7 September 2001

Chemical Physics Letters 345 (2001) 2528

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Determination of the acidic sites of puried single-walled carbon nanotubes by acidbase titration
H. Hu, P. Bhowmik, B. Zhao, M.A. Hamon, M.E. Itkis, R.C. Haddon *
Departments of Chemistry and Chemical and Environmental Engineering, University of California, Riverside, CA 92521-0403, USA Received 17 March 2001; in nal form 13 July 2001

Abstract We report the measurement of the acidic sites in three dierent samples of commercially available full-length puried single-walled carbon nanotubes (SWNTs) as obtained from CarboLex (CLI), Carbon Solutions (CSI) and Tubes@Rice (TAR) by simple acidbase titration methods. Titration of the puried SWNTs with NaOH and NaHCO3 solutions was used to determine the total percentage of acidic sites and carboxylic acid groups, respectively. The total percentage of acidic sites in full length puried SWNTs from TAR, CLI and CSI are about 13%. 2001 Published by Elsevier Science B.V.

1. Introduction Single-walled carbon nanotubes (SWNTs) have attracted attention due to their unique electronic and mechanical properties [1]. To fully realize these properties it is necessary to chemically process the SWNTs in order to purify current preparations, and to bring about appropriate functionalization. Most purications of SWNTs make use of oxidative methods that typically involve treatment with nitric acid [24]. These reagents remove the caps of the SWNTs and introduce defects involving oxygen functionalities mainly in the forms of carboxylic acid groups on the surface and at the ends of the SWNTs [57]. It is important to determine the concentration of these defects, since they not only change the properties of SWNTs, but also serve as reactive

Corresponding author. E-mail address: haddon@citrus.ucr.edu (R.C. Haddon).

sites for SWNT dissolution chemistry [8,9]. Previous determinations of the density of the surface defect sites of SWNTs have been reported. The evolution of CO2 (g) and CO (g) from puried SWNTs heated above 1200 K has been measured [7], and used to estimate a concentration of $5 at.% defective carbon atoms in puried SWNTs. Calibrated energy dispersive X-ray spectroscopy indicated $4 at.% oxygen atoms in puried SWNTs [10]. Acidbase titration methods have been used to determine the acidic and basic characters of the surfaces of a wide variety of carbon materials [11 14], including multi-walled carbon nanotubes (MWNTs) [1517]. The reported density of surface acidic groups in the MWNTs treated with nitric acid is in the range 0.20.5 at.% [15,17]. The total acidic sites (including carboxylic acids, lactones and phenols), can be determined by titration with NaOH, while the carboxylic acid groups can be individually determined by titration with NaHCO3 . In this Letter we report the measure-

0009-2614/01/$ - see front matter 2001 Published by Elsevier Science B.V. PII: S 0 0 0 9 - 2 6 1 4 ( 0 1 ) 0 0 8 5 1 - X

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H. Hu et al. / Chemical Physics Letters 345 (2001) 2528

ment of the acidic sites in full-length nitric acid puried SWNTs, by use of acidbase titration methods.

2. Experimental We examined three dierent kinds of full-length puried (P) SWNT samples by titiration: CarboLex, Inc. (CLI)-P, Carbon Solutions, Inc (CSI)-P, and Tubes @Rice (TAR)-P. According to company literature, all of the samples were rst subjected to a nitric acid treatment to remove catalyst, amorphous carbon and to begin to break up the nanoparticulate impurities. TAR-P SWNTs (purity $90%) are from laser-produced SWNTs, [18] while the CLI-P (purity 6080%) and CSI-P SWNTs were produced in a modied electric arc method [19]. In addition, we studied a low functionality form of full-length puried SWNTs (CSIP-LF), in which CSI-P material had been further processed to reduce the oxygen functionality. The SWNT samples were rst washed with deionized water to remove any acidic residues left in the samples. The air-dried samples were then heated at 100 C for 0.5 h under vacuum to degas absorbed carbon dioxide and water. After this pretreatment, the SWNT samples were ready for the titration experiments. The titration procedure is exemplied below for the sodium bicarbonate analysis of carboxylic groups in the SWNT (SWNTCOOH). Forward titration SWNTCOOH NaHCO3 excess 3 SWNTCOO Na NaHCO3 determined by titration Backward titration SWNTCOO Na HCl excess 3 SWNTCOOH HCl determined by titration In a typical experiment, 98.86 mg of TAR-P SWNTs was stirred in 50.00 ml of 0.05 N NaHCO3 aqueous solution under argon for 48 h. Prolonged stirring was required to allow the solid SWNTs to

