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Highly efcient electroosmotic ow through functionalized carbon nanotube membranes

Ji Wu, Karen Gerstandt, Mainak Majumder, Xin Zhan and Bruce J. Hinds*
Received 22nd March 2011, Accepted 16th May 2011 DOI: 10.1039/c1nr10303b Carbon nanotube membranes with inner diameter ranging from 1.57 nm were examined for enhanced electroosmotic ow. After functionalization via electrochemical diazonium grafting and carbodiimide coupling reaction, it was found that neutral caffeine molecules can be efciently pumped via electroosmosis. An electroosmotic velocity as high as 0.16 cm s1 V1 has been observed. Power efciencies were 25110 fold improved compared to related nanoporous materials, which has important applications in chemical separations and compact medical devices. Nearly ideal electroosmotic ow was seen in the case where the mobile cation diameter nearly matched the inner diameter of the singlewalled carbon nanotube resulting in a condition of using one ion is to pump one neutral molecule at equivalent concentrations.

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Introduction
Electro-osmotic ow (EOF) can be the primary method to control uid ux for applications including lab-on-chip diagnostics, medical implants, drug delivery and chemical separations.16 The key advantage of EOF compared to pressure driven pumps is the ability for compact integration of numerous ow paths that can be electrically addressed. Unfortunately EOF is a relatively inefcient process based on interfacial ow that has shown limited but promising success in device applications.79 EOF relies on a high density of xed surface charge (usually anionic) that allows only the counterion (cation) to ow in the direction of electric eld pumping neutral solvent and solutes in the ow without the interference of free anions moving in the opposite direction. This is a surface phenomenon seen only within the Debye screening length ($2 nm) of the surface, and hence requires a nanoporous membrane or channel. The ideal conditions for efcient EOF are to have high surface charge density, small diameter and a slippery interface to efciently transmit ow through the membrane. Currently, signicant scientic attention has been focused on carbon nanotube membranes due to their potential applications in chemical separations, water purication, chemical sensors and drug delivery.1016 Carbon nanotubes (CNTs) have three key attributes (1) atomically at graphitic planes allowing fast uid ow (2) ability to covalently functionalize entrances of CNT pores with charged groups and (3) they are electrically conductive allowing for the concentration of electric eld at the CNT tip. Molecular Dynamic (MD) simulations predicted a 10 000

Department of Chemical and Materials Engineering, University of Kentucky, Kentucky, 40506, USA. E-mail: bjhinds@engr.uky.edu Current address: Dept. Mech. Engr. Monash University, Australia.

fold uid ow enhancement over the slippery graphitic interface17 and the ability to support ionic ow.18,19 Both predictions were experimentally conrmed1113 and are the basis for examining EOF efciency within CNT membranes. By placing anionic charged groups at the entrance to the CNT to exclude mobile anions, cations alone will be accelerated down the tube and generate EOF. The primary hypothesis of this report is that the slippery graphite core, that supports fast pressure driven ow, will yield high efciency EOF. Power efciency is a particularly important parameter for compact medical devices such as programmable transdermal drug delivery or in large scale chemical separations. CNT membranes can be fabricated via several approaches11,12,2023 and the electroosmotic ow had been initially examined in non-graphitic CNTs. Sun and Crooks embedded a single carbon nanotube into an epoxy matrix and then microtomed CNT membranes.22 However no enhanced uid ux or electroosmosis compared to classical materials was observed since the diameter of their CNTs was large (500 nm) and they were not highly ordered graphitic tubes.22 A chemical vapor deposition (CVD) method was used to coat a layer of amorphous carbon (a-C) on the wall of the Anodized Alumina Oxide (AAO) membrane template to obtain a-CNT membranes. This electro-osmotic investigation showed signicant improvement in the electro-osmotic velocity however this was signicantly less than the electrophoretic ow of charged ions21 presumably because the tubes were much larger (120 nm i.d.) than the Debye screening length ($1.5 nm) of the pore surface. Using ordered graphitic MWCNTs Majumder et al. found that the conformational change of gate-keeper molecules can be utilized to effectively separate chemical species of different sizes but did not directly study the phenomenon of electroosmosis.14 Recently functionalized DWCNT membranes have been used for
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very power efcient electrophoretic/osmotic pumping of nicotine through human skin at therapeutically useful doses6 and extremely high Li+ and K+ mobilities are reported in SWCNT channels.24 Needed is an electroosmotic study on ordered graphitic CNTs to examine whether there are large gains in EOF power efciency due to the slippery CNT interface. We report herein efcient electro-osmotic ow (EOF) across CNT membranes that were fabricated by microtoming multiwalled CNTs (7 nm i.d.) and single walled CNT (1.5 nm i.d.) epoxy composites. The EOF was studied by measuring the uxes of both charged and neutral probe molecules through the membranes under external electric eld. An electrochemical diazonium grafting method was employed to enhance the surface anionic charge density of CNTs, which was further enhanced via a carbodiimide coupling reaction with the dye molecule containing four negatively charged SO3 groups. Improvements in EOF power efciencies of 2540 folds are seen in the system.

