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Electric Polarization-Dependent Absorption and Photocurrent Generation in Limnospira indica Immobilized on Boron-Doped Diamond

MetadataDetails
Publication Date2024-07-17
JournalACS Omega
AuthorsNikolay V. Ryzhkov, Nora Colson, Essraa Ahmed, Paulius Pobedinskas, Ken Haenen
InstitutionsSwiss Federal Laboratories for Materials Science and Technology, Belgian Nuclear Research Centre
Citations2
AnalysisFull AI Review Included

Technical Documentation & Analysis: Electric Polarization-Dependent Absorption and Photocurrent Generation in Limnospira indica Immobilized on Boron-Doped Diamond

Section titled “Technical Documentation & Analysis: Electric Polarization-Dependent Absorption and Photocurrent Generation in Limnospira indica Immobilized on Boron-Doped Diamond”

This research validates the critical role of Boron-Doped Diamond (BDD) as a high-performance, biocompatible current collector for biophotoelectrochemical cells (BPECs) utilizing live cyanobacteria.

  • Core Material Validation: MPCVD-grown BDD thin films (180 nm thick) were successfully used as semiconducting electrodes for immobilizing Limnospira indica (P6) cyanobacteria.
  • High-Density Doping: The BDD synthesis utilized a high B/C ratio (20,000 ppm) via MPCVD at 730 °C, confirming the need for heavily doped diamond to achieve efficient charge transfer.
  • Polarization Effect: External electrical polarization significantly modulated the light absorption characteristics of the cyanobacteria, demonstrating a direct causal relationship between the electric field and photosynthetic properties.
  • Enhanced Absorption: Negative polarization (-0.6 V vs Ag/AgCl) resulted in a substantial increase (up to 12%) in light absorbance, particularly in the green-red spectrum, opening avenues for biophotocathode optimization.
  • Superior Performance: The BDD electrode paired with the conductive polymer PEDOT:PSS showed superior charge flow and conductivity compared to agar hydrogel matrices.
  • Photocurrent Generation: The BDD/PEDOT/PSS biophotoelectrode demonstrated efficient cathodic photocurrent generation, utilizing the entire visible spectrum, with maximum output under UV light (375 nm).
  • Application Focus: The findings are crucial for the rational design and optimization of regenerative life support systems and durable self-sustaining environments for space travel and colonization.

The following hard data points were extracted from the MPCVD synthesis and electrochemical testing described in the paper.

ParameterValueUnitContext
Diamond MaterialBDD Thin FilmN/ABoron-Doped Diamond
Film Thickness180nmDeposited on fused silica substrate
Substrate Dimensions40 x 10mmFused silica
Reactor TypeASTeX 6500 seriesN/AMicrowave Plasma-Enhanced CVD (MPCVD)
Growth Temperature730°CSubstrate temperature
Microwave Power4000WCVD process parameter
Growth Pressure40TorrCVD process parameter
Boron-to-Carbon (B/C) Ratio20,000ppmHigh doping level for conductivity
Methane Concentration1%CH₄/H₂/TMB plasma gas mixture
Anodic Polarization Bias+0.6VApplied potential vs Ag/AgCl
Cathodic Polarization Bias-0.6VApplied potential vs Ag/AgCl
Maximum Absorbance Increase11-12%Observed under -0.6 V bias (PEDOT:PSS + P6)
Peak Photocurrent Wavelength375nmUV light illumination
Exposed Electrode Area1cm2Used for current density calculations

The BDD electrodes were fabricated using standard MPCVD techniques, followed by specialized surface preparation and biological immobilization.

  1. Substrate Preparation: Fused silica substrates (40 mm x 10 mm) were cleaned using an O₂ gas discharge plasma.
  2. Seeding: Substrates were drop-cast with an ultradispersed detonation nanodiamond colloidal suspension (7 nm size) followed by deionized water rinsing and spin-coating.
  3. MPCVD Growth: BDD films were grown in an ASTeX 6500 series reactor using a CH₄/H₂/trimethylboron (TMB) plasma. Key parameters included 4000 W power, 40 Torr pressure, and a substrate temperature of 730 °C.
  4. Doping Control: A high B/C ratio of 20,000 ppm was maintained using TMB diluted in H₂ to achieve the necessary electronic conductivity for the current collector.
  5. Biophotoelectrode Assembly: Live L. indica trichomes were harvested and embedded in either 0.75% agar hydrogel or 0.5-1% conductive PEDOT/PSS polymer matrices.
  6. Electrochemical Testing: A three-electrode setup (BDD working electrode, Pt counter electrode, Ag/AgCl reference electrode) was used for chronoamperometry and spectroelectrochemical measurements under switched electric fields (+0.6 V and -0.6 V).
  7. Illumination: Monochromatic light was provided by mounted LEDs across the UV-visible spectrum (375 nm to 625 nm).

