Citation: | WANG Baoli,ZHANG Yijun,ZHANG Yuhang,et al. Research Progress of Biochar Based Materials and Their Applications Using Electrochemical Sensors[J]. Rock and Mineral Analysis,2024,43(6):967−981. DOI: 10.15898/j.ykcs.202403170058 |
Electrochemical sensors have become a research hotspot in the field of analytical chemistry due to their high sensitivity, good selectivity, and fast reaction rate. Using biochar materials to construct electrochemical sensors is a low cost, accessible and effective route to achieve excellent detection performance. This review summarizes the research progress of biochar based electrochemical sensors in the detection of environmental pollutants, drugs and biomolecules on the basis of briefly describing the synthesis methods and the structural properties of biochar-based materials. The synthesized biochar and the corresponding constructed sensors indicate that electrochemical sensors hold significant advantages in high-precision and high-stability chemical-signal testing. Further research will focus on optimizing the structure of carbon materials, regulating the composition of them, and preparing high-performance biochar-based materials that are more suitable for electrochemical sensors, so as to reduce the detection limit and improve the sensitivity. Besides, it is urgent to fabricate portable sensors based on biochar to determine rapid and intelligent analysis and detection, and the sensing mechanism and testing performance improvement mechanism are problems that must be deeply explored. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202403170058.
An electrochemical sensor is a device used for qualitative or quantitative detection and analysis by measuring the electrochemical signal of the target substance[1]. Compared to traditional instrument analysis methods, such as high-performance liquid chromatography, inductively coupled plasma-mass spectrometry, and ultraviolet spectroscopy, electrochemical sensing technology has become a research hotspot due to its convenience, high sensitivity, good selectivity, and fast reaction rate[2-6]. During the analysis and detection process, the working electrode determines the specific capture and recognition of the substance to be measured, which is the crucial factor that affects the performance of the electrochemical sensor[7-9]. Effectively modifying electrode sensitive materials on the electrode surface to achieve electrochemical signal amplification is the key to enhancing the detection performance of electrochemical sensors.
Biochar based materials have attracted extensive research interest from scholars due to their unique structure, wide availability, high sustainability, economic compatibility, and renewable characteristics[10]. Their applications mainly include catalysis[11], carbon dioxide capture[12], adsorption and separation[13], hydrogen storage[14], solar cells[15], water treatment[16], energy storage[17], and electrochemical sensors[18]. In recent years, scholars have been committed to improve the performance of electrochemical sensors based on biochar materials. The main methods include activation, heteroatoms doping, and loading of metal/metal alloy/metal oxide nanoparticles[19-20].
The applications and research status of biochar-based electrochemical sensors were summarized in this review. The main synthesis strategies of biochar and the applications of biochar-based electrochemical sensors in the analysis of environmental pollutants, drugs and biomolecules were summarized. Besides, the detection parameters were evaluated and compared, and the related technical difficulties were discussed in detail. On this basis, the existing difficulties in this field were analyzed, and the future development direction was proposed.
1. The synthesis methods of biochar materials
(1) Pyrolysis carbonization method. When the pyrolysis carbonization method is used to prepare carbon materials, the biomass can be treated simply, and no other reagents are introduced to direct carbonization. For example, Yin et al.[21] collected crab gills for simple pre-treatment, such as crushing and drying and then carbonized to a prepared biochar. By introducing other catalysts and activators into the biomass, the graphitization degree and pore structure of the prepared carbon materials can be effectively improved[22-23]. The steps involved in pyrolysis carbonization are very complicated, the mechanism is still not completely clear because of the complexity of reaction conditions. According to the analysis of the current research results, the biochar prepared by pyrolysis at a lower temperature (400−500℃) has rich functional groups on its surface, which is more suitable for the field of pollutant adsorption[24-25].
(2) Hydrothermal carbonization method. In 1913, Bergius et al.[26] used the hydrothermal carbonization method to transform cellulose into carbon-like materials for the first time. The biochar prepared by the hydrothermal method is mostly carbon quantum dots[27-29]. As the hydrothermal method was employed to prepare biochar, the solvent used can be pure water or other solvents, and other activation reagents or catalysts can be introduced into the reaction system[30-31]. The advantages of the hydrothermal method are that the reagents used are less toxic, the shape of the carbon material can be adjusted by changing the reaction temperature, and the instruments used are facile. One of the main disadvantages is that the hydrothermal reaction is carried out in a closed high-pressure hydrothermal kettle, which can easily cause accidents if it is improperly operated.
(3) Molten salt carbonization method. The process of molten salt carbonization is similar to that of pyrolysis carbonization, in which the carbonization and activation of biomass are carried out simultaneously in a molten salt medium, thus greatly reducing energy consumption. The main difference between the two methods is that molten salt can act as a catalyst to accelerate the conversion of biomass to biochar. Single NaCl, KCl, LiCl and ZnCl2, or a combination of them are commonly used as the molten salt medium[32-35]. At present, the main problem of the molten salt carbonization method is how to deal with the salt used in the synthesis process. After the reaction, the obtained material is usually a mixture of carbon materials and molten salt. When the product is treated, the molten salt is generally removed by filtering and washing, and the filtrate is a large amount of molten salt waste liquid, which is difficult to recycle. In addition, the corrosion problem of the reaction vessel is also difficult to solve[36-38].
