Abstract
The role of edge-plane-like defects at the open ends of multiwalled carbon nanotubes (MWCNTs) and at hole defects in the tube walls is explored using cyclic voltammetry with two charged redox probes, namely potassium ferrocyanide and hexaamineruthenium(III) chloride in unbuffered aqueous solutions, and one neutral redox probe, norepinephrine, in pH 5.7 buffer. Further, the presence of oxygen-containing functional groups (such as phenol, quinonyl and carboxyl groups), which decorate the edge-plane defect sites on the voltammetric response of the MWCNTs, is also explored. To this end, three different pre-treatments were performed on the pristine MWCNTs made using the arc-discharge method (arc-MWCNTs). These were (a) arc-MWCNTs were subjected to acid oxidation to form acid-MWCNTs—open-ended MWCNTs also possessing numerous hole defects revealing a large number of edge-plane-like sites heavily decorated with surface functional groups; (b) acid-MWCNTs, which were subsequently vacuum-annealed at 900 °C to remove the functional groups but leaving the many undecorated edge-plane-like sites exposed (ann-MWCNTs); (c) ann-MWCNTs, which were subjected to a further vacuum “super-annealing” stage at 1,750 °C (sup-MWCNTs), which caused the hole defects to close and also closed the tube ends, thereby, restoring the original, pristine, almost edge-plane defect-free MWCNTs structure. The results of the voltammetric characterisation of the acid-, ann- and sup-MWCNTs provide further evidence that edge-plane-like sites are the electroactive sites on MWCNTs. The presence of oxygen-containing surface groups is found to inhibit the rate of electron transfer at these sites under the conditions used herein. Finally, the two charged, “standard” redox probes used were found to undergo strong interactions with the oxygen-containing surface groups present. Thus, we advise caution when using these redox probes to attempt to voltammetrically characterise MWCNTs, and by extension, graphitic carbon surfaces.
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References
Monthioux M, Kuznetsov VL (2006) Carbon 44:1621
Oberlin A, Endo M (1976) J Cryst Growth 32:335
Wiles PG, Abrahamson J (1978) Carbon 16:341
Iijima S (1991) Nature 354:56
Wildgoose GG, Banks CE, Leventis HC, Compton RG (2006) Microchim Acta 152:187
Leonhardt R, Ritschel M, Bartsch K, Graff A, Taschner C, Fink J (2001) J Physique IV: Proc 11:Pr3/445
Wang YY, Tang GY, Koeck FAM, Brown B, Garguilo JM, Nemanich RJ (2004) Diamond Rel Mater 13:1287
Ebbesen TW (1994) NATO ASI Ser C 443:11
Kratschmer W, Lamb LD, Fostiropoulos K, Huffman DR (1990) Nature 347:354
Liu C, Cong HT, Li F, Tan PH, Cheng HM, Lu K, Zhou BL (1999) Carbon 37:1865
Dai X, Wildgoose GG, Compton RG (2006) Analyst 131:901
Kruusma J, Mould N, Jurkschat K, Crossley A, Banks CE (2007) Electrochem Commun 9:2330
Jones CP, Jurkschat K, Crossley A, Compton RG, Riehl BL, Banks CE (2007) Langmuir 23:9501
Jurkschat K, Ji X, Crossley A, Compton RG, Banks CE (2007) Analyst 132:21
Sljukic B, Banks CE, Compton RG (2006) Nano Lett 6:1556
Banks CE, Crossley A, Salter C, Wilkins SJ, Compton RG (2006) Angew Chem Int Ed 45:2533
Batchelor-McAuley C, Wildgoose GG, Compton RG, Shao L, Green MLH (2008) Sens Act B. DOI 10.1016/j.snb.2008.01.049
Banks CE, Compton RG (2005) Anal Sci 21:1263
Banks CE, Compton RG (2006) Analyst 131:15
Banks CE, Davies TJ, Wildgoose GG, Compton RG (2005) Chem Commun 7:829
Thorogood CA, Wildgoose GG, Crossley A, Jacobs RMJ, Jones JH, Compton RG (2007) Chem Mater 19:4964