6CCVD is uniquely positioned to supply the advanced MPCVD diamond materials required to replicate, scale, and optimize the BPEC systems described in this research. Our capabilities directly address the material specifications and customization needs of bioelectrochemistry engineers.

To replicate the high-performance current collector used in this study, 6CCVD recommends:

  • Heavy Boron-Doped PCD/BDD: The research explicitly requires high conductivity achieved through a B/C ratio of 20,000 ppm. 6CCVD offers Heavy Boron-Doped Polycrystalline Diamond (PCD/BDD) films with precisely controlled doping levels, ensuring the wide electrochemical window and low background current critical for BPEC stability and efficiency.
  • Thin Film SCD/PCD: The 180 nm thickness is well within our standard range. We offer SCD (Single Crystal Diamond) and PCD (Polycrystalline Diamond) films from 0.1 ”m to 500 ”m thick, allowing researchers to explore the impact of film thickness on charge carrier diffusion and overall BPEC performance.

The success of this research relies on precise material dimensions and integration with other components (e.g., PEDOT:PSS). 6CCVD offers comprehensive customization services:

Customization Requirement6CCVD CapabilityEngineering Advantage
Custom DimensionsPlates/wafers available up to 125 mm (PCD/BDD).Allows for direct scale-up from the 40 mm x 10 mm lab samples to inch-size prototypes for commercial viability or large-scale space applications.
Substrate IntegrationBDD films can be deposited on various substrates (e.g., Fused Silica, Silicon, Sapphire).Ensures compatibility with existing experimental setups and allows for optimization of optical transparency and thermal management.
Integrated MetalizationIn-house deposition of Au, Pt, Pd, Ti, W, and Cu contacts.We can pre-metalize the BDD electrodes (e.g., with Pt contacts for counter electrodes or Ti/Au for stable ohmic contacts) to simplify assembly and enhance interface stability.
Surface FinishUltra-smooth polishing: Ra < 1 nm (SCD) and Ra < 5 nm (Inch-size PCD).While the paper focused on thin films, highly polished surfaces are essential for uniform cell immobilization and minimizing surface defects that could interfere with bioelectronic charge transfer.

The observed polarization-dependent absorption and cathodic efficiency underscore the complexity of the bioelectronic interface. 6CCVD’s in-house PhD team provides expert consultation:

  • Material Selection for Biophotovoltaics: We assist researchers in selecting the optimal BDD doping concentration and film morphology (SCD vs. PCD) to maximize charge extraction efficiency in similar Biophotoelectrochemical Cell (BPEC) projects.
  • Interface Optimization: Our team offers technical guidance on surface termination (e.g., hydrogen or oxygen termination) and metalization strategies to ensure stable, long-term operation and robust connectivity between the diamond electrode and biological matrices like PEDOT:PSS.
  • Global Logistics: We ensure reliable, global shipping (DDU default, DDP available) of sensitive diamond materials, supporting international research collaborations.

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

View Original Abstract

We present the change of light absorption of cyanobacteria in response to externally applied electrical polarization. Specifically, we studied the relation between electrical polarization and changes in light absorbance for a biophotoelectrode assembly comprising boron-doped diamond as semiconducting electrode and live <i>Limnospira indica</i>PCC 8005 trichomes embedded in either polysaccharide (agar) or conductive conjugated polymer (PEDOT-PSS) matrices. Our study involves the monitoring of cyanobacterial absorbance and the measurement of photocurrents at varying wavelengths of illumination for switched electric fields, i.e., using the bioelectrode either as an anode or as cathode. We observed changes in the absorbance characteristics, indicating a direct causal relationship between electrical polarization and absorbing properties of <i>L. indica</i>. Our finding opens up a potential avenue for optimization of the performance of biophotovoltaic devices through controlled polarization. Furthermore, our results provide fundamental insights into the wavelength-dependent behavior of a bio photovoltaic system using live cyanobacteria.