Research Article Green Synthesis and Characterization of...

Research ArticleGreen Synthesis and Characterization of CarbonNanotubesPolyaniline Nanocomposites

Van Hoa Nguyen12 and Jae-Jin Shim1

1School of Chemical Engineering Yeungnam University Gyeongsan Gyeongbuk 712-749 Republic of Korea2Department of Chemistry Nha Trang University 2 Nguyen Dinh Chieu Nha Trang Vietnam

Correspondence should be addressed to Jae-Jin Shim jjshimyuackr

Received 16 October 2014 Revised 10 January 2015 Accepted 12 January 2015

Academic Editor Dhananjay Bodas

Copyright copy 2015 V H Nguyen and J-J ShimThis is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Carbon nanotubespolyaniline (CNTPANI) nanocomposites were synthesized by the interfacial polymerization of aniline inthe presence of CNTs using two green solvents water and an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate[bmim][BF

4]) as the two phasesThe formation and incorporation of PANI on the surface of the CNTswere confirmed by scanning

electron microscopy transmission electron microscopy X-ray diffraction Fourier transform infrared spectroscopy ultraviolet-visible spectroscopy and X-ray photoelectron spectroscopy The analyses showed that the surface of the CNTs was coated withdifferent morphologies of thin PANI layers depending on whether a HCl or HNO

3solution was used The thermal stability of the

composites was much better than that of the bare CNTs and pure PANI The as-prepared composites were also used to modify thenickel foam electrodes for characterization of the electrochemical properties

1 Introduction

Polyaniline (PANI) has attracted considerable attentionbecause of its unique and controllable chemical and electricalproperties environmental thermal and electrochemical sta-bility and interesting electronic optical and electroopticalproperties [1ndash4] PANI has a wide range of tunable propertiesemanating from its structural flexibility leading to poten-tial applications in many fields such as battery electrodesanticorrosive coatings energy storage systems gas sensorsand electrocatalytic devices [3 4] Moreover PANI has thehighest environmental stability and is recognized as the onlyconducting polymer stable in air [5] However PANI has lowconductivity which limits its electrochemical performanceand applications in developing electrical devices To over-come this problem CNTs have been assessed as potentialcandidates owing to their unique structure and excellentmechanical electrical and thermal properties as well as theirhigh surface area [6ndash8] A method to prepare composites ofthe two materials is needed to combine the advantages ofPANI and CNTs

Composites consisting of CNTs and PANI have beendeveloped for different applications in lithium ion batteriessupercapacitors catalysts solar cells nanodevices chemicalsensors and biosensors [6ndash10] Improved stability of thecomposites has been achieved by the synergistic combinationof the excellent conducting and mechanical properties ofCNTs sheets with the high pseudo capacitance of PANI [9]Moreover a coating of CNTs with polyaniline enhances theconductivity and mechanical strength remarkably resultingin excellent performance as an electrode material [10] How-ever most of these studies normally require toxic organicsolvents which may be harmful to the environment Toaddress this it is important to develop a facile and efficientmethod without toxic organic solvents Green solvents suchas supercritical carbon dioxide and ionic liquids (ILs) shouldbe developed to overcome these environmental concernsILs have unique properties such as extremely low volatilitywide liquid temperature range good thermal stability gooddissolving ability designable structures high ionic conduc-tivity wide electrochemical window and excellentmicrowave

Hindawi Publishing CorporationJournal of SpectroscopyVolume 2015 Article ID 297804 9 pageshttpdxdoiorg1011552015297804

2 Journal of Spectroscopy

absorbing ability [11 12] Previous studies successfully pre-pared polymers and nanocomposites in ILs [12ndash15]

In the present study CNTPANI nanocomposites wereprepared by in situ interfacial polymerization using two greensolvents water and [bmim][BF

4]Thismethodminimizes the

use of toxic organic solvents The products obtained werecharacterized using standard techniques The compositeswere also used to modify the nickel foam electrodes for char-acterization of the electrochemical properties

2 Experimental

21 Materials MWNTs (gt90 Aldrich) have a diameterand length of 10ndash50 nm and 01ndash10 120583m respectively Aniline(99 Aldrich) was distilled under reduced pressure priorto use [Bmim][BF

4] (gt98 Ionic Liquids Tech Germany)

was kept in a vacuum oven at 100∘C for 24 h to removethe volatile impurities prior to use Potassium persulfate(KPS) and the other reagents were of analytical grade andused as received Water was deionized in the laboratory Thecarboxylic acid-functionalized CNTs (CNT-COOH) wereobtained by sonication in a mixture of concentrated H