equilibrate with the NaHCO3 solution. The mixture was then ltered through a membrane (pore size of 1.2 lm). The SWNTs collected on the membrane were washed with de-ionized water to remove all of the NaHCO3 residues. The combined ltrate and washings were added to 50.00 ml of 0.05 N aqueous HCl solution and boiled for 20 min to degas the CO2 from the solution. After cooling to room temperature, the excess HCl in the solution was titrated with 2.20 ml of 0.05 N aqueous NaOH solution to reach the neutral point (pH 7.00), as monitored by a pH meter (Corning pH meter 445). By calculation, the amount of SWNTCOOH groups in the SWNTs is 0.143 mmol. The amount of carbon in the SWNTs is estimated to be 8.231 mmol by assuming that the SWNTs are solely composed of carbon. The mole percentage of the SWNTCOOH groups in the TAR-P SWNT sample is 1.7%. We also back titrated, in order to ensure the reliability of the results (see above). From the forward titration we collected 60.92 mg of the NaHCO3 -treated SWNTs, now in the form of the conjugate base, SWNTCOO Na . After drying and weighing the sample, it was soaked in 50.00 ml of 0.05 N aqueous HCl solution for 48 h with stirring under argon to re-acidify the conjugate base of the SWNTCOOH. The mixture was ltered through a membrane and the solid washed with de-ionized water to remove residual HCl from the sample. The combined ltrate and washings were neutralized (pH 7.00), with 48.50 ml of 0.05 N NaOH. By a similar calculation to that given above, the percentage of the SWNTCOO Na groups to the total amount of carbon is 1.5% in the NaHCO3 -treated SWNTs, which is roughly consistent with the forward titration. To determine the total percentage of acidic sites in the SWNTs, 0.05 N NaOH was used instead of NaHCO3 in the forward titrations. 3. Results and discussion The mole percentages of acidic sites in the original puried SWNT samples together with the mole percentages of basic sites in the conjugate base SWNT samples are summarized in Table 1.

H. Hu et al. / Chemical Physics Letters 345 (2001) 2528 Table 1 Acidity of puried SWNTs Sample SWNTCOOH titration (%) Forward TAR-P CLI-P CSI-P CSI-P-LF
a

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Total SWNTacid titration (%) Backward 1.5 1.6 2.1 0.8 Forward 1.5 6.9 (2.0)a 3.2 2.2 Backward 1.5 2.0 2.7 1.0

1.7 2.0 2.2 0.7

Repeat result after recycling sample.

The dierent commercial samples give fairly consistent results: the SWNTCOOH functionality is about 12% and the total SWNT acid functionality is about 13%. The TAR-P SWNTs gave very close values for the total acidic sites and for the carboxylic acid groups; thus virtually all of the acidic sites in this sample are carboxylic acid groups. A number of the samples gave a higher acidity count in the forward direction (leading to, for example, SWNTCOO Na ), than in the backward step (to produce SWNTCOOH). We attribute this to a partial purication of the SWNTs by basic extraction, in the forward titration. We experience mechanical losses in each step, due to the ltration process and re-isolation of the SWNTs, so this cannot be quantied but it seems reasonable that some of the carboxylated carbons [3] are taken into aqueous solution and removed by base in the forward titrations. This is particularly obvious with the CLI-P sample, in which the percentage of total acid sites was rst measured to be 6.9%. During the backward titration, the total basic site percentage of the NaOH treated SWNTs decreased to 2.0%. When we repeated the forward titration of the total acidic sites in this re-acidied sample, the total acidity remained constant at 2.0%. 4. Conclusion We report a quantitative study of the acidic sites in full-length puried SWNTs from the three dierent commercial suppliers using acidbase titration methods. This approach provides a simple and inexpensive method for the routine evaluation

of the acidic surface defects in puried SWNT samples. The dierent commercial samples give fairly consistent results: the SWNTCOOH functionality is about 12% and the total SWNT acid functionality is about 13%. Acknowledgements This work was supported by the MRSEC Program of the National Science Foundation under Award Number DMR-9809686 and by the oce of Naval Research under Award Number N0001499-1-0770. References
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