Investigation of solar-induced photoelectrochemical water splitting and photocatalytic dye removal activities of camphor sulfonic acid doped polyaniline -WO3- MWCNT ternary nanocomposite

doi:10.1016/j.jmst.2019.08.020

Abstract

Abstract:

The camphor sulfonic acid doped polyaniline-WO₃-multiwall carbon nanotube (CSA PANI-WO₃-CNT) ternary nanocomposite was synthesized during in-situ oxidative polymerization and characterized by Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Transmission electron microscopy (TEM), and Energy-dispersive X-ray spectroscopy (EDS). The application of CSA PANI-WO₃-CNT ternary nanocomposite was investigated as the photocatalyst in the degradation of methylene blue dye (MB) and as the noble metal-free photoanode in photoelectrochemical water splitting under solar light irradiation. The degradation percentage of MB dye after 60 min illumination by CSA PANI-WO₃-CNT ternary nanocomposite reached 91.40% which was higher than that of pure WO₃ (43.45%), pure CSA PANI (48.4%) and CSA PANI-WO₃ binary nanocomposite (85.15%). The photocurrent density of indium tin oxide (ITO)/CSA PANI-WO₃-CNT photoanode obtained 0.81 mA/cm² at 1.23 V vs. reversible hydrogen electrode under illumination which was 1.27, 2.13, and 4.26 times higher than that of the ITO/CSA PANI-WO₃ (0.64 mA/cm²), ITO/pure CSA PANI (0.38 mA/cm²), and ITO/pure WO₃ (0.19 mA/cm²). Also, the applied bias photon-to-current efficiency (ABPE) of ITO/CSA PANI-WO₃-CNT was obtained 0.11% which showed two-fold, four-fold, and five-fold enhancements compared to the ITO/CSA PANI-WO₃, ITO/CSA PANI, and ITO/WO₃, respectively. The electrochemical impedance spectroscopy, as well as the Mott-Schottky results, confirmed the better photoelectrocatalytic activity of ITO/CSA PANI-WO₃-CNT in comparison with ITO/WO₃, ITO/CSA PANI, and ITO/CSA PANI-WO₃. The observed improvement in the photocatalytic and photoelectrocatalytic performances of WO₃ in the presence of CSA PANI is due to the formation of type -II heterojunction between WO₃ and CSA PANI which allows the separation of charge carriers easier and faster. On the other hand, MWCNT addition to the CSA PANI-WO₃ nanocomposite provided the conducting substrate for efficient interfacial charge separation as well as transferring.

Key words: Camphor sulfonic acid, Polyaniline, WO₃, Photocatalyst, Water splitting

Mir Ghasem Hosseini, Pariya Yardani Sefidi, Ahmet Musap Mert, Solen Kinayyigit. Investigation of solar-induced photoelectrochemical water splitting and photocatalytic dye removal activities of camphor sulfonic acid doped polyaniline -WO₃- MWCNT ternary nanocomposite[J]. J. Mater. Sci. Technol., 2020, 38: 7-18.

Figures/Tables 15

Fig. 1. Schematic illustration of CSA PANI-WO3-CNT synthesis process.

Fig. 2. FTIR spectra of (a) pure WO3, (b) CSA PANI-WO3 and (c) CSA PANI-WO3-CNT.

Fig. 3. Raman spectra of (a) pure WO3, (b) CSA PANI-WO3 and (c) CSA PANI-WO3-CNT.

Fig. 4. XRD patterns of (a) pure WO3, (b) pure CSA PANI, (c) CSA PANI-WO3 and (d) CSA PANI-WO3-CNT.

Fig. 5. XPS analysis of CSA PANI-WO3-CNT (a), survey spectrum (b), C 1s (c) N 1s and (d) W 4f core levels.

Fig. 6. SEM images of (a1, a2) pure WO3 NPs, (b1, b2) pure CSA PANI, (c1, c2) CSA PANI-WO3 and (d1, d2) CSA PANI-WO3-CNT.

Fig. 7. TEM images of CSA PANI-WO3-CNT ternary nanocomposite.

Fig. 8. EDS analysis of (a) pristine WO3, (b) pure CSA PANI, (c) CSA PANI-WO3 and (d) CSA PANI-WO3-CNT.

Fig. 9. Absorbance spectra and band gap energies of (a, b) WO3 NPs, (c, d) CSA PANI-WO3 and (e, f) CSA PANI-WO3-CNT.

Fig. 10. Absorption spectra of MB in the presence of (a) WO3 NPs, (b) CSA PANI, (c) CSA PANI-WO3, (d) CSA PANI-WO3-CNT; (e) the photodegradation efficiency versus irradiation time, (f) calculated pseudo-first-order rate constants of photocatalysts.

Fig. 11. Schematic presentation of photocatalytic mechanism for MB degradation in the presence of CSA PANI-WO3-CNT.

Fig. 12. (a) Linear sweep voltammograms, (b) variation of the photoconversion efficiency vs. potential of the ITO/WO3, ITO/CSA PANI, ITO/CSA PANI-WO3, and ITO/CSA PANI-WO3-CNT photoanodes in dark and under illumination.

Fig. 13. (a1, a2) Nyquist, (b1, b2) Bode plots of ITO/WO3, ITO/CSA PANI, ITO/CSA PANI-WO3 and ITO/CSA PANI-WO3-CNT photoelectrodes and (c) equivalent circuit model for fitting EIS data.

Table 1 Obtained charge transfer resistance values for WO3, CSA PANI, CSA PANI-WO3 and CSA PANI-WO3-CNT coatings on ITO electrode in dark and under illumination.

Compound	R_ct dark (Ω cm²)	R_ct illumination (Ω cm²)
Pure WO₃	11210	7720
Pure CSA PANI	9501	5530
CSA PANI-WO₃	9095	2441
CSA PANI-WO₃-CNT	2641	1165

Fig. 14. Mott Schottky plots of WO3 NPs, CSA PANI-WO3 and CSA PANI-WO3-CNT thin films on ITO.

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Investigation of solar-induced photoelectrochemical water splitting and photocatalytic dye removal activities of camphor sulfonic acid doped polyaniline -WO₃- MWCNT ternary nanocomposite

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