Chemically Deposited Boron‐Doped Diamond Screen‐Printed Electrodes for the Detection of Manganese
At a Glance
Section titled “At a Glance”| Metadata | Details |
|---|---|
| Publication Date | 2025-05-01 |
| Journal | Electroanalysis |
| Authors | Larissa M.A. Melo, Elena Bernalte, Robert D. Crapnell, Marián Vojs, Marián Marton |
| Institutions | Manchester Metropolitan University, Universidade Federal de Uberlândia |
| Citations | 2 |
| Analysis | Full AI Review Included |
Technical Documentation & Analysis: MPCVD BDD for High-Performance Electroanalysis
Section titled “Technical Documentation & Analysis: MPCVD BDD for High-Performance Electroanalysis”Executive Summary
Section titled “Executive Summary”This documentation analyzes the fabrication and performance of Boron-Doped Diamond (BDD) screen-printed electrodes (SPEs) for highly selective and sensitive detection of Manganese (Mn2+) in environmental water, highlighting 6CCVD’s capabilities to support and scale this research.
- High-Performance Material: MPCVD-grown BDD films were successfully integrated into screen-printed electrodes (SPEs), significantly enhancing electroactive area and conductivity compared to pure carbon black (CB) electrodes.
- Ultra-Low Detection Limits: The optimized BDD SPE configuration (L1:CB + L2:D + BDD, chlorinated) achieved ultra-low Limits of Detection (LOD) down to 0.06 µM for Mn2+, suitable for monitoring regulatory limits (1.0 µM).
- Enhanced Conductivity: Incorporation of BDD reduced the charge transfer resistance (RCT) from 136.9 kΩ (CB pure) to 29.6 kΩ in D- and BDD-containing electrodes, confirming superior electrochemical kinetics.
- Robust Stability and Selectivity: The method demonstrated excellent stability (Relative Standard Deviation, RSD, < 7% for peak current) and high selectivity, successfully rejecting interference from common heavy metals (Cu, Pb, Cr, Cd, Zn, Hg).
- On-Site Applicability: The system is optimized for Differential Pulse Cathodic Stripping Voltammetry (DPCSV) and requires minimal sample volume (35 µL), making it ideal for rapid, portable, and on-site environmental screening.
- 6CCVD Readiness: 6CCVD provides the necessary high-quality, highly doped BDD films and custom fabrication services (thickness control, metalization, and custom dimensions) required to replicate and scale these advanced sensors.
Technical Specifications
Section titled “Technical Specifications”The following hard data points were extracted from the electrochemical characterization and analytical performance results:
| Parameter | Value | Unit | Context |
|---|---|---|---|
| BDD Film Thickness | 3 | µm | Grown via MPCVD on screen-printed nucleation layers |
| Boron Concentration (Calculated) | 1.35 x 1021 | cm-3 | Raman sensitive boron concentration in BDD films |
| Lowest Limit of Detection (LOD) | 0.06 | µM | Achieved using CB + D + BDD (Plain) configuration |
| Optimal Linear Range | 1-100 | µM | L1:CB + L2:D + BDD (Chlorinated) |
| Charge Transfer Resistance (RCT) | 29.6 (±40.6) | kΩ | D- and BDD-containing electrodes (Plain) |
| Solution Resistance (RS) | 671 (±41) | Ω | D- and BDD-containing electrodes (Plain) |
| Peak Current Stability (RSD) | < 7 | % | L1:CB + L2:D + BDD (Chlorinated) |
| Peak Potential Stability (RSD) | < 1.0 | % | L1:CB + L2:D + BDD (Chlorinated) |
| Optimal Deposition Potential | +0.80 | V | DPCSV technique for Mn2+ detection |
| Optimal Deposition Time | 45 | s | DPCSV technique for Mn2+ detection |
| Working Electrode Area | 3.14 | mm2 | Inner diameter of 2 mm |
Key Methodologies
Section titled “Key Methodologies”The fabrication of the high-performance BDD SPEs involved a multi-step process combining screen-printing and MPCVD diamond growth:
- Stencil Preparation: A stencil defining the electrode design was prepared photochemically using a positive film template and light-sensitive emulsion.
- Nucleation Layer Printing: Carbon-based inks (Carbon Black, CB) and diamond nanoparticle dispersions (0.4 wt%, <10 nm particle size) were screen-printed onto the substrate using polyester meshes.
- Layer Configurations: Tested configurations included D + BDD, L1:CB + L2:D + BDD, CB + D + BDD, and CB pure.
- Drying and Curing: CB layers were dried at 120°C for 30 min. Diamond nanoparticle layers were dried at room temperature.
- BDD Film Growth (MPCVD): A 3 µm thick BDD film was grown via Chemical Vapor Deposition (CVD) on the nucleated substrates.
- Gas Recipe: 1% trimethyl borate (B source) and 0.2% CO2 in H2 gas mixture.
- Resulting Material: Highly doped, microcrystalline BDD films.
- Contact and Reference Electrode Printing: Silver printing paste (AST6025) was used for RE and contact electrodes, followed by drying at 150°C for 30 min.