Functionalization of CNT membranes As-prepared MWCNT membranes were grafted with benzoic acid by electrochemically reducing 5 mM 4-carboxy phenyl diazonium tetrauoroborate in 0.1 M HCl and 0.1 M KCl electrolyte at 0.6 V for 4 minutes. The MWCNT membrane was grafted using a static approach without internal uid ow, and named S.G. CNT.14 After the grafting reaction, the membrane was thoroughly rinsed using de-ionized (DI) water, 0.1 (M) KCl, and IPA to dissolve any unwanted byproducts. In the next step, Direct Blue 71 dye was coupled to benzoic acid via one step carbodiimide chemistry method: 10 mg of EDC and 5 mg Sulfo-NHS were dissolved into 4 ml of 50 mM Direct Blue 71 (dye, Aldrich) in 0.1 (M) MES buffer for 12 h at ambient temperature, after which the membrane was washed with 0.1 M MES buffer, 0.1 M KCl solution and DI water to remove the excess reagents. These functionalized membranes are referred to as S.G. MWCNTsdye, as diagrammed in Fig. 1d. For SWCNT membranes, functionalization was achieved by H2O plasma oxidation to produce carboxylate groups at CNT tips.11,27 Functionalization of AAO membranes Anodic aluminium oxide (AAO) membrane with an average pore diameter of 20 nm and a thickness of 60 mm was purchased from Whatman Company. AAO membranes were immersed in 20 ml toluene containing 2 ml 3-(triethoxysilyl)propylamine (C6H17NO3Si, Sigma) that was reuxed overnight with argon gas protection. The amine functional group was further coupled to sulfoacetic acid (HO3SCH2CO2H, Sigma Aldrich) using the same one step carbodiimide chemistry as described above to make the AAO membrane negatively charged. Characterization of CNT membranes Electrochemical impedance spectroscopy28 measurements were employed to characterize the surface chemistry of CNT membranes, which were performed in the frequency range of 100 kHz0.2 Hz with a sinusoidal amplitude modulation of 10 mV

