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6CCVD Research

The Importance of Cannizzaro-Type Reactions during Electrocatalytic Reduction of Carbon Dioxide

At a Glance

Section titled “At a Glance”
MetadataDetails
Publication Date2017-01-18
JournalJournal of the American Chemical Society
AuthorsYuvraj Y. Birdja, Marc T. M. Koper
InstitutionsLeiden University
Citations185
AnalysisFull AI Review Included

Technical Documentation & Analysis: MPCVD Diamond for Electrocatalysis

Section titled “Technical Documentation & Analysis: MPCVD Diamond for Electrocatalysis”

Executive Summary

Section titled “Executive Summary”

This analysis focuses on the application of Boron-Doped Diamond (BDD) in the electrocatalytic reduction of carbon dioxide (CO₂R), validating BDD’s role as a robust and active electrode material.

  • Material Validation: Boron-Doped Diamond (BDD) is confirmed to be an active electrocatalyst for the reduction of CO₂ and CO, producing volatile products including formaldehyde (HCHO) and methane (CH₄).
  • Mechanistic Insight: The study critically distinguishes between direct CO₂R products and secondary products (carboxylic acids and alcohols) formed via base-catalyzed Cannizzaro disproportionation reactions.
  • Local pH Effects: The formation of these secondary products is driven by a local alkaline environment near the electrode surface, caused by the competing Hydrogen Evolution Reaction (HER).
  • Material Robustness: BDD demonstrated exceptional stability and a wide potential window, operating effectively under highly cathodic potentials (down to -2.0 V vs RHE) in acidic media.
  • Generalizability: The findings regarding disproportionation reactions are generalizable to other electrode materials and C₂/C₃ aldehydes, emphasizing the need for high-purity, stable BDD substrates for accurate mechanistic studies.
  • 6CCVD Value: 6CCVD provides the high-quality, customizable BDD required to replicate and extend this research, offering tailored doping levels, dimensions, and integrated metalization services.

Technical Specifications

Section titled “Technical Specifications”

The following hard data points were extracted from the research paper detailing the experimental setup and results for CO₂ reduction on BDD.

ParameterValueUnitContext
Electrode MaterialBoron-Doped Diamond (BDD)N/AWorking electrode
Electrode Dimensions Used3 or 10mm diameterDiscs embedded in Teflon
Electrolyte Composition0.001 M HClO₄ + 0.099 M NaClO₄MAcidic media, low buffer capacity
Potential Range Tested-2.0 to 0.0V vs RHEHighly cathodic conditions
Voltammetry Scan Rate1mV s⁻ÂčUsed for product detection
HCOOH Standard Equilibrium Potential (pH < 4)-0.20V vs RHEFor CO₂ + 2(e⁻ + Hâș) → HCOOH
HCHO Standard Equilibrium Potential-0.08V vs RHEFor CO₂ + 4(e⁻ + Hâș) → HCHO + H₂O
CO Standard Equilibrium Potential-0.11V vs RHEFor CO₂ + 2(e⁻ + Hâș) → CO + H₂O
Liquid Product Detection Limit< 0.05mMConcentration threshold for HPLC uncertainty
Cleaning ProcedureUltrasonication in concentrated HNO₃N/AUsed to ensure clean surface

Key Methodologies

Section titled “Key Methodologies”

The electrochemical experiments utilized BDD electrodes in a conventional three-electrode cell setup, focusing on precise control and advanced product detection.

  1. Electrode Fabrication: BDD discs (3 mm or 10 mm diameter) were embedded in Teflon for use as working electrodes.
  2. Surface Cleaning: Electrodes were rigorously cleaned via ultrasonication in concentrated HNO₃, followed by stabilization using cyclic voltammetry (approx. 50 cycles) until a stable voltammogram was achieved.
  3. Cell Configuration: A three-electrode cell was used, separating the working and counter electrode compartments via a Nafion 115 membrane.
  4. Reference System: A Reversible Hydrogen Electrode (RHE) was used as the reference, with all reported current densities being IR corrected.
  5. Volatile Product Analysis: Online Electrochemical Mass Spectrometry (OLEMS) was employed for real-time detection of volatile species (H₂, CO, CH₄, HCHO).
  6. Liquid Product Analysis: Online High-Performance Liquid Chromatography (HPLC) was used to quantify nonvolatile liquid products (e.g., HCOOH, CH₃OH, acetic acid).