Masheter AT, Xiao L, Wildgoose GG, Crossley A, Jones JH, Compton RG (2007) J Mater Chem 17:3515
Thorogood CA, Wildgoose GG, Jones JH, Compton RG (2007) New J Chem 31:958
Dumitrescu I, Wilson NR, Macpherson JV (2007) J Phys Chem C 111:12944
Du Vall S, Yang H-H, McCreery RL (1999) Proc Electrochem Soc 99-5:33
McCreery RL, Cline KK, McDermott CA, McDermott MT (1994) Coll Surf A 93:211
Cline KK, McDermott MT, McCreery RL (1994) J Phys Chem 98:5314
McDermott CA, Kneten KR, McCreery RL (1993) J Electrochem Soc 140:2593
Ranganathan S, Kuo T-C, McCreery RL (1999) Anal Chem 71:3574
Chou A, Boecking T, Singh NK, Gooding JJ (2005) Chem Commun 7:842
Banks CE, Ji X, Crossley A, Compton RG (2006) Electroanalysis 18:2137
Ji X, Banks CE, Crossley A, Compton RG (2006) ChemPhysChem 7:1337
Liu J, Chou A, Rahmat W, Paddon-Row MN, Gooding JJ (2005) Electroanalysis 17:38
Henstridge MC, Shao L, Wildgoose GG, Compton RG, Tobias G, Green MLH (2008) Electroanalysis 20:498
Liu J, Rinzler AG, Dai H, Hafner JH, Bradley RK, Boul PJ, Lu A, Iverson T, Shelimov K, Huffman CB, Rodriguez-Macias F, Shon Y-S, Lee TR, Colbert DT, Smalley RE (1998) Science 280:1253
Kuznetsova A, Mawhinney DB, Naumenko V, Yates JT, Liu J, Smalley RE (2000) Chem Phys Lett 321:292
Yudasaka M, Ichihashi T, Kasuya D, Kataura H, Iijima S (2003) Carbon 41:1273
Bougrine A, Dupont-Pavlovsky N, Naji A, Ghanbaja J, Mareche JF, Billaud D (2001) Carbon 39:685
Brown SDM, Corio P, Marucci A, Dresselhaus MS, Pimenta MA, Kneip K (2000) Phys Rev B 61:R5137
Delhaes P, Couzi M, Trinquecoste M, Dentzer J, Hamidou H, Vix-Guterl C (2006) Carbon 44:3005
Paillet M, Michel T, Meyer JC, Popov VN, Henrard L, Roth S, Sauvajol J-L (2006) Phys Rev Lett 96:257401
Shanmugan S, Gedanken A (2006) J Phys Chem B 110:2037
Sveningsson M, Morjan R-E, Nerushev OA, Sato Y, Bäckström J, Campbell EEB, Rohmund F (2001) Appl Phys A 73:409
Vix-Guterl C, Couzi M, Dentzer J, Trinquecoste M, Delhaes P (2004) J Phys Chem B 106:19361
Wang YY, Tang GY, Koeck FAM, Brown B, Garguilo JM, Nemanich RJ (2004) Diamond Rel Mater 13:1287
Tuinistra F, Koenig JL (1970) J Chem Phys 53:1126
Masheter AT, Abiman P, Wildgoose GG, Wong E, Xiao L, Rees NV, Taylor R, Attard GA, Baron R, Crossley A, Jones JH, Compton RG (2007) J Mater Chem 17:2616
Compton RG, Banks CE (2007) Understanding voltammetry. World Scientific, Singapore
Bard AJ, Faulkner LR (2001) Electrochemical methods fundamentals and applications. Wiley, New York
Greenwood NN, Earnshaw A (1984) Chemistry of the elements. Pergamon, London
Sendt K, Haynes BS (2007) J Phys Chem C 111:5465
Zhu Z, Lu GQ, Finnerty J, Yang RT (2003) Carbon 41:635
Diao P, Guo M, Hou Q, Xiang M, Zhang Q (2006) J Phys Chem B 110:20386
Sabatani E, Rubinstein I (1987) J Phys Chem 91:6663
Abiman P, Crossley A, Wildgoose GG, Jones JH, Compton RG (2007) Langmuir 23:7847
Kenakin TP (1981) J Pharm Experiment Therap 216:210
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GGW thanks St John’s College, Oxford for a Junior Research Fellowship.
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Holloway, A.F., Wildgoose, G.G., Compton, R.G. et al. The influence of edge-plane defects and oxygen-containing surface groups on the voltammetry of acid-treated, annealed and “super-annealed” multiwalled carbon nanotubes. J Solid State Electrochem 12, 1337–1348 (2008). https://doi.org/10.1007/s10008-008-0542-2
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DOI: https://doi.org/10.1007/s10008-008-0542-2