Experimental section
Fabrication of carbon nanotube (CNT) membranes CNT membranes were fabricated using an approach similar to a prior report for single CNT membrane ow22 and modied for a high CNT loading. To describe it briey, multi-walled CNTs with an average core diameter of $7 nm and length of 150 mm were prepared via a chemical vapor deposition (CVD) approach using ferrocene/xylene as the feeding gas.25 SWCNTs were purchased from CheapTubes.com. Next, 5 wt% CNTs were mixed with Epon 862 epoxy resin (Miller Stephenson Chem. Co.), hardener methylhexahydrophthalic anhydride (MHHPA, Broadview Tech. Inc.) and 0.1 g surfactant Triton-X 100 (Sigma) using a Thinky centrifugal shear mixer. As-prepared CNTsepoxy composite was cured at 85  C according to the commercial epoxy procedure before being cut into CNT membranes using a microtome equipped with a glass blade. The typical thickness of the as-cut CNT membrane is about 5 microns. Modest pullout of only a few percent of the membrane thickness is seen on regions of the sample after microtoming. Finally, the residual epoxy on the tips of CNTs was removed by H2O plasma oxidation. Synthesis of 4-carboxy phenyl diazonium tetrauoroborate The diazonium compound was synthesized following a method reported by DAmour and Belanger.26 2.74 g (0.02 mol) of p-aminobenzoic acid (Aldrich) was dissolved in 20 ml of water, which was heated at about 50  C until it was dissolved. 0.044 mol of concentrated HCl was added dropwise to the solution, followed by cooling of the solution to 3  C. 0.022 mol of NaNO2 (Sigma) in 10 ml of water at 0  C was added slowly to the solution in $30 minutes followed by 1 h reaction time. The solution was ltered, and then 0.022 mol of NaBF4 (Aldrich) solution was added to the ltrate at 3  C. A light yellow precipitate was formed. The precipitate was ltered and washed with ice water and cold ether. The product was dried in vacuum and preserved in a desiccator at 4  C. 1H NMR (400 MHz, CDCl3, d): (4-carboxyphenyl)-diazonium tetrauoroborate, two doublets at 8.878.83 and 8.468.42 ppm.
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Fig. 1 SEM images of MWCNT membrane (a) cross-section view; (b) top view; (c) TEM image of microtome-cut MWCNTs with open tips; (d) the molecular structure on the functionalized CNT membrane (S.G. CNTsdye, grey: C; red: O; blue: N; yellow: S).

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using a Model 263A Potentiostat and FRD 100 Frequency Response Analyzer from Princeton Applied Research. Faradaic EIS measurements were carried out at 230 mV using an electrolyte consisting of 5 mM K3Fe(CN)6 and K4Fe(CN)6, 0.1 M KCl, and 10 mM K2CO3 (pH 10.8). A Ag/AgCl reference cell (BASI Corp.) was used with Pt wire counter electrodes. An S-4300 HITACHI Scanning Electron Microscope (SEM) and a JEOL 2010F Transmission Electron Microscope (TEM) were used to examine the microstructure of the CNT membranes. For the preparation of TEM samples several pieces of CNT membranes were dissolved in 1 ml 98% concentrated sulfuric acid to remove the epoxy matrix. The acidic solution was then added to 100 ml deionized water and centrifuged. A drop of centrifuged solution containing CNTs was applied to a TEM grid coated with lacey carbon. Permeation measurements A U-shape tube installed with three electrodes was employed for all the permeation studies as shown in Fig. 3c. CNT membrane, platinum wire and Ag/AgCl in saturated KCl were employed as working electrode, counter electrode and reference electrode, respectively. Constant potential was provided using a Model 263A Potentiostat. A 50 nm thick Au/Pd lm was sputtered onto the edge of the CNT membrane area as a contact for applying biases. The distance between counter and working electrodes is about 10 cm and all membrane sample areas were 0.07 cm2. Two model molecules, Ru(bpy)32+ and caffeine were used to investigate the electrophoresis and electro-osmosis properties of CNT membranes. Typically, the donor solution is composed of 5 mM Ru(bpy)32+ or 5 mM caffeine in 0.01 M KCl aqueous solution. Permeate solution is 0.01 M KCl in DI water, which is used to balance any potential osmosis pressure from the donor solution. The concentration of the molecules was measured using an Ocean Optics UV-Vis spectrometer (USB4000, Ocean Optics Inc.). 286 nm and 272 nm peaks were used to calculate Ru(bpy)32+ and caffeine concentrations, respectively. Concentrations of metallic ions, including potassium and calcium were quantied using inductively coupled plasma-atomic emission spectrometry (Varian Vista-PRO CCD Simultaneous ICP-AES). Potassium and calcium standards were purchased from ULTRA Scientic.

