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Source: Reprinted with permission from Ref. [85]. © 2015, Royal Society of Chemistry After the whole surface was covered by phenol, the triboelectrification process might only happen between PTFE and phenol instead of the original PTFE and TiO2. Whereas, compared with TiO2, phenol has lower tendency to give electron to PTFE, and therefore jeopardized the TENG output. To render a direct view of the detecting efficiency, the current ratio ((I0 − I )/I0 ) was plotted as a function of phenol concentrations, where I0 was the original current output and I was the current output after phenol treatment. As shown in Fig. 9(f), the sensitivity of the TENG sensor was calculated to be 0.01 μM−1 in the sensing range of 10–100 mM. Besides the good sensitivity, this β-CD modified TENG sensor exhibited excellent selectivity and reusability. The detecting performance of this sensor for a number of other organic species that possessed similar molecular structures with phenol were tested and presented in Fig. 9(g). With the same concentration of 50 mM, the recorded current ratio from phenol detecting was appreciably larger than all other organic species, implying the good selectivity of this sensor. Additionally, after the sensing process, the device could be completely recovered by ethyl alcohol rinsing without losing any electric output. The exceptional sensitivity, selectivity, reusability, low cost, environmentally friendly and self- powered characteristics promise this β-CD modified TENG in future phenol sensing field. Jie et al. developed a self-powered TENG sensor for dopamine (DA) detection with PTFE-Al triboelectric pair [88]. The operation of this DA sensor relies on the chemical modification of PTFE with the polydopamine (PDA). Under slightly alkaline condition, DA molecule would go through a self-polymerization and produced PDA chains on the PTFE surfaces (Fig. 10(a)). Fig. 10(b) schematically depicts the PDA modification process, where PTFE film was first soaked in the buffer solution containing different concentrations of dopamine. After adjusting the PH to 8.5, considerable amount of PDA was formed on the PTFE surface, turning the film color from white to brown and increased the hydrophobicity of PTFE. Since the electron affinity of PDA layer was substantially smaller than PTFE, the PDA layer would significantly reduce the surface charge density of the PTFE film, and therefore reduce the TENG output. Fig. 10(c) manifests the current output ratio of TENG under a series of DA concentrations. In general, current output diminished with the increase of DA concentration. As shown in the inset of Fig. 10(c), a proximately linear relationship was identified between the current ratio and Napierian logarithm of the DA concentration within the testing range (10 μM and 1 mM). The detection limit of this TENG sensor was found to be 0.5 μM, indicating its good sensitivity. The selectivity of the TENG sensor was further studied by purposely introducing other interference factors into the DA solution including uric acid (UA) and ascorbic acid (AA). Conventional electrochemical detections of DA usually suffer from the fouling effect resulted from the oxidation of UA and AA. However, in this TENG sensor, UA and AA can be well excluded since these two molecules have poor interaction between PTFE. Y. Yu, X. Wang / Extreme Mechanics Letters ( ) – 13 Fig. 9. (a) Schematic of TENG device with β-cyclodextrin (β-CD) modified surface for phenol detection. (b) Schematic illustrations of electron transfer from hydroxyl group of β-CD to TiO2 nanowires. (c) A photograph of as-fabricated TENG device. The scale bar is 2 cm. (d) Voltage output increment of β-CD modified TENGs with the increase of β-CD concentrations. (e) Current density reduction of phenol treated TENGs with the increase of phenol concentration. (f) The determination of sensitivity and detecting range of the TENG sensor in terms of both current and voltage output. (g) The current ratios of TENGs treated by various chemicals, showing particular effective sensing function for phenol. Inset is the demonstration of reaction mechanism between β-CD and organic species.PDF Image | Chemical modification of polymer surfaces for advanced triboelectric nanogenerator development
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