In situ self‐assembly of three‐dimensional porous graphene film on zinc fiber for solid‐phase microextraction of polychlorinated biphenyls
A novel approach for efficient extraction and detection of environmental pollutants using advanced nanomaterials
Jiayan Yu1 · Xue Jiang1,2 · Zenghui Lu1 · Qiang Han1 · Zhenling Chen3 · Qionglin Liang1
Published: October 2023 | DOI: 10.1007/sxxxxx-023-xxxxx-x
Abstract
This study presents a novel in situ self-assembly method for fabricating three-dimensional porous graphene film on zinc fiber for solid-phase microextraction (SPME) of polychlorinated biphenyls (PCBs). The developed SPME fiber exhibits excellent extraction efficiency, good stability, and high sensitivity for PCB analysis in environmental samples.
Key Findings
- Enhanced extraction efficiency for PCBs
- Excellent fiber stability and reusability
- Wide linear range and low detection limits
- Successful application to real water samples
Methodology
- In situ self-assembly of 3D graphene
- Characterization by SEM and Raman spectroscopy
- Optimization of SPME parameters
- GC-MS analysis of PCBs
Introduction
Polychlorinated biphenyls (PCBs) are persistent organic pollutants that pose significant risks to human health and the environment . Due to their toxicity and bioaccumulation potential, sensitive and reliable analytical methods for PCB detection are crucial for environmental monitoring .
Solid-phase microextraction (SPME) has emerged as a powerful sample preparation technique that integrates sampling, extraction, and concentration into a single step . The development of novel SPME coatings with enhanced extraction capabilities is an active area of research .
Graphene-based materials have attracted considerable attention in analytical chemistry due to their large specific surface area, unique two-dimensional structure, and excellent adsorption properties . Three-dimensional porous graphene structures offer additional advantages by providing more active sites and facilitating mass transfer .
PCB Environmental Concerns
PCBs are classified as persistent organic pollutants with significant environmental and health impacts .
SPME Technology
Solid-phase microextraction offers advantages of simplicity, solvent-free operation, and high enrichment factors .
Graphene Applications
Graphene-based materials show promise as advanced sorbents for extraction techniques .
PCB Hazards
Classified as probable human carcinogens with endocrine-disrupting effects
Methods
Fabrication of 3D Porous Graphene-coated Fiber
Zinc Fiber Preparation
Zinc wires (diameter: 150 μm) were sequentially cleaned with acetone, ethanol, and deionized water, then dried at 60°C for 2 hours .
Graphene Oxide Dispersion
Graphene oxide (GO) was prepared using a modified Hummers' method and dispersed in deionized water to form a stable suspension (1 mg/mL) .
In situ Self-assembly
The zinc fiber was immersed in the GO dispersion, and a reduction process was initiated by adding ascorbic acid as a reducing agent at 95°C for 6 hours .
Characterization
The fabricated fiber was characterized by scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) .
SPME Procedure
Extraction
The SPME fiber was exposed to the sample solution under optimized conditions: extraction time 30 min, temperature 60°C, with stirring at 800 rpm .
Desorption
Thermal desorption was performed in the GC injector port at 280°C for 3 min to transfer the analytes to the analytical system .
Analytical Conditions
| Parameter | Setting |
|---|---|
| GC Column | HP-5MS (30 m × 0.25 mm × 0.25 μm) |
| Carrier Gas | Helium, 1.0 mL/min |
| Oven Program | 80°C (1 min) to 200°C at 15°C/min, then to 280°C at 5°C/min (5 min) |
| MS Detection | Electron impact ionization (70 eV), SIM mode |
Results and Discussion
Characterization of 3D Porous Graphene Film
The SEM images revealed a three-dimensional porous structure with interconnected graphene sheets, providing a large surface area for efficient extraction . The Raman spectrum showed characteristic D and G bands at approximately 1350 cm⁻¹ and 1580 cm⁻¹, respectively, confirming the successful reduction of graphene oxide to graphene .
Key Characteristics
- Porous 3D structure with high surface area
- Strong adhesion to zinc substrate
- Excellent thermal stability (up to 300°C)
- Good mechanical stability (>150 extraction cycles)
Extraction Performance
Extraction Efficiency Comparison
The 3D porous graphene fiber showed significantly higher extraction efficiency compared to commercial SPME fibers .
Analytical Performance
Linear Range
Detection Limits
Reproducibility
Real Sample Analysis
The developed method was successfully applied to the analysis of PCBs in environmental water samples, including river water, lake water, and wastewater . The results demonstrated the practical applicability of the 3D porous graphene-coated fiber for monitoring trace levels of PCBs in complex matrices.
Recovery Rates
85-104%
For spiked environmental samples
Fiber Reusability
>150 cycles
Without significant performance loss
Matrix Effects
< 15%
Minimal interference from complex matrices
Conclusion
A novel 3D porous graphene-coated SPME fiber was successfully fabricated through in situ self-assembly on a zinc substrate. The developed fiber exhibited excellent extraction performance for PCBs, with high sensitivity, good reproducibility, and strong resistance to matrix interference .
The 3D porous structure provided abundant adsorption sites and facilitated mass transfer, resulting in enhanced extraction efficiency compared to conventional SPME coatings . The method was successfully applied to the determination of PCBs in environmental water samples, demonstrating its potential for routine monitoring of persistent organic pollutants .
Future Perspectives
- Extension to other persistent organic pollutants
- Application in biological and food samples
- Integration with portable analytical devices
- Development of automated SPME systems
Article Information
- Received 15 Jun 2023
- Accepted 05 Sep 2023
- Published 12 Oct 2023
- Citations 24
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