membrane is defect-free. Typically, the CNT membrane has a thickness of $5 mm as shown in Fig. 1a. Regions of CNTs can extend out of the membrane surface as shown in Fig. 1b. TEM imaging (Fig. 1c) conrms that CNTs were cut open by the microtome glass knife, allowing mass transport through CNT cores. It is notable that frequent change of glass knives is required since the blade will become blunt after $20 cuttings. H2O plasma oxidation was carried out to remove polymeric residuals from the cutting process. Fig. 1d shows the schematic structure of the CNT membrane with chemical functionalization. The integrity of CNT membranes from defects was tested by the Au colloid permeation experiment.11,13 It was found there is no permeation of 10 nm Au colloids (520 nm optical absorption peak) through the CNT membrane with an average pore size of 7 nm. The porosity of the CNT membrane was evaluated from the steady-state Ru(bpy)32+ or K+ ux through MWCNT and SWCNT membranes using the following equation:13 Ap (JDx)/(DDC), 3 100 (Ap/Am) (1)

Results and discussion

CNT membranes used for all the studies were prepared using a microtome-cut method22 modied for high CNT loadings (510%) of multi-walled (MWCNTs) or single-walled (SWCNTs) to give more porosity.6 Triton X-100 surfactant was added to disperse CNTs more uniformly in the polymeric epoxy matrix. The surfactant containing phenyl functional group has a strong interaction with the graphitic plane via pp stacking so that CNTs can be well dispersed.29,30 The as-prepared CNT membranes were characterized using a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) as shown in Fig. 1. To obtain TEM images of CNTs, the polymeric epoxy was removed by dissolution in concentrated sulfuric acid. SEM cross-section view of CNT membranes (Fig. 1a) clearly shows that the space between CNTs is completely lled with the epoxy resin, which indicates that the
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where Ap (cm2) is the available pore area, J (mol s1) is the experimental steady-state ux of Ru(bpy)32+, Dx (cm) is the thickness of the membrane measured by scanning electron microscopy, DC (mol cm3) is the concentration difference between the feed and the permeate, 3 is the porosity of the membrane, and Am (cm2) is the membrane area exposed to the solution. It is assumed that Ru(bpy)32+ can diffuse with a bulk diffusivity (5.16 106 cm2 s1) inside the CNTs with $7 nm core diameter.13,14 Porosities of 0.003% are typically seen for MWCNT and 0.009% for SWCNT membranes. As-prepared MWCNT membranes were functionalized with benzoic acid via a static electrochemical diazonium grafting method.14,28 Electro-chemical grafting of aryl diazonium salts is an efcient method to modify inert conductive materials such as graphite and glassy carbon with covalently bonded organic molecules of high density.31,32 The pKa of benzoic acid is near 4.2, thus the surface of CNTs is negatively charged at the pH value used (pH 7).33 It should be pointed out that a high charge density is critical to obtaining an efcient electro-osmosis pumping.1,21 The charge density can be further quadrupled via a carbodiimide coupling reaction with Direct Blue 71 dye.14 Schematically the overall composite is shown in Fig. 1d. Surface chemistry of functionalized CNT membranes was characterized using Faradaic Electrochemical Impedance Spectroscopy28 and it is an effective method demonstrating surface modications of electrodes.34 Fig. 2 shows the Faradaic EIS Nyquist plots of the Fe(II/III)(CN)6 redox couple using asprepared and functionalized CNT membranes as the working electrode surface. The semicircle portion (Fig. 2a), observed at higher frequencies, corresponds to the electron transfer-limited process, whereas the linear part at the lower frequencies represents the electrochemical process limited by diffusion.35 When electron transfer processes are very fast, such as in the case of Fig. 2b, a linear diffusion tail can be clearly seen. However, a very slow electron-transfer step results in a large semicircle region that is not accompanied by a straight line, such as shown in Fig. 2a after diazonium grafting. The Nyquist plots have a single semicircle, the diameter of which is corresponding to the electron transfer resistance (Ret). The intercept of the semicircle with the
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positive biases (Fig. 3a), consistent with both electrophoresis and EOF. Compared to the diffusional ux at 0 mV, the ux of Ru (bpy)32+ can be enhanced by more than 8 times applying a 300 mV using an electrolyte solution containing 0.01 M KCl. Using a feed solution of stronger ionic strength (0.1 M), however, the ux of Ru(bpy)32+ was reduced by four fold consistent with increased screening of surface charge. Without the inuence of external electric eld, the diffusional uxes of both molecules are similar (<20% variation) in the electrolyte solutions of different ionic strengths (0.1 M and 0.01 M). The steady state ux of Ru (bpy)32+ through the CNT membrane can be calculated using the NernstPlanck equation:
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J(x) DdC(x)/d(x) zDFC(x)/RTdf(x)/dx + Cyeo