6CCVD Solutions & Capabilities

Section titled “6CCVD Solutions & Capabilities”

This research confirms BDD as a superior material for fundamental electrochemistry, particularly in CO₂ reduction studies where stability and a wide potential window are paramount. 6CCVD is uniquely positioned to supply the high-specification diamond materials required to replicate and advance this work.

Applicable Materials

Section titled “Applicable Materials”

To replicate the high performance and stability demonstrated in this study, 6CCVD recommends the following materials:

  • Heavy Boron Doped Polycrystalline Diamond (PCD-BDD): Ideal for large-area electrocatalysis, offering high conductivity and robustness under extreme cathodic potentials. 6CCVD can supply PCD wafers up to 125mm in diameter.
  • Heavy Boron Doped Single Crystal Diamond (SCD-BDD): Recommended for highly controlled fundamental studies requiring the highest material purity and lowest defect density, ensuring reproducible results in mechanistic investigations.

Customization Potential

Section titled “Customization Potential”

The paper utilized specific BDD disc dimensions (3 mm, 10 mm). 6CCVD’s manufacturing capabilities exceed these requirements, offering flexibility for both R&D and scale-up:

Research Requirement6CCVD Customization Capability
Custom DimensionsWe provide custom laser cutting and shaping for BDD plates/wafers up to 125mm (PCD) and custom SCD sizes, allowing precise integration into specialized electrochemical cells.
Thickness ControlBDD layers can be grown from 0.1”m up to 500”m, with robust diamond substrates available up to 10mm thick for high-power applications.
Surface FinishFor studies sensitive to surface effects (like local pH gradients), 6CCVD offers ultra-smooth polishing: Ra < 1nm (SCD) and Ra < 5nm (Inch-size PCD).
Catalyst IntegrationThe paper notes BDD is often used as a substrate for catalysts (RuO₂, Cu NPs). 6CCVD offers in-house metalization services (Au, Pt, Pd, Ti, W, Cu) to create highly stable, integrated electrode assemblies ready for catalyst deposition.

Engineering Support

Section titled “Engineering Support”

The complexity of CO₂ reduction, particularly the identification of secondary Cannizzaro reactions, highlights the need for expert material selection.

  • Material Selection for CO₂R: 6CCVD’s in-house PhD team specializes in diamond material science and can assist researchers in selecting the optimal BDD doping level and crystal orientation (SCD vs. PCD) to maximize Faradaic efficiency and minimize competing reactions like HER.
  • Electrochemical Interface Design: We provide consultation on surface termination and polishing requirements to ensure the BDD electrode surface is optimized for specific CO₂ utilization projects, whether acting as a direct catalyst or a robust substrate.
  • Global Logistics: We ensure reliable, global shipping (DDU default, DDP available) of sensitive diamond materials directly to your lab, minimizing lead times for critical research.

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

View Original Abstract

A seemingly catalytically inactive electrode, boron-doped diamond (BDD), is found to be active for CO<sub>2</sub> and CO reduction to formaldehyde and even methane. At very cathodic potentials, formic acid and methanol are formed as well. However, these products are the result of base-catalyzed Cannizzaro-type disproportionation reactions. A local alkaline environment near the electrode surface, caused by the hydrogen evolution reaction, initiates aldehyde disproportionation promoted by hydroxide ions, which leads to the formation of the corresponding carboxylic acid and alcohol. This phenomenon is strongly influenced by the electrolyte pH and buffer capacity and not limited to BDD or formaldehyde, but can be generalized to different electrode materials and to C<sub>2</sub> and C<sub>3</sub> aldehydes as well. The importance of these reactions is emphasized as the formation of acids and alcohols is often ascribed to direct CO<sub>2</sub> reduction products. The results obtained here may explain the concomitant formation of acids and alcohols often observed during CO<sub>2</sub> reduction.

Tech Support

Section titled “Tech Support”

Original Source

Section titled “Original Source”

References

Section titled “References”
  1. 2008 - Modern Aspects of Electrochemistry [Crossref]

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