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A Free-Standing Boron-Doped Diamond Grid Electrode for Fundamental Spectroelectrochemistry
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    A Free-Standing Boron-Doped Diamond Grid Electrode for Fundamental Spectroelectrochemistry
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    • Hannah K. Patenaude
      Hannah K. Patenaude
      Radiochemistry Program, Department of Chemistry and Biochemistry, University of Nevada, Las Vegas, Las Vegas, Nevada 89154, United States
      Inorganic, Isotope, and Actinide Chemistry, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States
    • Nastasija Damjanovic
      Nastasija Damjanovic
      Radiochemistry Program, Department of Chemistry and Biochemistry, University of Nevada, Las Vegas, Las Vegas, Nevada 89154, United States
    • Jason Rakos
      Jason Rakos
      Radiochemistry Program, Department of Chemistry and Biochemistry, University of Nevada, Las Vegas, Las Vegas, Nevada 89154, United States
      Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, United States
      Nuclear and Chemical Engineering, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
      More by Jason Rakos
    • Dustyn C. Weber
      Dustyn C. Weber
      Radiochemistry Program, Department of Chemistry and Biochemistry, University of Nevada, Las Vegas, Las Vegas, Nevada 89154, United States
      Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, United States
    • Aaron I. Jacobs
      Aaron I. Jacobs
      Department of Chemistry, Michigan State University, East Lansing, Michigan 48823, United States
    • Samuel A. Bryan
      Samuel A. Bryan
      Nuclear and Chemical Engineering, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
    • Amanda M. Lines
      Amanda M. Lines
      Nuclear and Chemical Engineering, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
    • William R. Heineman
      William R. Heineman
      Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221, United States
    • Shirmir D. Branch
      Shirmir D. Branch
      Nuclear and Chemical Engineering, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
    • Cory A. Rusinek*
      Cory A. Rusinek
      Radiochemistry Program, Department of Chemistry and Biochemistry, University of Nevada, Las Vegas, Las Vegas, Nevada 89154, United States
      Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, United States
      *Email: [email protected]. Tel.: 01-513-529-2457.
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    Analytical Chemistry

    Cite this: Anal. Chem. 2024, 96, 47, 18605–18614
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    https://doi.org/10.1021/acs.analchem.4c00906
    Published November 13, 2024
    Copyright © 2024 American Chemical Society

    Abstract

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    Spectroelectrochemistry (SEC) is a powerful technique that enables a variety of redox properties to be studied, including formal potential (Eo), thermodynamic values (ΔG, ΔH, ΔS), diffusion coefficient (D), electron transfer stoichiometry (n), and others. SEC requires an electrode which light can pass through while maintaining sufficient electrical conductivity. This has been traditionally composed of metal or metal oxide films atop transparent substrates like glass, quartz, or metallic mesh. Robust electrode materials like boron-doped diamond (BDD) could help expand the environments in which SEC can be performed, but most designs are limited to thin films (∼100–200 nm) on transparent substrates less resilient than free-standing BDD. This work presents a free-standing BDD grid electrode (G-BDD) for fundamental SEC measurements, using the well-characterized Fe(CN)63–/4– redox couple as proof-of-concept. With a combination of cyclic voltammetry (CV), thin-layer SEC, and chronoabsorptometry, several of the redox properties mentioned above were calculated and compared. For Eo′, n, and D, similar results were obtained when comparing the CV [Eo′ = +0.279 (±0.002) V vs Ag/AgCl; n = 0.97; D = 4.1 × 10–6 cm2·s–1] and SEC [Eo′ = +0.278 (±0.001) V vs Ag/AgCl; n = 0.91; D = 5.2 × 10–6 cm2·s–1] techniques. Both values align with what has been previously reported. To calculate D from the SEC data, modification of the classical equation used in chronoabsorptometry was required to accommodate the G-BDD electrode geometry. Overall, this work expands on the applicability of SEC techniques and BDD as a versatile electrode material.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.analchem.4c00906.

    • Experimental details include chemicals, materials, and instrumentation used throughout the work; SIMS plot is also presented to determine the boron concentration in the BDD grid electrode; the CV iE responses for the potential window studies are shown as well as the data for the SEC control studies (PDF)

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    Analytical Chemistry

    Cite this: Anal. Chem. 2024, 96, 47, 18605–18614
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.analchem.4c00906
    Published November 13, 2024
    Copyright © 2024 American Chemical Society

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