(2)

where D, C and z are diffusion coefcient, concentration, charge of the permeate molecule, respectively. F is Faraday constant and yeo is the electro-osmosis velocity. dC(x)/d(x) and df(x)/dx are trans-membrane concentration and potential gradients, respectively. In this case the ux J(x) is through open CNT pore area, not the total area of the sample. The porosity of the MWCNT membrane used for Fig. 3 is 0.0027% and sample area is 0.07 cm2. The three terms of eqn (2) are passive diffusional, electrophoretic, and electro-osmotic transport processes, respectively. According to the NernstPlanck equation, electrophoresis does not vary with the ionic strength of electrolyte solutions, given that the trans-membrane concentration and potential gradients remain xed. Thus electroosmotic convective ow is the only remaining mechanism for the enhanced ow of Ru(bpy)32+ using a feed solution of low ionic strength. However a more direct measure of electroosmotic ow is the ux of neutral molecule, caffeine.36 Eqn (2) can be simplied as:
Fig. 2 (a) Nyquist plots of Faradaic Electrochemical Impedance Spectra of bare, static diazonium grafted and S.G. CNTdye membranes; solution used is 5 mM K3Fe(CN)6 and K4Fe(CN)6 in 0.1 M KCl and 10 mM K2CO3 aqueous solution (pH 10.8), and applied bias is +230 mV; (b) amplied Fig. 3a.

J(x) DdC(x)/d(x) + Cyeo Jdiff. + Jeo

(3)

Subtracting diffusion (Jdiff.) from total ux, J(x), gives electroosmotic ow (Jeo). Electroosmotic velocity yeo can be calculated from eqn (4): yeo Jeo/C (4)

Zreal axis at high frequencies is equal to the sum of solution and contact resistances.28,35 EIS Nyquist plots (Fig. 2a) show that the charge transfer resistance (Ret) has increased from 200 to $300 000 ohms after electrochemical diazonium grafting. The grafted molecule, benzoic acid, is anionic at a pH value of 10.8 (pKa 4.2), and repels the ferro/ferri cyanide anions resulting in an increased Ret. After coupling anionic dye molecules, the density of negative charge is quadrupled and further steric bulk leads to a further Ret increase as shown in Fig. 2a. The experimental setup for permeation, electrophoretic and electro-osmotic studies is shown in Fig. 3c, and the area of the CNT membrane is 0.07 cm2. Two model molecules, charged Ru (bpy)32+ and electrically neutral caffeine were used for the investigation (Fig. 3b). Fig. 3a shows the ux of Ru(bpy)32+ and caffeine through a S.G. MWCNTdye membrane applying biases ranging from 300 to +300 mV. The voltage dependent transport of neutral caffeine molecules is direct evidence of the EOF process. Under an external electric eld, the general trend is that uxes of both cationic and neutral molecules were enhanced under negative biases, whereas the uxes were decreased applying
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Applying 300 mV bias, the observed yeo is as high as 0.036 cm s1 (0.12 cm s1 V1) for a S.G. MWCNTdye membrane as was calculated using the data shown in Fig. 3 and Table 1. This compares favorably to Takamura et al. who reported a very high electroosmotic ow velocity of up to 0.035 cm s1 V1 in SiO2 microuidic channel with a depth of 400 nm, which was fabricated using photolithography.37 The increase in EOF was nearly proportional to the negative applied bias while for the positive bias there was a slight decrease in ux consistent with a small EOF in the opposite direction due to a low concentration of caffeine in the permeate solution. Notably, this asymmetric EOF was also observed in carbonaceous AAO membranes.21 Diazonium salts of benzoic acid can be electrochemically grafted onto CNTs14,31,32 to increase surface charge density and electroosmotic ow. Fig. 4 shows the plots of caffeine uxes vs. the applied trans-membrane voltage for as-fabricated CNTs and S.G. CNT membranes. After diazonium grafting, the caffeine electroosmotic ow has been enhanced by 90% consistent with surface functionalization. It should be pointed out that
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Fig. 3 (a) Flux rates of caffeine and Ru(bpy)32+ through the S.G. CNT-dye membrane (0.07 cm2) with a porosity of 0.0027% under external electric eld; the solution used is 5 mM caffeine or Ru(bpy)32+ in 0.01 M or 0.1 M KCl aqueous solution. (b) Molecular structures of caffeine (1,3,7-trimethylxanthine) and Ru(bpy)32+ permeates; (c) diagram of the experimental setup for the permeation studies. Note: C.E, R.E and W.E represent counter, reference and working electrodes, respectively.

