deposition, either on modified electrodes or showing transient impact spikes indicating copper deposition, which was confirmed via SEM/EDX and ICP-MS analysis.

AI snapshot

Written from the paper’s full text.

TL;DR

This paper shows that copper can be electrodeposited onto metallic nanoparticles and non-metallic fly-ash cenospheres during particle–electrode impacts, with deposition onset and coverage depending on substrate and potential. It demonstrates the feasibility of impact electrochemistry for depositing metals onto low-value/waste core particles, though analysis is semi-quantitative and coverage estimates are sensitive to aggregation.

Key findings

  • Cu impact deposition on AgNPs was observed at potentials negative of −0.3 V vs MSE, with average impact frequencies of 2.3–3.7 GHz m⁻²; at −0.4 V an average coverage of 479% was observed, though removing larger spikes gave 60–170% of a monolayer.
  • Cu impact deposition on AuNPs was observed at potentials negative of −0.1 V vs MSE; underpotential deposition gave an average coverage of ca. 103% ± 8%, while bulk deposition gave an average coverage of 215% ± 37% (the abstract reports up to 261% at −0.8 V vs MSE).
  • Fly-ash cenospheres were sufficiently electrochemically active for Cu deposition: SEM/EDX Cu content was 7.43 ± 2.47% for impacted particles versus 0.07 ± 0.08% for pristine particles (N = 7), and ICP-MS showed 2.0 ppb Cu for modified versus 1.0 ppb for unmodified cenospheres (detection limit 0.174 ppb).
  • Cenosphere characterization showed a size distribution centred around 1 μm and average SEM/EDX composition of Si 52.3%, Al 29.4%, Fe 9.0%, Ca 6.7%, Mg 2.3%, and Cu 0.2%.

Methods

  • Three-electrode impact chronoamperometry used carbon fibre microelectrodes (9, 11, or 33 μm) or a glassy carbon macroelectrode (3 mm), a mercury sulphate reference electrode, and a graphite counter electrode; typical solutions contained 0.5 mM CuSO₄, 19 mM K₂SO₄, and 1 mM H₂SO₄ with 50/60 nm AuNPs, 60 nm AgNPs, or fly-ash cenospheres.
  • Transient current spikes were analysed after digital filtration at 250 Hz; charge was integrated to calculate coverage using spherical-particle equations, and onset potentials were compared with linear sweep/cyclic voltammetry.
  • Deposits were characterized by SEM/EDX, ICP-MS, and handheld XRF; cenospheres were modified via a 12 h chronoamperometric scan at −0.75 V vs MSE for deposition evidence.

Limitations

  • Stated: impact data are semi-quantitative at best because acquisition is limited by the 100 kS s⁻¹ sampling rate, so comparisons are relative rather than absolute; coverage calculations assume a single mean particle diameter and are highly sensitive to aggregation.
  • Stated: impact deposition is uncontrolled and cenosphere composition/conductivity is nonuniform, so not all cenospheres collide or deposit Cu; detailed quantitative analysis of Cu deposition onto the GC substrate was outside the study’s scope.
  • Evident: the SEM/EDX copper-content comparison uses N = 7 and ICP-MS reports single modified/unmodified values, limiting statistical strength; the abstract’s 261% Au coverage at −0.8 V differs from the results’ 215% ± 37% average, indicating variability in coverage estimates.

Model-written summary. Check it against the paper before relying on it.

Integrity signals

Registry

Crossref · 10.1016/j.electacta.2022.139838

Cites

101 of 101 references verified0 citation errors · 0 not checkable

Statistics

Nothing to recompute.

Claims the paper makes

0 of 12 cited sources checked · 0 supported · 0 flagged

  • Findingown data

    Copper deposition occurred on nanoparticle collisions at potentials negative of -0.3 V vs. MSE.

    “where copper deposition occurred on nanoparticle collisions occurring at a potential negative of -0.3 V vs. MSE.”
    Quote in the paperSubstantial claim
  • Findingcitation

    The onset of bulk copper deposition on the surface of silver is approximately -0.33 V vs. MSE.