- Chlorination Process: Chronoamperometry was used to transform the printed silver pseudo-RE into Ag/AgCl (chlorinated reference) by applying +700 mV for 30 s in 0.1 mol L-1 KCl solution.
6CCVD Solutions & Capabilities
Section titled “6CCVD Solutions & Capabilities”6CCVD is uniquely positioned to supply the high-quality MPCVD diamond materials and custom fabrication services necessary to replicate, optimize, and scale the BDD SPE technology described in this research.
Applicable Materials
Section titled “Applicable Materials”To replicate the high electrochemical performance demonstrated in this study, researchers require highly conductive, microcrystalline BDD films.
| Research Requirement | 6CCVD Applicable Material | Key Specification |
|---|---|---|
| Highly Conductive BDD (1.35 x 1021 cm-3) | Heavy Boron-Doped PCD (Polycrystalline Diamond) | Optimized for electrochemical sensing, ensuring ultra-low RCT and high electron transfer rates. |
| Diamond Nanoparticles (<10 nm) | Diamond Nanoparticle Precursors | Available for use in custom screen-printing inks or for pre-nucleation of substrates prior to CVD growth. |
| Microcrystalline Structure | Custom MPCVD Growth Recipes | 6CCVD can tune gas mixtures (e.g., CH4/H2/B source/O2) to control crystal morphology, ensuring the microcrystalline structure required for optimal electrical parameters. |
Customization Potential
Section titled “Customization Potential”The fabrication of these SPEs requires precise control over film thickness, doping, and integration with complex electrode geometries. 6CCVD’s advanced capabilities directly address these needs:
- Precision Thickness Control: The paper utilized a 3 µm BDD film. 6CCVD offers precise thickness control for SCD and PCD films from 0.1 µm up to 500 µm, allowing engineers to fine-tune the BDD layer for optimal sensitivity and stability.
- Custom Dimensions and Patterning: While the working electrode (WE) diameter was 2 mm, 6CCVD can supply PCD plates/wafers up to 125 mm in diameter. We offer advanced laser cutting and patterning services to create complex electrode geometries and arrays required for high-throughput SPE manufacturing.
- Metalization Integration: The study relied on a chlorinated silver (Ag/AgCl) pseudo-reference electrode. 6CCVD offers internal metalization capabilities (including Au, Pt, Pd, Ti, W, Cu) for contact pads and specialized reference electrode formation, ensuring robust electrical contacts and stable pseudo-reference performance.
- Custom Substrate Compatibility: 6CCVD can grow high-quality BDD films on various customer-supplied substrates or pre-nucleated wafers, facilitating seamless integration with existing screen-printing fabrication lines.
Engineering Support
Section titled “Engineering Support”The successful development of this Mn2+ sensor hinges on optimizing the BDD material properties (doping level, morphology) and the electrochemical recipe (DPCSV parameters).
- Material Selection for Electroanalysis: 6CCVD’s in-house PhD team specializes in diamond electrochemistry and can assist researchers in selecting the optimal BDD material specifications (doping concentration, surface termination, and thickness) for similar heavy metal detection or stripping voltammetry projects.
- Global Logistics: We ensure reliable, global shipping (DDU default, DDP available) of sensitive diamond materials, supporting international research and manufacturing efforts.
Call to Action: For custom specifications or material consultation regarding high-performance BDD films for electrochemical sensing, visit 6ccvd.com or contact our engineering team directly.
View Original Abstract
Manganese (Mn 2+ ) is widely used in industrial applications, including steel production, battery manufacturing, and fertilizers. These activities, along with natural processes, contribute to its presence in environmental water. This study investigates the electrochemical behavior of manganese using laboratory‐fabricated screen‐printed carbon electrodes (SPEs) combining diamond (D), carbon black (CB), and boron‐doped diamond (BDD) in eight different configurations: D + BDD, first layer (L1): CB + second layer (L2): D + BDD, CB + D + BDD, or CB pure, each of them with a chlorinated or plain pseudo ‐reference. The screen‐printed electrodes were characterized physicochemically and electrochemically, with their electroactive areas and electron transfer resistances calculated to select the best configuration for the electroanalytical application. A voltammetric screening method for Mn 2+ using differential pulse cathodic stripping voltammetry was developed with no preconcentration required with the SPEs L1: CB + L2: D + BDD (chlorinated) and CB + D + BDD (plain). The method exhibited broad linear ranges (1-100 and 10-100 µM) and low limits of detections (0.18 and 0.06 µM), for each SPE configuration, respectively, making it suitable for detecting Mn 2+ in contaminated environmental water samples. The electrochemical responses showed good stability across all SPEs produced, with a relative standard deviation of less than 10% ( N = 3), whether using the same or different electrodes. Interference studies with other metals confirmed the high selectivity of the proposed sensor. Additionally, Mn 2 + was successfully detected in spiked river and lake water samples, achieving recoveries close to 100%. The analytical performance demonstrates strong potential as a simple, rapid, and selective screening method for manganese detection in environmental samples.