2SO4

and HNO3(3 1 vv) at 50∘C for 10 hours followed by

centrifugation of 15000 rpm and washing with deionizedwater until the decanted solution was neutral

22 Synthesis of CNTPANIComposite TheCNTPANI com-posites were prepared using a methodology reported else-where [14] In a typical experiment 05 g anilinewas dissolvedin 10mL IL and 50mg CNT-COOH was dispersed in 10mLDI water which was followed by the addition of 05mLhydrochloric acid (1M HCl) or nitric acid (1M HNO

3) and

29 g of KPS The KPS to aniline molar ratio was 2 1 Thetwo solutions were transferred carefully to a vial and aninterface was formed between the aqueous phase and the ILphase Green PANI that formed at the interface was thendiffused gradually into the aqueous phase After 3 h the entirewater phase was filled homogeneously with a dark-greenCNTPANI nanocomposite The aqueous phase was thencollected and washed with ethanol and water to remove theunreacted chemicals and aniline oligomers The CNTPANIcomposite obtained was dried in a vacuum oven at 40∘C for24 h

23 Characterization The samples were characterized byscanning electronmicroscopy (SEM Hitachi S-4200) trans-mission electron microscopy (TEM Philips CM-200) atan acceleration voltage of 200 kV X-ray diffraction (XRDPANalytical XrsquoPert-PRO MPD) using Cu K120572 radiation andX-ray photoelectron spectroscopy (XPSULVAC-PHIQuan-tera SXM) using an Al X-ray source The Fourier transforminfrared (FTIR Nicolet iS10 Thermo Scientific) spectra wererecorded over 500ndash4000 cmminus1 at a resolution of 16 cmminus1within 32 scans using a diamond ATR attachment Theultraviolet-visible (UV-vis) spectra were recorded over 200ndash800 nm using a UV-Vis-NIR spectrophotometer (Cary 5000Varian) Thermogravimetric analysis (TGA) was performedon a simultaneous TGAdifferential scanning calorimetry

(DSC) analyzer (SDT Q600 TA Instrument) from 25 to600∘C at a heating rate of 10∘Cmin under a nitrogen atmos-phere

All electrochemical experiments were performed on aVersaSTAT 3 AMETEKModel (Princeton Applied ResearchUSA) in a three-electrode configuration Platinum foil anda saturated calomel electrode were used as the counter andreference electrodes respectively The working electrodeswere fabricated by mixing the as-prepared powder (3mg80wt ) with 15 wt acetylene black and 5wt pol-ytetrafluorene-ethylene (PTFE) binder and pressed ontonickel foam current-collectors (10 cm times 10 cm) The mea-surements were carried out in a 1MKOH aqueous electrolyteat room temperature The specific capacitance (119862

119904) of the

electrode was calculated using the following equation

119862 =

119868119905

119898Δ119881

(1)

where 119862 119868 119905 119898 and Δ119881 are the specific capacitance(F gminus1) discharging current (A) discharging time (s) massof active materials (g) and discharging potential range (V)respectively

3 Results and Discussion

Scheme 1 presents the preparation process of the CNTPANIcomposites The aniline monomer was dissolved in[bmim][BF

4] and the functionalized CNTs were dispersed

in an aqueous acid solution with the oxidant KPS Thewater layer was spread carefully onto an equal volume ofIL forming a waterIL interface After approximately 1mingreen PANI formed at the interface and migrated graduallyto the aqueous phase Finally the entire water phase was filledhomogeneously with a dark-green CNTPANI compositewhereas the IL phase showed a red-orange color possiblydue to the formation of aniline oligomers The compositewas collected and purified Scheme 1 also presents typicalsnapshots of the synthetic process of CNTPANI compositesin the waterIL system

The surface morphology of the as-prepared compositeswas examined by SEM and TEM Figure 1 presents SEMand TEM images of the CNTPANI composites prepared intwo different media HCl and HNO

3aqueous solution The

surfaces of the CNTs were covered completely with PANIlayers On the other hand themorphology of the PANI layerswas different nanosheet-like for the HCl medium and nano-particle-like for the HNO

