Intercalation of ClO₄^- into HOPG Investigated by EC-STM

Authors

Xiao-yan HU, State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China;
Alice ALIWOWE, State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China;
Jia-wei YAN, State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China;
Bing-wei MAO, State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China;Follow

Corresponding Author

Bing-wei MAO(bwmao@xmu.edu.cn)

Abstract

The electrochemical intercalation and surface morphology of highly oriented pyrolytic graphite (HOPG) electrode in 2 mol•L^-1 HClO₄ were studied by in situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV). Based on the step-height changes observed before and after the intercalation, the effects of different step sites on intercalation are compared. The feasibility, reversibility and speed of intercalation are discussed. The intercalation of ClO₄^- into HOPG can be divided into three types depending on the number of graphite layers at the step site: When the layers of graphite are more than three, the intercalation becomes feasible; when the layers of graphite are four to eight, the intercalation can take place reversibly; However, when the graphite layers are one or two only, the intercalation cannot be observed because of the required high potential at which drastic oxidation reaction occurs concurrently. Exfoliation and etching of HOPG are the main morphological changes in this situation.

Graphical Abstract

Keywords

graphite intercalation compound, HClO4, anion intercalation, electrochemical scanning tunnelling microscopy

DOI Link

https://doi.org/10.13208/j.electrochem.150715

Publication Date

2015-12-23

Online Available Date

2015-08-18

Revised Date

2015-08-16

Received Date

2015-07-14

Recommended Citation

Xiao-yan HU, Alice ALIWOWE, Jia-wei YAN, Bing-wei MAO. Intercalation of ClO₄^- into HOPG Investigated by EC-STM[J]. Journal of Electrochemistry, 2015 , 21(6): 560-565.
DOI: 10.13208/j.electrochem.150715
Available at: https://jelectrochem.xmu.edu.cn/journal/vol21/iss6/8

References

[1] Noel M, Santhanam R. Electrochemistry of graphite intercalation compounds[J]. Journal of Power Sources, 1998, 72(1): 53-65.

[2] Wisendanger R, Guentherodt H J. Scanning tunneling microscopy I-II[M]. Berlin: Springer, 1992-1993.

[3] Kinoshita K. Carbon: Electrochemical and physicochemical properties[M]. New York: Wiley, 1988.

[4] Beck F, Junge H, Krohn H. Graphite intercalation compounds as positive electrodes in galvanic cells[J]. Electrochimica Acta, 1981, 26(7): 799-809.

[5] Alsmeyer D C, McCreery R L. In situ Raman monitoring of electrochemical graphite intercalation and lattice damage in mild aqueous acids[J]. Analytical Chemistry, 1992, 64(14): 1528-1533.

[6] Goss C A, Brumfield J C, Irene E A, et al. Imaging the incipient electrochemical oxidation of highly oriented pyrolytic-graphite[J]. Analytical Chemistry, 1993, 65(10): 1378-1389.

[7] Hathcock K W, Brumfield J C, Goss C A, et al. Incipient Electrochemical oxidation of highly oriented pyrolytic graphite-correlation between surface blistering and electrolyte anion intercalation[J]. Analytical Chemistry, 1995, 67(13): 2201-2206.

[8] Zhang B L, Wang E K, et al. Effects of anodic oxidation on the surface structure of highly oriented pyrolytic graphite revealed by in situ electrochemical scanning tunnelling microscopy in H₂SO₄ solution[J]. Electrochimica Acta, 1995, 40(16): 2627-2733.

[9] Alliata D, Kötz R, Hass O, et al. In situ AFM study of interlayer spacing during anion intercalation into HOPG in aqueous electrolyte[J]. Langmuir, 1999, 15(24): 8483-8489.

[10] Alliata D, Häring P, Hass O, et al. Anion intercalation into highly oriented pyrolytic graphite studied by electrochemical atomic force microscopy[J]. Electrochemistry Communications, 1999, 1(1): 5-9.

[11] Singh P R, Zeng X Q. Size-dependent intercalation of ions into highly oriented pyrolytic graphite in ionic liquids: An electrochemical atomic force microscopy study[J]. The Journal of Physical Chemistry C, 2011, 115(35): 17429-17439.

[12] Pierson H.O. Handbook of carbon, graphite, diamond and fullerenes[M]. Park Ridge: Noyes Publications, 1993.

[13] Aronson S, Lemont S, Weiner J. Determination of the H₂SO- 4-HSO- 4 and HC1O- 4-C1O- 4 ratios in graphite lamellar compounds[J]. Inorganic Chemistry, 1971, 10(6): 1296-1298.