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. 2021 Feb 10;6(7):4988-4994.
doi: 10.1021/acsomega.0c06035. eCollection 2021 Feb 23.

Freestanding and Flexible β-MnO2@Carbon Sheet for Application as a Highly Sensitive Dimethyl Methylphosphonate Sensor

Wooyoung Kim  1 , Jun Seop Lee  2
Affiliations

Freestanding and Flexible β-MnO2@Carbon Sheet for Application as a Highly Sensitive Dimethyl Methylphosphonate Sensor

Wooyoung Kim et al. ACS Omega. .

Abstract

Research on wearable sensor systems is mostly conducted on freestanding polymer substrates such as poly(dimethylsiloxane) and poly(ethylene terephthalate). However, the use of these polymers as substrates requires the introduction of transducer materials on their surface, which causes many problems related to the contact with the transducer components. In this study, we propose a freestanding flexible sensor electrode based on a β-MnO2-decorated carbon nanofiber sheet (β-MnO2@CNF) to detect dimethyl methylphosphonate (DMMP) as a nerve agent simulant. To introduce MnO2 on the surface of the substrate, polypyrrole coated on poly(acrylonitrile) (PPy@PAN) was reacted with a MnO2 precursor. Then, phase transfer of PPy@PAN and MnO2 to carbon and β-MnO2, respectively, was induced by heat treatment. The β-MnO2@CNF sheet electrode showed excellent sensitivity toward the target analyte DMMP (down to 0.1 ppb), as well as high selectivity, reversibility, and stability.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Illustrative diagram of β-MnO2-decorated carbon nanofiber sheet (β-MnO2@CNF).
Figure 2
Figure 2
Field effect scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) (inset) images of each fabrication step: (a) electrospun PAN sheet; (b) PPy-coated PAN sheet (PPy@PAN); (c) amorphous MnO2-decorated PPy@PAN (MnO2-PPy@PAN) sheet; and (d) β-MnO2-decorated carbon nanofiber sheet (β-MnO2@CNF). Inset: scale bars indicate 500 nm.
Figure 3
Figure 3
(a) Fully scanned X-ray photoelectron spectroscopy (XPS) of the pristine CNF sheet (black) and β-MnO2@CNF sheet (red): (b) Mn 2p, (c) O 1s, and (d) C 1s XPS spectra of the β-MnO2@CNF sheet.
Figure 4
Figure 4
(a) X-ray diffraction (XRD) spectra of MnO2-PPy@PAN sheet (black) and β-MnO2@CNF sheet (red). (b) Raman spectra of pristine CNF sheet (black) and β-MnO2@CNF sheet (red).
Figure 5
Figure 5
(a) FE-SEM and energy-dispersive X-ray spectroscopy (EDX) dot mapping of (b) Mn, (c) N, and (d) O atoms of the β-MnO2@CNF sheet.
Figure 6
Figure 6
Reversible and reproducible responses are measured at a current value (10–6 A) with the different carbon sheets. (a) Normalized resistance changes upon sequential exposure to various concentrations of DMMP (black: pristine CNF sheet; red: β-MnO2@CNF sheet). (b) Normalized resistance change of β-MnO2@CNF sheet upon sequential periodic exposure to different DMMP concentrations (black: 100 ppb; green: 10 ppb; orange: 1 ppb; red: 0.1 ppb). (c) Sensing performance of β-MnO2@CNF sheet electrode during 60 days. Measurements were obtained in day intervals. (d) Selectivity responses of the β-MnO2@CNF sheet electrode toward 0.1 ppm of DMMP and 100 ppm of other chemicals.
Figure 7
Figure 7
(a) Current–voltage curve with various bending angles of the β-MnO2@CNF sheet electrode. (b) Normalized resistance change of the β-MnO2@CNF electrode upon 0.1 ppb DMMP exposures with various bending angles.
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