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Electrochemically Catalytic Activity of Boron-doped Diamond for I<sup>−</sup>/I<sup>0</sup> Redox Couple

MetadataDetails
Publication Date2015-01-01
JournalElectrochemistry
AuthorsJin Kawakita, Yasuo Hashimoto Shinoda, Yukihiro Sakamoto
InstitutionsChiba Institute of Technology, National Institute for Materials Science
Citations4
AnalysisFull AI Review Included

This study successfully validates Boron-Doped Diamond (BDD) as a chemically stable, high-performance electrocatalyst alternative to Platinum (Pt) for the Iodide/Iodine (I-/I0) redox couple, critical for applications like Dye-Sensitized Solar Cells (DSSCs).

  • Core Achievement: BDD demonstrates electrocatalytic activity with a peak exchange current density of 0.94 ”A/cm2, exceeding that of conventional graphite (0.87 ”A/cm2).
  • Material Optimization: Catalytic activity exhibits a strong, parabolic dependence on the boron doping level, underscoring the necessity of precision-controlled CVD growth parameters.
  • Stability Advantage: BDD provides superior chemical stability compared to Pt electrodes, which suffer from dissolution in high-exposure electrolyte environments.
  • Methodology: BDD was synthesized via Microwave Plasma Chemical Vapor Deposition (MPCVD) using trimethyl borate (B(OCH3)3) for controlled boron incorporation.
  • Surface Enhancement: The study confirms that post-growth UV irradiation, which promotes C=O termination on the diamond surface, enhances the charge transfer kinetics and catalytic efficiency.
  • 6CCVD Value Proposition: 6CCVD specializes in producing high-uniformity, heavily doped BDD wafers necessary to replicate and scale these optimized results, offering custom doping profiles and surface modification capabilities.
ParameterValueUnitContext
Peak Exchange Current Density (j0)0.94”A/cm2Optimized BDD material
Comparative j0 (Graphite)0.87”A/cm2Standard benchmark material
Comparative j0 (Platinum, Pt)73.8”A/cm2Current industry standard
Doping Control Parameter Range1.0 - 6.0SCCMH2 flow carrying B(OCH3)3
Synthesis Pressure20kPaMPCVD Growth Environment
Microwave Power1.0kWMPCVD Power Input
H2 Gas Flow Rate (Standard)100SCCMPrimary Carrier Gas
CH4 Gas Flow Rate15SCCMCarbon Source
Substrate Size Used10 x 10 x 1.0mmSilicon Wafer Coupon
Electrolyte Composition0.5 M LiI, 0.05 M I2ConcentrationAcetonitrile solvent
BDD Thickness Range0.1 - 500”mTypical BDD thickness range (6CCVD standard)

The BDD films were synthesized using the MPCVD technique, with specific attention paid to precise gas flow control for doping consistency, followed by targeted surface treatments.

  1. CVD Setup: BDD was prepared via a mode-transformation MPCVD method utilizing a silicon wafer coupon (10 x 10 x 1.0 mm) as the substrate.
  2. Pre-Growth Treatment: Substrate surface was scratched with diamond powder and ultrasonically cleaned in acetone to ensure strong adhesion.
  3. Gas Mixture & Doping Control: Standard growth gases (H2 at 100 SCCM, CH4 at 15 SCCM) were used. Boron doping was controlled by flowing H2 gas (1.0-6.0 SCCM) over vaporized trimethyl borate (B(OCH3)3).
  4. Synthesis Parameters: Growth occurred at 20 kPa synthesis pressure, 1.0 kW microwave power, for a duration of 3.0 hours.
  5. Surface Modification: After CVD, samples were irradiated with UV light (185 nm and 254 nm low-pressure mercury lamp) for 5 minutes at a 10 mm distance. This treatment was confirmed by XPS to promote C=O termination, enhancing catalytic activity.
  6. Electrochemical Evaluation: Linear sweep voltammetry was performed using a three-electrode cell configuration (BDD working electrode, Pt counter and reference electrodes) in a 0.5 M LiI / 0.05 M I2 acetonitrile electrolyte.

6CCVD provides the high-quality, reproducible BDD materials and engineering customization required to replicate and significantly scale this electrocatalysis research for commercial or industrial adoption (e.g., high-efficiency DSSCs, electrochemical sensing, or chemical remediation).

The research critically relies on highly controllable, heavy boron doping (p-type). 6CCVD offers two primary solutions tailored for this application:

  • Heavy Boron-Doped Polycrystalline Diamond (PCD/BDD): Ideal for cost-sensitive, large-area applications. We offer wafers up to 125mm diameter with high dopant uniformity across the entire plate, ensuring reproducible parabolic activity dependence.
  • Boron-Doped Single Crystal Diamond (SCD/BDD): Recommended for R&D applications where ultra-precise doping control, crystal orientation, and minimal grain boundary effects are paramount for resolving catalytic mechanisms. Available thicknesses from 0.1”m up to 500”m.

6CCVD’s in-house capabilities directly address the limitations and opportunities identified in the paper:

Research Requirement / Opportunity6CCVD Capability & Advantage
Doping Uniformity & Control: Parabolic dependence requires reproducible boron incorporation across large areas.Precision MPCVD: We guarantee tight control over the B/C ratio during growth for highly uniform doping profiles across inch-size wafers.
Substrate Size & Thickness: Paper used small 10x10 mm coupons.Scalability: We provide custom plates and wafers up to 125mm (PCD), enabling direct transition from lab-scale coupons to pilot-scale production.
Surface Termination: UV irradiation was used to form active C=O bonds.Controlled Surface Engineering: 6CCVD offers various termination services (e.g., controlled O-termination, H-termination) that provide more consistent and scalable surface activation than batch UV processes.
Working Electrode Preparation: The paper used Pt for counter and reference electrodes, despite acknowledging Pt dissolution issues.Custom Metalization: We offer internal metalization (Au, Pt, Pd, Ti, W, Cu) services to deposit chemically resistant contacts or define active electrode areas (e.g., Ti/W/Au stack) on the diamond back-side, ensuring long-term stability in harsh electrolytes.
Polishing Requirements: High-quality interfaces are essential for electrochemical testing reproducibility.Ultra-Smooth Surfaces: We achieve polishing down to Ra < 5nm for inch-size PCD and Ra < 1nm for SCD, minimizing scattering and maximizing the electrochemical active surface area.

6CCVD maintains an in-house PhD-level engineering team specializing in diamond growth and surface physics. We can assist researchers and manufacturers in material selection and optimization for high-stability, high-efficiency electrocatalytic projects, including:

  • Determining the optimal B/C ratio to achieve the peak catalytic current density (0.94 ”A/cm2).
  • Developing robust surface termination protocols (e.g., controlled O-termination) to bypass the need for post-growth UV irradiation.
  • Designing large-format BDD electrodes for scalable dye-sensitized solar cell (DSSC) applications, addressing the instability issues of conventional Pt cathodes.

For custom specifications or material consultation, visit 6ccvd.com or contact our engineering team directly.

View Original Abstract

Boron-doped diamond (BDD) is promising as electrocatalyst for alternative material to platinum (Pt) because of its superior chemical stability. Electrochemically catalytic activity of BDD on the redox couple of I−/I0 was studied by using the electrochemical method. It showed the parabolic dependence on the doping level of boron in diamond and the maximum value was 0.94 ”A/cm2 in terms of the exchanging current density. This value is slightly higher than graphite and smaller than Pt. Additional surface modification of BDD could improve the catalytic activity.