    “This agrees with the data shown in Fig. 1 (and in literature [ 61 , 81 ]) indicating that the onset of bulk copper deposition on the surface of silver is approximately -0.33 V (vs.MSE).”
    • Also stated in: § 4. Conclusion · hedged
      “indicating that the onset of bulk copper deposition on the surface of silver is approximately -0.33 V (vs.MSE).”
    Quote in the paperSubstantial claim0 of 2 sources checked
    • cites [61] Dietterle, 1995, The initial stages of copper deposition on Ag(111): an STM study, Surf. Sci. source
    • cites [81] Thiel, 2008, A new approach on the Cu UPD on Ag surfaces, J. Electroanal. Chem. source
  • Findingown data

    Copper can be deposited onto the surface of fly-ash cenospheres via electrochemical impacts.

    “The deposition of copper onto the surface of fly-ash cenospheres via electrochemical impacts is reported”
    Quote in the paperSubstantial claim
  • Findingown data

    Reductive peaks can be observed at potentials more negative than -0.3 V vs. MSE.

    “At potentials more negative than -0.3 V vs. MSE, reductive peaks can be observed.”
    Quote in the paperSubstantial claim
  • Findingown data

    Reductive impact events for copper deposition on Au nanoparticles are observed at potentials negative of -0.1 V vs. MSE.

    “and -0.1 V (for Au) (vs.MSE)”
    Quote in the paperSubstantial claim
  • May combine two claims. 20
  • Classified as probably not a substantial claim. 3
  • The quote only partly states this claim. 3

  • May combine two claims.

    Findingown data

    The cyclic voltammetry for bare GC depicts two peaks with currents of -7.2 μA and -2.1 μA, where the first peak is ascribed to copper deposition on bare GC and the second to deposition on the copper-modified GC surface.

    “The cyclic voltammetry (see Fig. 5 ) for the bare GC depicts two peaks with currents of -7.2 μA and -2.1 μA where the first peak is ascribed to copper deposition on the bare GC (peak 1) followed by deposition on the copper-modified GC surface (peak 2).”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Findingreasoning

    The background current varies quite widely, especially at more negative potentials.

    “It is also noted that the background current varies quite widely, especially at more negative potentials”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    Removal of the larger impacts yields coverages in the range 60-170% of a monolayer, which is comparable with the AuNP result.

    “Removal of these larger impacts yields coverages in the range 60-170% of a monolayer, which is comparable with the AuNP result.”
    Quote in the paperSubstantial claim
    • The authors state this as an assumption: The impacting nanoparticles are spherical.

  • May combine two claims.

    Findingown data

    Upon addition of silver nanoparticles, reductive transient peaks were observed, suggesting copper deposition during impact events at -0.8 V vs. MSE.

    “Upon the addition of silver nanoparticles, reductive transient peaks can be observed (see Fig.2 B) suggesting the occurrence of copper deposition during impact events at this potential.”
    Quote in the paperSubstantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing). May combine two claims.

    Findingcitation

    Cenospheres are mainly comprised of metal oxides, with varying compositions reflecting those of their starting materials.

    “The SEM/EDX analysis in Table 1 is in agreement with both the XRF data obtained and literature reports (see Supplementary Information Section G Table T4) that cenospheres are mainly comprised of metal oxides, with varying compositions reflecting those of their starting materials [ 57 , 92 , 93 ]”
    Quote in the paperNot a substantial claim0 of 3 sources checked
    • cites [57] Blissett, 2012, A review of the multi-component utilisation of coal fly ash, Fuel source
    • cites [92] Ahmaruzzaman, 2010, A review on the utilization of fly ash, Prog. Energy Combust. Sci. source
    • cites [93] Ranjbar, 2017, Cenospheres: a review, Fuel source

  • May combine two claims.

    Findingown data

    Upon addition of silver nanoparticles, reductive transient peaks can be observed, suggesting the occurrence of copper deposition during impact events at -0.8 V vs. MSE.

    “Upon the addition of silver nanoparticles, reductive transient peaks can be observed (see Fig. 2 B) suggesting the occurrence of copper deposition during impact events at this potential.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    The size distribution of cenospheres ranged from hundreds of nanometres to hundreds of microns, with a population centred at 1 μm.

    “A size distribution analysis was conducted indicating a wide range of sizes from 100 s of nanometres to 100 s of microns with a population centred at 1 μm.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    The apparent coverages on Ag are skewed by several significantly larger impact spikes, which are consistent with the impacts of larger aggregates of NPs.