z potential of unmodied CNT membranes is negligible and little EOF is seen. The effective electrophoretic mobilities of K+ and Ca2+ ions through MWCNTs and SWCNTs were also calculated and

compared with their bulk values.38,39 The effective electrophoretic mobility (m) is measured by the ion ux as a function of bias: m Jpore Dx/eCV (5)

Table 1 Effect of applied voltage on the ux, enhancement factor (E), and electro-osmotic velocity of caffeine through the S.G. MWCNTdye membrane Jappa/mA cm2 0 1.8 3.7 5.3 Fluxa/nanomoles per cm2 per h 6.8 9.3 11.7 18.2 yeo/cm s1 0 0.018 0.023 0.036

E 1.0 1.4 1.7 2.7

V/mV 0 100 200 300

a The area of the MWCNT membrane used is 0.07 cm2 and the porosity is 0.0027%, the same as Fig. 3a.

where Jpore is ionic ux through the open pore area, Dx membrane thickness, C concentration of ion, e elemental charge, V applied bias across the membrane. Table 2 shows mobilities of 5 108 m2 V1 s1 in the SWCNT cores which is very close to the bulk values, supporting the hypothesis that CNTs are a relatively non-interacting CNT surface. It should be noted that the MWCNTs have sterically bulky dye molecules at pore entrances while SWCNTs have only carboxylate functionality from plasma oxidation. The increased steric hindrance reduces the mobility in MWCNTs compared to the bulk case, while in the unhindered SWCNT case is close to bulk mobility. Recently, the mobilities of ions within CNTs have been indirectly measured, through lifetimes of current pulse events, to be dramatically
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Fig. 4 Caffeine ux through the as-prepared and diazonium grafted MWCNT membrane with a porosity of 0.0025% as a function of bias; donor solution used is 5 mM caffeine in 0.01 M KCl aqueous solution. A much lower electro-osmosis effect is observed in the case of bare CNT membrane due to the low surface charge density.

enhanced by 2 orders of magnitude.24 This dramatic mobility enhancement is not seen under our conditions and may reect a mass transport limitation of ions to CNT pore entrance in the large area membrane geometry. However dramatic EOF velocities are not seen in this study, suggesting that mobilities within CNTs are closer to bulk value. Mobilities of a variety of ions through CNT membranes are an object of ongoing research. It is important to compare EOF performance in CNT membranes to other nanoporous systems to see if there is an advantage of the fast CNT cores. This would become apparent in