2. Applications of biochar materials in electrochemical sensors
(1) Application in the analysis of environmental pollutants. Biochar materials have been widely used in electrochemical detection of environmental pollutants, and are often used to detect organic compounds and heavy metals. For example, N2H4 and phenolic compounds can be detected by biochar based electrochemical sensors with a low detection limit and good sensitivity. Bedsides, electrochemical sensors based on biochar are widely used in the detection of phenolic compounds[43-46]. By optimizing the structure and composition of biochar, different phenolic compounds in water can be detected simultaneously. The detection mechanism is relatively clear. As for heavy metals, electrochemical sensor technology is widely used in the analysis of Hg2+, Pb2+, Cd2+ and Cu2+, and its detection mechanism is mainly that the redox reaction between the electrode sensitive material and the measured substance causes the current signal of the electrode to change, so as to achieve the purpose of quantification[30,48-52]. Recently, electrochemical sensors have made a breakthrough in the detection of environmental microplastics[53-54]. Although the qualitative and quantitative detection of ~100nm polystyrene microplastics is realized through material regulation, the detected polystyrene microplastics is only a theoretical model of microplastics, and the actual microplastics in water are much more complex in terms of composition and particle size, which is also a common problem encountered in the detection of microplastics. Further research is needed in the use of electrochemical sensors to detect microplastics in actual water samples.
(2) Application in drug analysis. In drug analysis, biochar based electrochemical sensors have made some progress in chemical drugs[22,56-60] and traditional Chinese medicine[61-62]; the more common detection targets in chemical drugs are acetaminophen and antibiotic substances. This is mainly because the surface functional groups of the synthesized carbon materials, including —OH and —COOH, interact relatively easily both physically and chemically with such substances, resulting in significant changes in electrochemical signals, and the detection mechanism is relatively clear. In the analysis of traditional Chinese medicine, more flavonoids were reported, while relatively few other traditional Chinese medicine substances were analyzed, which may be related to factors such as the complex composition of the measured substances in traditional Chinese medicine. The current research focus is also inclined to reduce the detection limit of such sensors and expand the detection range. In addition, the detection mechanism of flavonoids has always been thought to indicate that the hydroxyl group is oxidized to the carbonyl group by the electrode material, which produces an obvious redox peak signal.
(3) Application in biomolecule analysis. Biochar based sensors in the detection of biomolecules mainly concentrated in the analysis of several substances such as glucose, dopamine, uric acid and ascorbic acid, whereas other biomolecules detection is relatively rare[63-66]. Most of the sensors constructed are not based on pure biochar materials, but non-metallic N and P doped biochar, or loaded with metal compounds such as CuO and CoS. It may be determined by the special structure of biomolecules, which is difficult to interact with a pure biochar skeleton. The reaction must be facilitated by the introduction of other non-metals or metals. In addition, biomolecule detection can be achieved indirectly by introducing other substances on the electrode.
3. Future perspectives
The detection performance of electrochemical sensors based on biochar is mainly affected by factors such as the composition, structure, surface functional groups, and morphology of the biochar materials. In addition, the detection limit, detection range, and sensitivity of the sensor are related to detecting conditions, such as electrolyte type, volume of carbon material modified on the electrode surface, electrolyte pH, and ion strength. At present, sensors constructed for the analysis of environmental pollutants, drugs, and biomolecules mainly adopt traditional large-scale electrochemical workstations as detection systems, and the development of portable sensors is relatively lacking. In addition, the performance enhancement mechanism and detection mechanism of the constructed sensors need to be further explored in depth. For the development of biochar-based electrochemical sensors, the following three aspects need to be focused on:
(1) The improvement of the detection performance of electrochemical sensors depends on the rational design of modified electrodes, mainly related to the intrinsic electrochemical activity of electrode sensitive materials, surface modification techniques, and sensor detection parameters. In the future, in the synthesis of carbon materials, clear composition and adjustable morphology and structure of biochar should be achieved, which is conducive to improving detection performance and exploring sensing mechanisms.
(2) Electrochemical sensor devices have a promising development trend in detecting various environmental samples, and biochar based electrochemical sensors are gradually moving towards portable sensors. The combination of new 3D printing technology and miniaturized electrochemical workstations can develop low-cost, high-sensitivity portable electrochemical sensor devices. In the future, this technology can be further expanded to build biochar based intelligent portable sensors, achieving on-site, rapid, and intelligent analysis and detection.
(3) The exploration of sensing and performance enhancement mechanisms is also a problem that must be deeply studied in the development of biochar based electrochemical sensors. In the future, it will be necessary to combine experimental results with theoretical calculation to clarify results, further optimizing the performance of sensors and promoting the development of biochar based electrochemical sensors.
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