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 | Slovak University of Technology in Bratislava, Manchester Metropolitan University |
| Citations | 2 |
| Analysis | Full AI Review Included |
Executive Summary
Section titled “Executive Summary”The research details the fabrication and electrochemical validation of chemically deposited Boron-Doped Diamond (BDD) Screen-Printed Electrodes (SPEs) for the selective detection of Manganese (Mn2+) in environmental water.
- Core Value Proposition: Development of a simple, rapid, and highly selective screening method for Mn2+ detection in contaminated aquatic matrices, suitable for portable, on-site analysis.
- Optimal Configuration: The L1:CB + L2:D + BDD (chlorinated pseudo-RE) SPE demonstrated the best overall analytical performance, combining wide linear range and low detection limits.
- Enhanced Performance: The incorporation of Diamond (D) and BDD into the working electrode significantly improved electrical conductivity and electroactive surface area compared to pure Carbon Black (CB) SPEs.
- Analytical Sensitivity: The method, utilizing Differential Pulse Cathodic Stripping Voltammetry (DPCSV), achieved low Limits of Detection (LODs) of 0.18 µM (L1:CB + L2:D + BDD) and 0.06 µM (CB + D + BDD), with a wide linear range up to 100 µM.
- Simplified Procedure: The DPCSV method requires no preconcentration step and uses a minimal sample volume (35 µL), simplifying field procedures and maximizing throughput.
- Selectivity and Reliability: The sensor exhibited high selectivity, successfully resolving Mn2+ peaks from common interferents (Cu, Hg, Pb, Cr, Cd, Zn). Recovery rates in spiked river and lake water samples were close to 100%.
Technical Specifications
Section titled “Technical Specifications”| Parameter | Value | Unit | Context |
|---|---|---|---|
| Working Electrode (WE) Area | 3.14 | mm2 | Inner diameter 2 mm |
| BDD Film Thickness | 3 | µm | Deposited via Chemical Vapor Deposition (CVD) |
| BDD Boron Concentration | 1.35 x 1021 | cm-3 | Calculated from Raman B1 maximum |
| Optimal Supporting Electrolyte | 0.2 M Acetate Buffer | pH 4.0 | For Mn2+ detection |
| Optimal DPCSV Deposition Potential | +0.80 | V | Vs. pseudo-RE |
| Optimal DPCSV Deposition Time | 45 | s | No preconcentration required |
| LOD (L1:CB + L2:D + BDD Chlorinated) | 0.18 | µM | DPCSV method |
| LOD (CB + D + BDD Plain) | 0.06 | µM | DPCSV method (Lowest LOD) |
| Linear Range (L1:CB + L2:D + BDD) | 1-100 | µM | Widest range achieved |
| Charge Transfer Resistance (RCT) | 29.6 (±40.6) | kΩ | L1:CB + L2:D + BDD (Plain) configuration |
| Solution Resistance (RS) | 327 (±7) | Ω | D + BDD (Plain) configuration (Lowest RS) |
| Heterogeneous Electron Transfer Rate (kº) | 4.22 x 10-3 | cm s-1 | D + BDD and CB + D + BDD (Plain) |
| Electrochemical Stability (RSD) | < 7 | % | Peak current (Ip) stability across measurements |
| BDD Raman ZCPD Mode | 1300 | cm-1 | Shifted from 1332.9 cm-1 due to Fano effect |
Key Methodologies
Section titled “Key Methodologies”The SPEs were fabricated using a novel selective nucleation method combined with screen-printing techniques and Chemical Vapor Deposition (CVD).
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Screen Printing of Nucleation Layers:
- Four WE configurations were produced: D + BDD, L1:CB L2:D + BDD, CB + D + BDD, and CB pure.
- Carbon Black (CB) layers were printed using 20 wt% CB dispersion in ethylcellulose/diethylene glycol butyl ether binder.
- Diamond (D) nucleation layers used 0.4 wt% diamond nanoparticles (<10 nm) in ethyl cellulose/butyl alcohol binder.
- Layers were dried sequentially (room temperature or 120°C for 30 min).
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BDD Film Growth (CVD):
- A 3 µm thick BDD film was grown on the screen-printed nucleation layers.
- The CVD gas mixture was optimized for microcrystalline structure and electrical parameters: 1% trimethyl borate and 0.2% CO2 in H2.
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Reference Electrode (RE) Fabrication:
- Silver paste (AST6025) was printed for the RE and contact electrodes, followed by drying at 150°C for 30 min.
- Chlorinated pseudo-REs (Ag/AgCl) were formed by chronoamperometry: +700 mV applied for 30 s in stirred 0.1 mol L-1 KCl solution.
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Electrochemical Characterization:
- Cyclic Voltammetry (CV) was used for initial cleaning (10 cycles in 0.1 M H2SO4, -1.0 V to +1.0 V).
- Electrochemical Impedance Spectroscopy (EIS) and CV using [Ru(NH3)6]3+ and [Fe(CN)6]4-/3- probes determined RCT, RS, kº, and electroactive area (Ae).
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Manganese Detection (DPCSV):
- Manganese (Mn2+) was detected using Differential Pulse Cathodic Stripping Voltammetry (DPCSV).
- The optimal supporting electrolyte was 0.2 M Acetate Buffer at pH 4.0.
- The detection mechanism involves oxidative preconcentration (Mn2+ to MnO2) at +0.80 V, followed by cathodic stripping (MnO2 back to Mn2+).
Commercial Applications
Section titled “Commercial Applications”The developed BDD SPE technology is highly relevant for applications requiring robust, portable, and selective electrochemical sensing platforms.
- Environmental Water Quality Monitoring:
- On-site, rapid screening for Mn2+ contamination in drinking water sources, rivers, and lakes, ensuring compliance with EU regulatory limits (1.0 µM).
- The high selectivity minimizes false positives in complex environmental matrices.
- Industrial Process Control:
- Monitoring manganese levels in industrial wastewater streams (e.g., steel production, battery manufacturing, fertilizer production) before discharge.
- Portable Analytical Devices:
- Integration into handheld potentiostats for field deployment, leveraging the small sample volume requirement (35 µL) and disposable nature of SPEs.
- Advanced Diamond Electrochemistry:
- The use of chemically deposited BDD films provides a stable, low-background electrode material suitable for harsh chemical environments and wide potential windows, a core offering of diamond material suppliers.
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.