Skip to content

Fabrication of a boron-doped nanocrystalline diamond grown on an WC–Co electrode for degradation of phenol

MetadataDetails
Publication Date2022-01-01
JournalRSC Advances
AuthorsTao Zhang, Zhe Xue, Ying Xie, Guodong Huang, Guangpan Peng
InstitutionsWuxi Institute of Technology, Shanghai Ocean University
Citations11
AnalysisFull AI Review Included

This research focuses on fabricating highly stable and efficient Boron-Doped Nanocrystalline Diamond (BDD) electrodes on a novel Cemented Carbide (WC-Co) substrate for electrochemical oxidation.

  • Novel Substrate: WC-Co was successfully used as the substrate via Hot Filament Chemical Vapor Deposition (HFCVD), offering superior adhesion and lower thermal expansion mismatch compared to conventional Si, Ti, or Nb substrates.
  • Material Quality: The resulting nanocrystalline BDD films (4 µm thick, 100 nm grain size) were highly uniform, pinhole-free, and exhibited low compressive stress (-2.3 GPa).
  • Electrochemical Performance: The WC-Co/BDD electrode demonstrated a wide electrochemical window of 3.8 V and extremely low background currents in 0.5 mol L-1 H2SO4.
  • Stability Achievement: The electrode showed excellent electrochemical stability, achieving a service life exceeding 400 hours in an Accelerated Life Test (ALT) at a high current density (1 A cm-2).
  • Pollutant Degradation: The electrode exhibited high activity in degrading high-concentration phenol (25 mmol L-1), reducing the Chemical Oxygen Demand (COD) from 5795 mg L-1 to 85 mg L-1.
  • Efficiency: The mineralization process achieved an average instantaneous current efficiency (ICE) of approximately 46%.
ParameterValueUnitContext
Substrate MaterialWC-Co (6% Co)N/AUsed for enhanced adhesion
Film TypeNanocrystalline BDDN/ADeposited via HFCVD
Film Thickness4µmAfter 270 min growth
Grain Size~100nmHighly uniform morphology
Residual Stress (Calculated)-2.3GPaCompressive stress (Raman shift)
Boron Concentration ([B]/[C]gas)5000ppmAtomic ratio in gas phase
Boron Concentration (Raman Est.)3.5 x 1021cm-3Estimated via 500 cm-1 band
Resistivity (WC-Co/BDD)0.2mΩ cmHigh electrical conductivity
Electrochemical Window3.8VIn 0.5 mol L-1 H2SO4
ALT Service Life>400hours@ 1 A cm-2 in 3 mol L-1 H2SO4
Initial Phenol Concentration25mmol L-1High concentration test
Initial COD5795mg L-1Phenol solution
Final COD85mg L-1After 43 Ah L-1 charge loading
Average Current Efficiency (ICE)~46%For phenol mineralization
Phenol Oxidation Potential~1.5VLower than water decomposition potential
Redox Behavior (K3[Fe(CN)6])Quasi-reversibleN/AIp,a/Ip,c ratio close to 1

The nanocrystalline BDD films were fabricated using a self-made Hot Filament Chemical Vapor Deposition (HFCVD) system.

  1. Substrate Preparation (WC-Co):
    • WC-Co rods (3 mm diameter, 6% Co) were chemically pretreated using Murakami’s reagent (30 min) and Caro’s acid (60 s) to remove cobalt binder from the surface.
    • Substrates were subsequently abraded using 5 µm commercial diamond powders to increase surface defects and enhance diamond nucleation density.
  2. HFCVD Setup:
    • Tantalum wires (Φ 0.5 mm) were used as hot filaments.
    • The system employed a dynamic boron-doping method.
  3. Nucleation and Growth Parameters (Table 1):
ParameterNucleation PhaseGrowth Phase
CH4/H2 Ratio2.0%1.5%
[B]/[C]gas Ratio5000 ppm5000 ppm
Pressure2 kPa2 kPa
Substrate Temperature800 °C850 °C
Filament Temperature2000 ± 200 °C2200 ± 200 °C
Duration30 min270 min
  1. Electrochemical Testing:
    • Potential Window/CV: Tested in a three-electrode cell using 0.5 mol L-1 H2SO4 electrolyte.
    • Accelerated Life Test (ALT): Conducted in 3 mol L-1 H2SO4 at a constant current density of 1 A cm-2.
    • Pollutant Degradation: Phenol (25 mmol L-1) was degraded using a constant current density of 100 mA cm-2. COD was measured using a visible spectrophotometer.

The WC-Co/BDD electrode technology is highly relevant to industries requiring robust, long-life, and highly efficient electrochemical anodes.

  • Wastewater Treatment (Primary Application):
    • Refractory Organics: Effective mineralization of highly hazardous, non-biodegradable pollutants found in chemical, pharmaceutical, pesticide, and printing/dyeing effluents (e.g., phenol, aniline, dyes).
    • High Load Processing: Demonstrated capacity to handle high pollutant concentrations (25 mmol L-1 phenol) efficiently.
  • Industrial Electrochemistry:
    • Harsh Environments: Suitable for processes requiring high anodic stability and resistance to corrosion, particularly in strong acidic media (proven stability in 3 mol L-1 H2SO4).
    • Electrosynthesis: The wide potential window and low background current are ideal for selective oxidation reactions in organic synthesis.
  • Protective Coatings:
    • Tooling: WC-Co is a common material for cutting tools. The BDD coating provides extreme hardness and chemical inertness, extending tool life in aggressive machining or chemical environments.
  • Electrochemical Sensing:
    • The low background current and stable surface properties inherent to BDD make it an excellent platform for sensitive detection of trace organic and inorganic species.
View Original Abstract

WC-Co is applied as the substrate instead of conventional ones, on which nanocrystalline BDD films are deposited by HFCVD. WC-Co/BDD electrode like the standard BDD shows a wide potential window and a good mineralization capacity in phenol.