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Manganese Dioxide Analysis via UV-Vis Spectrophotometry

The document describes the use of X-ray photoelectron spectroscopy (XPS) to analyze the elemental composition and oxidation state of manganese dioxide (MnO2) samples electrodeposited without thermal treatment. XPS analysis revealed that the manganese was in the Mn4+ oxidation state. Deconvolution of the O1s spectra identified peaks corresponding to Mn-O-Mn, Mn-O-OH, H-O-H and chemisorbed oxygen bonds. References are provided relating to the use of MnO2 in electrode materials and the interpretation of XPS spectra.

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Carlos Lugo
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33 views2 pages

Manganese Dioxide Analysis via UV-Vis Spectrophotometry

The document describes the use of X-ray photoelectron spectroscopy (XPS) to analyze the elemental composition and oxidation state of manganese dioxide (MnO2) samples electrodeposited without thermal treatment. XPS analysis revealed that the manganese was in the Mn4+ oxidation state. Deconvolution of the O1s spectra identified peaks corresponding to Mn-O-Mn, Mn-O-OH, H-O-H and chemisorbed oxygen bonds. References are provided relating to the use of MnO2 in electrode materials and the interpretation of XPS spectra.

Uploaded by

Carlos Lugo
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Figure S1. Calibration curve for the determination of manganese dioxide in the samples.

The
absorbance maximum at 525 nm is plotted against the concentration of MnO 4− in aqueous solution.

MnO4− has a characteristic absorbance maximum at 525 nm, which can be used to qualitatively
determine the mass loading of MnO2 using UV–vis spectrophotometry [32]. The process was as
follows: first the sample with electrodeposited MnO2 is immersed into 10 mL of concentrated nitric
acid to dissolve the oxide; then, the manganese ions are oxidized to MnO4− using a definite amount
of K2S2O8 and AgNO3; the concentration of MnO4− ions is determined by UV–vis spectrophotometry
(using Figure S1 as the calibration curve); finally, the loading mass of MnO 2 is calculated based on
the concentration of MnO4− and the volume of the solution.

Figure S2. Energy dispersive x-ray spectrum of a MnO2/GNWs composite sample after galvanostatic
electrodeposition of MnO2.

Materials 2019, 12, x; doi: FOR PEER REVIEW [Link]/journal/materials


Materials 2019, 12, x FOR PEER REVIEW 2 of 2

Figure S3. XPS spectra of galvanostatically electrodeposited MnO2 without thermal treatment [33].

XPS was used to evaluate the elemental composition and oxidation state of manganese. Figure
S3a shows Mn 2p spectra of galvanostatically electrodeposited MnO2 without thermal treatment. The
Mn 2p spectrum exhibits three peaks; Mn 2p3/2 was positioned at (641.85 ± 0.1) eV, Mn 2p 1/2 at (653.5
± 0.1) eV [1], and a shoulder appears at around 644.5 eV. The binding energy difference between the
Mn 2p3/2 and Mn 2p1/2 peaks is about 11.7 eV which is very much like the reported values in other
studies [2]. These results indicate that manganese is in the Mn4+ oxidation state [3].
Deconvolution of the O1s spectra in 4 peaks (see Figure S3b) reveals the chemical environment
of oxygen. The peak located at (529.30 ± 0.1) eV can be ascribed to (Mn–O–Mn). Peaks around (530.9
± 0.1) eV, (532.7 ± 0.2) eV, and (535.10 ± 0.2) eV could be attributed to (Mn–O–H), (H–O–H), and
chemisorbed oxygen, respectively [4,5]. The position and percentage area of the deconvoluted O1s
peaks were 529.44 eV/33.79%, 530.88 eV/24.36%, 532.39 eV/13.89%, 535.26 eV/27.96%, which
correspond to Mn–O–Mn, Mn–O–OH, H–O–H and chemisorbed oxygen, respectively.

References
1. Sellers, M.C.K.; Castle, B.M.; Marsh, C.P. Threedimensional manganese dioxide-functionalized carbon
nanotube electrodes for electrochemical supercapacitors. J. Solid State Electr. 2013, 17, 175–182.
2. Shen, J.; Liu, A.; Tu, Y. Asymmetric deposition of manganese oxide in single walled carbon nanotube films
as electrodes for flexible high frequency response electrochemical capacitors. Electrochim. Acta 2012, 78,
122–132.
3. Nesbitt, H.W.; Banerjee, D. Interpretation of XPS Mn(2p) spectra of Mn oxyhydroxides and constraints on
the mechanism ofMnO2 precipitation. Am. Mineral. 1998, 83, 305–315.
4. Dubal, D.P.; Dhawale, D.S.; Salunkhe, R.R.; Lokhande, C.D. Conversion of chemically prepared interlocked
cubelike Mn3O4 to birnessite MnO2 using electrochemical cycling. J. Electrochem. Soc. 2010, 157, A812–
A817.
5. Biniak, S.; Szymánski, G.; Siedlewski, J.; Swiatkoski, A. The characterization of activated carbons with
oxygen and nitrogen surface groups. Carbon 1997, 35, 1799–1810.

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