    “Closer examination of the data indicates that the apparent coverages on Ag are skewed by several significantly larger impact spikes, which are consistent with the impacts of larger aggregates of NPs.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    Peaks in the upd region resulted in particle coverage of approximately a monolayer (average ca. 103% ± 8%), while peaks in the bulk region showed higher coverage (average ca. 215% ± 37%).

    “Evidence was found suggesting peaks occurring in the upd region resulted in particle coverage of approximately a monolayer (with an average of ca.103% ± 8%) while peaks in the bulk region showed indication of a higher coverage (with an average of ca.215% ± 37%).”
    Quote in the paperSubstantial claim

  • The quote only partly states this claim.

    Findingown data

    At potentials more negative than -0.3 V vs. MSE, reductive peaks can be observed for Ag nanoparticles.

    “At potentials more negative than -0.3 V vs. MSE, reductive peaks can be observed.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    The upd peak for copper deposition on gold occurred at ca. -0.3 V vs. MSE and bulk deposition occurred at potentials more negative than ca. -0.4 V vs. MSE.

    “Fig.1is broadly in agreement with this, with the upd peak at ca. -0.3 V (vs.MSE) and bulk deposition occurring at potentials more negative than ca.-0.4 V (vs.MSE).”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    The cenosphere sample has a particle size distribution centred around 1 μm, though a very large range of sizes occur.

    “Fig. 4 B shows the particle size distribution produced from SEM images of the cenosphere sample and highlights a population centred around 1 μm in size, though a very large range of sizes occur”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    The average copper content of impacted cenosphere particles determined by SEM/EDX was 7.43 ± 2.47% (by count, N = 7), compared to 0.07 ± 0.08% for pristine cenospheres, and the impacted FACs were significantly higher than non-impacted (pristine) FACs.

    “with an average Cu content of 7.43 ± 2.47% compared to 0.07 ± 0.08% (by count, N = 7).”
    Quote in the paperSubstantial claim

  • The quote only partly states this claim.

    Findingown data

    Upon addition of cenosphere particles in a Ru(NH3)6Cl3 solution, a reductive peak could be observed suggesting an increase in current rather than a blocking effect.

    “Upon the addition of cenosphere particles a reductive peak could be observed suggesting an increase in current rather than a blocking effect.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    Copper deposition was observed during silver nanoparticle impacts, with the switch on/off potential aligned with the onset potential at -0.4 V vs. MSE.

    “Using impact voltammetry, copper deposition was observed during silver nanoparticle impacts, where the switch on/ off potential aligned with the onset potential previously mentioned at -0.4 V vs. MSE.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    ICP-MS analysis showed the unmodified cenosphere had a copper content of 1.0 ppb and the modified cenosphere sample had 2.0 ppb.

    “The analysis showed that the unmodified cenosphere had a copper content in the sample of 1.0 ppb and the modified cenosphere sample had double the copper content at 2.0 ppb.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingreasoning

    Copper deposition on the gold-modified GC surface commences at a potential of -0.1 V vs. MSE whereas the onset onto other materials occurs at more negative potentials.

    “It can be observed that copper deposition on the gold-modified GC surface commences at a potential of -0.1 V vs. MSE whereas the onset onto other materials occurs at more negative potentials.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    Upon modification of bare GC with cenosphere particles, the cenosphere-modified electrode has increased reductive current without any discernible increase in capacitance.

    “Upon modification of the bare GC with cenosphere particles, the cenosphere-modified electrode has increased reductive current without any discernible increase in capacitance”
    Quote in the paperSubstantial claim

  • The quote only partly states this claim.

    Findingown data

    Cenosphere particles were electrochemically active.

    “chemically active.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    During impact voltammetry, cenospheres exhibited transient spikes and evidence of copper deposition.

    “During impact voltammetry cenospheres exhibited transient spikes and evidence of copper deposition.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Interpretationown data

    The ICP-MS copper content values are well above the detection limit (0.174 ppb) and provide further evidence that impacting cenospheres increases copper concentration.

    “These values are well above the detection limit (0.174 ppb) of the ICP-MS and as such provides further evidence of impacting cenosphere increasing in concentration of copper.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Interpretationown data

    Not all cenospheres collided with the GC electrode, or an impact occurred with little to no copper deposition.

