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Use of nano zero-valent iron to reduce inorganic species electrogenerated during anodic oxidation on boron doped diamond anodes

MetadataDetails
Publication Date2016-01-01
JournalIRIS Research product catalog (Sapienza University of Rome)
AuthorsElisabetta Petrucci, Luca Di Palma, Maria Monaco, Daniele Montanaro
Citations4
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Technical Documentation and Analysis: High-Stability BDD Electrodes for Water Decontamination

Section titled “Technical Documentation and Analysis: High-Stability BDD Electrodes for Water Decontamination”

This document analyzes the research focusing on the use of Boron-Doped Diamond (BDD) anodes for the anodic oxidation of chloride-containing water, a critical step in advanced environmental remediation.

  • Core Application: Electrochemical water decontamination, specifically targeting the removal of chloride-based pollutants (active chlorine, chlorate, perchlorate).
  • Material Validation: The study validates Boron-Doped Diamond (BDD) thin-film electrodes as the most attractive material due to their exceptional stability, chemical inertness, and wide potential window for water discharge.
  • Mechanism Confirmation: BDD anodes successfully utilized their high efficiency in electrogenerating physisorbed hydroxyl radicals to drive the oxidation process under galvanostatic conditions (300 A/m2).
  • Process Enhancement: Although BDD oxidation generates difficult-to-reduce byproducts (chlorate/perchlorate), the research demonstrates a viable nZVI post-treatment to achieve complete conversion of active chlorine and chlorate back to harmless chloride ions.
  • Required Material Specifications: The experiment utilized a custom 5 cm2 BDD anode, highlighting the need for highly controlled, application-specific electrode geometries provided by MPCVD experts like 6CCVD.
  • Viability for Scale-Up: The combined BDD oxidation and nZVI reduction technology is identified as a robust, environmentally sustainable method for treating solutions containing active chlorine and chlorate.

The following parameters define the operational conditions for the BDD-driven anodic oxidation step discussed in the paper:

ParameterValueUnitContext
Anode MaterialBoron-Doped Diamond (BDD)N/AThin-film electrode exhibiting high stability.
Anode Working Area5cm2Specified geometry for the experimental setup.
Cathode MaterialPlatinum (Pt) WireN/ACommercial counter electrode.
Electrolysis ModeGalvanostaticN/AConstant current used during oxidation.
Current Density (J)300A/m2Key operational parameter for oxidation kinetics.
Reactor TypeUndivided cellN/AMembrane-free glass reactor.
Reaction Volume100mLWorking fluid volume.
Operating Temperature23 ± 2°CNatural ambient laboratory temperature.
Initial Reagent50mMInitial concentration of NaCl (chloride source).
Target ByproductsActive Chlorine, Chlorate, PerchloratemgL-1Generated species requiring subsequent nZVI reduction.

The study utilized a two-stage process, critically relying on high-purity BDD for the primary electrochemical oxidation.

  1. Electrochemical Oxidation (BDD Anode):

    • Performed galvanostatically using a BDD anode and a Pt cathode in an undivided, thermostated, and stirred glass reactor.
    • Objective: Generate active chlorine, chlorate, and perchlorate from 50 mM NaCl solution.
    • Operating Conditions: Current density fixed at 300 A/m2 at ambient temperature (23 ± 2 °C).
  2. Nano Zero-Valent Iron (nZVI) Synthesis:

    • Prepared in the laboratory via the borohydride reduction method using FeSO4 and NaBH4.
    • Environment Control: Liquid reagents purged for 30 min with Nitrogen gas (N2) to maintain an oxygen-free atmosphere, crucial for stability.
  3. Post-Treatment Reduction (nZVI):

    • Tested nZVI dosage ranging from 0.5 gL-1 to 4 gL-1 and temperature from 25 °C up to 80 °C.
    • Stoichiometry Constraint: Complete chlorate reduction requires a molar ratio of Fe/ClO3 equal to 3 (minimum dosage of 0.8 gL-1 nZVI for the 400 mgL-1 chlorate solution).
    • Performance: Complete reduction of chlorate was achieved rapidly (in < 5 minutes at 80 °C with 2 gL-1 nZVI), while perchlorate required extreme conditions (4 gL-1 nZVI at 80 °C) and achieved only 30% removal.

This research confirms the essential role of specialized Boron-Doped Diamond (BDD) electrodes in advanced environmental electrochemical treatments. 6CCVD is uniquely positioned to supply the high-purity BDD materials, custom geometries, and integrated metalization necessary to replicate this research and scale it to industrial requirements.

To replicate or extend this electrochemical water treatment research, BDD electrodes with precise doping and geometry control are mandatory.

  • Primary Material: Heavy Boron-Doped Polycrystalline Diamond (BDD) thin films or thick substrates. 6CCVD specializes in MPCVD growth optimized for electrochemical applications, ensuring the high chemical inertness and wide potential window required for effective hydroxyl radical generation.
  • Material Formats: Available as polished thin films (0.1 ”m up to 500 ”m thickness) on conductive substrates, or as free-standing BDD plates up to 10mm thickness for robust industrial systems.
  • Polishing: We offer fine polishing to Ra < 5nm for inch-size BDD wafers, ensuring high surface uniformity crucial for repeatable electrochemical kinetics.

The paper used a standard lab-scale 5 cm2 electrode. 6CCVD’s capabilities facilitate immediate scale-up and complex integration requirements.

Paper Requirement6CCVD Customization ServiceTechnical Specification
Electrode SizeCustom laser cutting to any geometry required by the reactor cell (e.g., 5 cm2 or larger arrays).Plates/wafers up to 125mm in diameter (PCD/BDD).
Electrode ContactsIn-house metalization services for highly durable and low-resistance contacts, crucial for galvanostatic applications.Metalization layers include Au, Pt, Pd, Ti, W, and Cu.
Cathode IntegrationCustom supply of Pt-integrated diamond structures, allowing researchers to explore novel integrated reactor designs, moving beyond simple Pt wire cathodes.Pt metalization internal capability.
Research ScopeSupply of specialized Boron-Doped Diamond for testing the limits of oxidation, including varying doping concentrations for optimization.BDD wafers with tunable Boron concentration for specific conductivity requirements.

6CCVD’s in-house team of material scientists and PhD-level engineers possesses deep expertise in MPCVD diamond properties and electrochemical application requirements. We provide consultation services to assist researchers and industrial clients globally with material selection for similar Advanced Water Decontamination projects. This includes optimizing BDD surface morphology, doping profiles, and electrode design for maximum Faradaic efficiency and lifespan.

We handle all international logistics, offering global shipping with DDU (Delivered Duty Unpaid) default terms, and DDP (Delivered Duty Paid) options available upon request.

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

View Original Abstract

In this paper, the solution coming from an anodic oxidation on boron doped diamond of chloride-containing solution is treated with addition of nano zero-valent iron (nZVI) to reduce the amount of chlorinated byproducts into chloride ions. The electrolyzed solutions have been obtained under galvanostatic conditions in an undivided reactor. The evolution and depletion of all the chlorinated species have been monitored by spectrophotometry and ion chromatography. The nanoscale iron particles have been synthesized in our laboratory by a fast and facile method through reaction of FeSO4 and NaBH4 solutions without addition of dispersants. The effect on the conversion yield of several operative parameters has been investigated and discussed. The preliminary results indicate that a nZVI postreatment can be considered a viable technology for the treatment of solutions containing active chlorine and chlorate. However, the reduction of perchlorate, either in mixed solutions or alone, requires too drastic conditions to be completed.