the achieved electroosmotic velocity (normalized to voltage), power efciency, and ion pumping efciency. Table 3 summarizes the comparison of EOF performance for CNT membranes, AAO/a-CNT membranes, AAO without functionalization, and AAO with anionic surface functionalization (SO3). Electroosmotic velocity was 13 orders of magnitude faster for the CNT samples supporting the primary hypothesis of enhanced EOF. Pumping power efciency is a critical parameter for application of EOF, whether in compact medical devices or industrial separations. The power efciency here is dened as power, that is current times voltage drop, divided by moles transported. Improvements in power consumption range from 25112 fold. For the high performance template-prepared a-CNT membranes21 presumably the large diameter (120 nm), that is well beyond the 3 nm Debye screening length, was the primary limiting factor and could be improved with reduced diameter. It is important to note here that in that study, the voltage drop across the membrane could not be reported due to it being a constant current experiment. However this paper reported the formation of bubbles on the counter electrode thus the bias was above 1.2 V and the power efciencies shown here are the highest estimate. Because our membranes have low porosities, we used caffeine instead of phenol21 for its higher UV-Vis absorption coefcient in the permeate concentration assay. The caffeine should give comparable measures of EOF as phenol since both are a measure of neutral solvent volume ux. To increase the surface charge density AAO membranes were treated with strong acids to increase the functional density of hydroxyl groups and EOF has been systematically studied.40,41 It is difcult to directly compare the results of those papers to the CNT membranes since the applied biases ranged from 4 to 40 volts, well above the voltage to split water. This process generates bubbles and changes the pH which acts as electrophoretic ions. To make a more appropriate comparison, we functionalized the

Table 2 Electrophoretic mobility of K+ in MWCNT membrane and Ca2+ in SWCNT membranea Applied voltage/mV 0.3 0.3 Electrophoretic mobility/m2 V1 s1 6.4 109 5.0 108 Bulk electrophoretic mobility/m2 V1 s138,39 7.6 108 6.2 108

Types of membrane MWCNTs SWCNTs

a

Types of ions K+ Ca2+

Note: porosities of MWCNT and SWCNT membranes are 0.015 and 0.0085%, respectively.

Table 3 Comparison of electro-osmosis power consumption of MWCNT, SWCNT, a-CNT/AAO and AAO membranes Diameter/ nm MWCNTs SWCNTs AAO/a-CNT21 AAO membrane AAO membrane functionalized (SO3) 7 1.5 120 20 20 Veo/ cm s1 V1 1.6 1.8 2.2 1.1 3.7 101 101 103 104 104 Power consumption / W h per nanomole 2.5 108 3.3 108 9.9 107 2.8 106 6.2 107 Power consumption ratio 1 1.3 40 112 25 Ratio of cations to caffeine 18 1a b 172c 38c

a Larger hydrated Ca2+ used as cation for SWCNT, while all others use K+. b Due to water hydrolysis above 1.2 V, direct comparison to ref. 21 is not possible. c Ratios of cations to caffeine for AAO and functionalized AAO membranes were calculated using current data: ux of K+ (It/(eN))/T; I is current, t is time in second, e is elementary charge, T is time in hour and N is Avogadro constant. Note: porosities of MW and SWCNT membranes used are 0.015 and 0.0085%, respectively.

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Fig. 5 (a) Schematic of highly efcient electro-osmotic pumping of caffeine using various cations, such as Ru(bpy)32+ (dia. z 1 nm), Ca2+ or K+ in SW or MWCNTs functionalized with negatively charged carboxylate groups: MWCNTs have $7 nm inner diameter; SWCNTs have inner diameters ranging from 0.82 nm; CAF: caffeine ($0.5 nm in diameter); (b) TEM image of SWCNTs with $2 nm inner diameter; (c) 3dimensional model of Ru(bpy)32+ moving in a (12,12) SWCNT.