    “implying not all cenospheres collided with the GC electrode or else an impact occurred with little to no copper deposition.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Interpretationreasoning

    The variation in copper content among cenospheres is expected because the impact deposition process is uncontrolled and the cenosphere composition (and hence conductivity) is not uniform.

    “This variation is expected as the impact deposition process is uncontrolled, and the cenosphere composition (and hence conductivity) is not uniform”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Interpretationreasoning

    The degree of copper deposition onto the GC substrate depends on the potential at which the impact experiment was conducted.

    “The degree of deposition of Cu onto the GC substrate, will clearly be dependant on the potential at which the impact experiment was conducted”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Interpretationcitation

    The observed difference in deposition amounts between AgNP and AuNP is due to the degree of aggregation in the NPs, with AgNPs known to have rapid aggregation kinetics.

    “We postulate that the observed difference in deposition amounts is due to the degree of aggregation in the NPs, with AgNPs in particular, known to have rapid aggregation kinetics [27] .”
    Quote in the paperSubstantial claim0 of 1 sources checked
    • cites [27] Rees, 2011, The aggregation of silver nanoparticles in aqueous solution investigated via anodic particle coulometry, ChemPhysChem source
    • The authors state this as an assumption: The bulk deposition kinetics of Cu are not markedly different on Ag and Au.
25 of 25

  • The authors state this as an assumption.

    The impacting nanoparticles are spherical.

    “assuming a spherical NP”

  • The authors state this as an assumption.

    The cenosphere-modified GC macro electrode has an even distribution of cenospheres.

    “based on calculation assuming even distribution [78]”

  • The authors state this as an assumption.

    The bulk deposition kinetics of Cu are not markedly different on Ag and Au.

    “provided that the bulk deposition kinetics of Cu were not markedly different on Ag and Au.”

  • The paper relies on this without support.

    The Cu/Si count ratio accounts for variation in particle size and composition when comparing copper content of cenospheres.

    “Note that these values are quoted relative to the measured silicon (Si) content of the same FAC particle, to account for the variation in particle size and composition.”
4 of 4

Self-check

Percentages, sums and reported differences re-computed from the paper’s own numbers.

Each contradiction between two passages listed here was confirmed by an independent check.

  • Potential of the pre-AuNP scan differs between text and caption

    Minor

    The results describe the before-and-after AuNP scans as being conducted at −0.3 V and −0.8 V, whereas the Fig. 3 caption places the scan before AuNP addition at −0.55 V.

  • AgNP size used for the modified electrode is absent from the materials list

    Minor

    The preparation of the AgNP-modified electrode specifies 50 nm AgNPs, while the materials list identifies only 60 nm AgNPs among the chemicals used.

2 of 2

Cites

Flagged first, then by citations

Research works printed but not linked: 1

  1. Rees, 2014, Electrochemical insight from nanoparticle collisions with electrodes: a mini-review, Electrochem. Commun., 43, 83, 10.1016/j.elecom.2014.03.018 · DOI

Cited by

Still being checked.

Related

Authors
Oladeji, A. V., Courtney, J. M., & Rees, N. V.
Affiliations
University of Birmingham (GB)
Corresponding author
Rees, Neil V.
ORCID
Venue
Electrochimica Acta
Publisher
Elsevier BV
Published
2022-02
Volume
405
Pages
139838
ISSN
0013-4686 (ISSN-L)
DOI
10.1016/j.electacta.2022.139838
OpenAlex
W4210645414
Cited by
14
References
101
Citations by year
2026: 1 · 2025: 1 · 2024: 6 · 2023: 3 · 2022: 3
FWCI
1.12
Type
journal article
Language
en
Open access
Licence
Locations
  • Electrochimica Acta (publishedVersion, cc-by)
  • University of Birmingham Research Portal (University of Birmingham) (submittedVersion, cc-by)
  • University of Birmingham Research Portal (University of Birmingham) (submittedVersion, other-oa)
Funders
  • EPSRC (EP/G037116/1)
  • Leverhulme Trust (RPG-2019–146)
  • University of Nottingham
Topics
  • Physical Sciences › Chemistry › Electrochemistry › Electrochemical Analysis and Applications
  • Physical Sciences › Engineering › Electrical and Electronic Engineering › Electrodeposition and Electroless Coatings
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
Keywords
copper deposition, fly ash cenospheres, silver nanoparticles, gold nanoparticles, underpotential deposition, reductive deposition, transient current signals, modified electrode

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