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Photo-assisted electrochemical CO2reduction at a boron-doped diamond cathode

MetadataDetails
Publication Date2023-01-01
JournalEnergy Advances
AuthorsGoki Iwai, Andrea Fiorani, Jinglun Du, Yasuaki Einaga
InstitutionsKeio University
Citations9
AnalysisFull AI Review Included

Technical Documentation & Analysis: Photo-Assisted CO2 Reduction using MPCVD Boron-Doped Diamond

Section titled “Technical Documentation & Analysis: Photo-Assisted CO2 Reduction using MPCVD Boron-Doped Diamond”

6CCVD Analysis Reference: Iwai et al., Energy Advances, 2023, 2, 733-738. Application Focus: Photoelectrochemical (PEC) CO2 Reduction (CO2R) to Formic Acid (FA).


This research successfully demonstrates a highly efficient photoelectrochemical system for converting CO2 to formic acid (FA) using a Microwave Plasma-Assisted Chemical Vapor Deposition (MPCVD) Boron-Doped Diamond (BDD) cathode.

  • High Efficiency BDD Cathode: MPCVD BDD was confirmed as a superior cathode material for CO2R, achieving a stable Faradaic Efficiency (FE) for Formic Acid of approximately 86%.
  • Significant Energy Saving: The PEC system, coupling BDD with a TiO2 NT photoanode, reduced the required total cell voltage ($E_{tot}$) from 2.7 V (dark electrolysis) to 1.4 V.
  • Electrical Energy Input Reduction: This voltage reduction resulted in a 52% saving of the electrical energy input compared to previous dark electrochemical systems.
  • Conversion Efficiency Boost: The Electrical-to-Chemical Energy Conversion Efficiency ($\eta_{ECE}$) was dramatically increased from 50% (dark EC) to a stable 80% in the photo-assisted system.
  • Material Advantage: The BDD cathode’s wide potential window and high overpotential for proton reduction were critical for suppressing competing hydrogen evolution reactions, ensuring high selectivity for FA.
  • Overall Performance: The system achieved an overall Photo-Assisted Energy Throughput Conversion Efficiency ($\eta_{PAE}$) of 5.5%.

The following hard data points were extracted from the experimental results, focusing on the BDD cathode and system performance metrics.

ParameterValueUnitContext
Cathode MaterialPolycrystalline BDDN/AMPCVD on Si(100)
Boron Doping Level0.1% (B/C ratio)Optimized for CO2R to FA
Cathode Geometrical Area9.62cm2Used in PTFE flow cell
Optimal Total Voltage ($E_{tot}$)1.4VPEC system, stable operation
Electrical Energy Saving52%Compared to 2.7 V dark EC system
Faradaic Efficiency (FEFA)86 (Stable)%For Formic Acid production
Electrical-to-Chemical Efficiency ($\eta_{ECE}$)80%Achieved in PEC system (vs. 50% dark EC)
Photo-Assisted Efficiency ($\eta_{PAE}$)5.5%Overall energy throughput conversion
Operating Temperature23-25°CRoom temperature
Light Intensity (Optimal)25.2mW cm-2Used for Configuration 2 tests
Standard Potential ($E_{HCOOH/CO_{2}}$)1.3997VStandard potential for CO2 reduction to FA

The following steps outline the fabrication and operational parameters critical to the high-efficiency PEC system, focusing on the BDD cathode preparation.

  1. BDD Film Deposition: Polycrystalline BDD films were deposited on Si(100) wafer substrates using a Microwave Plasma-Assisted Chemical Vapor Deposition (MPCVD) system.
  2. Doping Control: Boron concentration was precisely set to 0.1% (B/C ratio) using methane (carbon source) and trimethylborane (boron source).
  3. Electrode Pretreatment: BDD electrodes underwent rigorous cleaning, including sonication in isopropanol and ultrapure water, followed by extensive electrochemical pretreatment (Cyclic Voltammetry scans: 10 cycles from -3.5 V to 3.5 V, and 20 cycles from 0 V to 3.5 V in 0.1 M H2SO4).
  4. Cell Configuration: Experiments were conducted in a two-chamber Polytetrafluoroethylene (PTFE) flow cell, separated by a Nafion NRE-212 membrane.
  5. Electrolytes: Catholyte (BDD side) was 0.5 M KCl (50 mL); Anolyte (TiO2 NT side) was 0.5 M KOH (90 mL).
  6. Gas Management: Oxygen was removed from the catholyte via N2 purging (30 min), followed by CO2 saturation (60 min at 200 mL min-1). CO2 flow was maintained at 30 mL min-1 during electrolysis.
  7. PEC Operation: The system was operated in a two-electrode configuration, fixing the total voltage ($E_{tot}$) between the BDD cathode and the TiO2 NT photoanode.

The successful replication and scale-up of this high-efficiency PEC-CO2R system rely entirely on the precise control and quality of the Boron-Doped Diamond (BDD) cathode. 6CCVD is uniquely positioned to supply the necessary materials and engineering support to advance this research toward commercial viability.

Research Requirement6CCVD Solution & CapabilityTechnical Advantage for PEC-CO2R
High-Quality BDD CathodeMPCVD Boron-Doped Diamond (BDD)We supply high-purity, highly crystalline BDD films, ensuring the wide potential window and long-term stability critical for suppressing H2 evolution and maintaining high Faradaic Efficiency (FE).
Precise Doping Control (0.1% B/C)Custom Doping Specifications6CCVD offers precise control over boron concentration, allowing researchers to fine-tune the BDD conductivity and electrocatalytic properties to optimize selectivity for specific products (e.g., Formic Acid, CO, or methanol).
Scale-Up Potential (9.62 cm2 used)Large Area PCD/BDD WafersWe manufacture Polycrystalline Diamond (PCD) and BDD plates/wafers up to 125 mm in diameter, facilitating the transition from laboratory-scale experiments to pilot-scale reactors for industrial CO2 utilization.
Electrode Integration & ContactCustom Metalization ServicesFor robust electrical connections and integration into complex PEC architectures, 6CCVD offers in-house deposition of metals including Ti, Pt, Au, Pd, Cu, and W, ensuring low-resistance ohmic contacts.
Thickness RequirementsFlexible Thickness RangeWe provide BDD films with thicknesses ranging from 0.1 ”m to 500 ”m, allowing optimization for specific electrochemical cell designs and mass transport requirements.
Surface FinishUltra-Precision PolishingOur polishing capabilities achieve roughness down to Ra < 5 nm for inch-size PCD/BDD, minimizing surface defects and maximizing the active electrochemical area.

The achievement of 80% $\eta_{ECE}$ highlights the critical role of high-quality BDD in sustainable energy applications. 6CCVD’s in-house PhD team specializes in diamond electrochemistry and can assist researchers and engineers with material selection, doping optimization, and interface engineering for similar Photoelectrochemical CO2 Reduction projects.

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

View Original Abstract

A photo-assisted electrochemical system converting CO 2 into formic acid by photoelectrochemical water oxidation at TiO 2 nanotubes coupled with electrochemical CO 2 reduction at boron-doped diamond.

  1. 2009 - Comprehensive Organic Name Reactions and Reagents