AAO membrane with a high density of anionic sulfonate groups (SO3) via a combination of silanol and carbodiimide chemistry. The applied voltages (0.3 to 0.6 V) are below the splitting water and similar to our CNT membrane EOF transport conditions. It should be pointed out that electrochemical diazonium grafting cannot be applied to the AAO membrane since it is an insulator. As shown in Table 3, the MWCNT membrane consumes 112 times less energy to pump the same amount of electrically neutral caffeine compared to the unmodied AAO membrane, which is attributed to the lack of high density charged functional groups.41 After surface functionalization, its electroosmotic velocity has been enhanced due to the presence of a high density of SO3 functional groups on its inner wall; however it is still 25 times less energy efcient compared to the MWCNT membrane, due to the non-ideal surface properties of the AAO pore structure. Though power efciency is important, another form of efciency is the number of ions required to pump neutral molecules. As shown in Fig. 5a, using the same concentration of ions and neutral molecules, a much higher EOF efciency could be achieved when the size of pumping ions (cations) ts the diameter of CNTs. Consequently, fewer ions are needed to pump the same amount of neutral molecules, which is energetically more favorable. Fig. 5c shows a 3-dimensional model of Ru(bpy)32+ moving in a (12,12) SWCNT channel. For the smallest diameter SWCNTs (nominal $1.5 nm i.d.) using large diameter Ca2+ (0.8 nm hydrated diameter) or Ru(bpy)32+ (1.1 nm diameter), a 1 to 1 ratio of ion to neutral was achieved which is a 40 fold
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Fig. 6 (a) Flux of caffeine and Ru(bpy)32+ through the water plasma etched SWCNT membrane; (b) ux of Ca2+ and caffeine through a water plasma etched SWCNT membrane with a pore diameter 1.4 0.5 nm; (c) ux of K+ and caffeine through a water plasma etched MWCNT membrane with an average pore diameter of 7 nm. Solutions used are 5 mM Ru(bpy)32+ and 5 mM caffeine for (a), 5 mM Ca2+ and 5 mM caffeine for (b), 10 mM K+ and 5 mM caffeine for (c). Porosities of CNT membranes used for (a), (b) and (c) are 0.0023, 0.0085 and 0.015%, respectively, and the membrane area is 0.07 cm2.

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improvement over other systems. This approaches the ideal case of a single ion pushing a column of solvent through the CNT cores. Fig. 6a and b show the efcient pumping of neutral caffeine compared to Ca2+ and Ru(bpy)32+ with EOF velocity, power consumption and comparative ratios summarized in Table 3. It is expected that even higher EOF efciency can be obtained through improving the size distribution of SWCNTs (CheapTubes.com) diameters since a signicant fraction (50%) is >1.5 nm i.d. with several SWCNT diameters as large as 5 nm being seen in our TEM analysis (Fig. 5b). In the case of MWCNTs, with larger inner diameter (7 nm), more solvent and neutral molecules are able to move around the cation, reducing the cation pumping efciency (Fig. 6c). Using a 10 mM KCl and 5 mM caffeine donor solution, as many as 18 K+ ions (with a hydrated ionic diameter of 0.66 nm) are required to pump one neutral caffeine molecule through the MWCNT membrane. In the case of unmodied AAO membrane, as many as 178 K+ ions are required to pump one caffeine molecule. As expected, the unmodied AAO membrane has inefcient electroosmotic pumping due to the lack of a high density of charged functional groups.41 After grafting with sulfonate functional groups only 38 potassium ions are needed per caffeine, which is signicantly higher than that needed for SWCNTs (Table 3).

Conclusion
A facile microtome-cutting method has been developed to fabricate MWCNT and SWCNT membranes that show enhanced electroosmotic ow rates and efciency. Direct observation of neutral molecular transport under bias demonstrated the phenomena of electroosmotic pumping with velocities as high as 0.16 cm s1 V1, 82 fold higher than related nanoporous AAO/ a-CNT materials. Changes in electroosmotic ow as a function of ionic strength and surface charge functionality were also consistent with the electroosmotic ow phenomena. Appreciable electroosmotic pumping was observed at voltages (0.30.6 V) that are far below voltages of water splitting. Importantly power efciencies were 25110 fold improved to comparable nanoporous materials which has important application in separations and portable medical devices. High electroosmotic efciency was seen in terms of the ratio of ions needed to pump neutral molecules. 1 : 1 ratios are seen in small diameter SWCNTs that is approaching the condition for ideal electroosmosis where a single ion pushes a column of solvent and neutral molecules.

Acknowledgements
We would like to thank Dali Qian and Rodney Andrews from the Center for Applied Energy, University of Kentucky, for supplying MWCNTs. Facility support was provided by the Center for Nanoscale Science and Engineering and Electron Microscopy Center at the University of Kentucky. Financial support from NIH NIDA (R01DA018822), NSF CAREER (0348544), and DARPA (W911NF-09-1-0267).

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Nanoscale

This journal is The Royal Society of Chemistry 2011