3medium The crystal structure of

conducting PANI has a considerable effect on its electricalconductivity A previous study reported that strong elec-trical conductivity could be induced by the highly orderedchain structure of conducting polymers [16] Figure 2 showsthe XRD pattern of the modified CNTs pure PANI andCNTPANI compositesTheCNT spectrum has a very strongpeak at 265∘ 2120579 Pure PANI showed a typical crystallinepattern which was similar to that of the CNTPANI compos-ites The main diffraction peaks at 2126∘ 2982∘ and 3089∘2120579 with hkl values of (100) (211) and (020) respectivelyrepresent emeraldine PANI [16] The peaks centered at 2126∘

Journal of Spectroscopy 3

Oxidation

Water

[Bmim][BF4]

0min 1min 30min 180min

ANI KPSHCl or HNO3

Bare CNTs CNT-COOH CNTPANI

PolymerizationH2SO4 HNO3

(3 1)

Scheme 1 Schematic diagram of the synthesis of the CNTPANI composite and the progress of the interfacial polymerization of aniline in awaterIL system in the presence of CNT

(a)

CNT

PANI

100nm

(b)

(c)

PANI

CNT

100nm

(d)

Figure 1 SEM (a c) and TEM (b d) images of CNTPANI composites prepared in HCl (a b) and HNO3(c d) medium


10 20 30 40 50 60 70 80

(020

)(211

)

(d)

(c)

(b)

Inte

nsity

(au

)

2120579 (deg)

(a)

(100

)

Figure 2 XRD patterns of pure PANI (a) CNTPANI compositesprepared in HCl (b) and HNO

3(c) medium and CNT-COOH (d)

3500 3000 2500 2000 1500 1000

1565

15621490

1493

1092

3224

Inte

nsity

(au

)

3224 1289

12861085

3440

(b)

(c)

(d)

2359

(a)

173629291636

1125

Wavenumber (cmminus1)

Figure 3 FTIR spectra of bare CNTs (a) CNT-COOH (b) purePANI (c) and CNTPANI composites prepared in HClmedium (d)

and 2383∘ 2120579 were assigned to the periodicity parallel andperpendicular respectively to the PANI chains XRD showedthat PANI has a relatively highly ordered crystal structurewhich improves the crystallinity of the composite consider-ably and is expected to exhibit high electrical conductivityThe decrease in peak height of the CNT planes and the shiftto the left in the composite might be caused by the polymercoating of the CNTs surface in the polymerization process

FTIR spectroscopy provides information on the chemicalstructures of the bare CNTs CNTminusCOOH pure PANI andCNTPANI composites (Figure 3) The spectrum of bareCNTs showed no clear peaks at 500ndash3800 cmminus1 (Figure 3(a))The FTIR spectrum fromCNTminusCOOH showed a broad peakat about 3440 cmminus1 which could be assigned to the OndashHstretch from carboxyl groups (O=CminusOH and CminusOH) whilethe peak at 2359 cmminus1 can be associated with the OminusH stretchfrom strongly hydrogen-bonded ndashCOOH (Figure 3(b)) [17]

0 100 200 300 400 500 60050

60

70

80

90

100

(d)

(c)(b)

Wei

ght (

)

(a)

Temperature (∘C)

Figure 4 TGA thermograms of CNT-COOH (a) CNTPANI com-posite prepared in HCl (b) and HNO

3(c) medium and pure

PANI (d) obtained with a ramping rate of 10∘Cmin under a N2

atmosphere

Moreover the curve showed the characteristic C=C stretch-ing at 1634 cmminus1 while C=O and CndashO stretching vibrationsare observed at 1713 and 1125 cmminus1 respectivelyThe spectrumof pure PANI showed usual characteristic stretching vibrationbands at 1562 cmminus1 (C=C quinoid rings) 1490 cmminus1 (C=Cbenzenoid rings) 1286 cmminus1 (CndashN) and 1085 cmminus1 (CndashH) (Figure 3(c)) In the case of the CNTPANI composite(Figure 3(d)) the FTIR spectrumwas similar to that of PANIThese results confirmed that the surface of the CNTs waswrapped completely with PANI

Figure 4 shows the TGA data of the modified CNTs purePANI and CNTPANI composites under a nitrogen atmos-phere All the samples showed similar decomposition curvesOn the other hand pure PANI had much lower thermal sta-bility than the CNTs and CNTPANI composite The gradualweight loss of PANI between 100 and 280∘C was attributed tothe deprotonation of PANI through the loss of dopant HClThe major weight loss (sim30) before 600∘C was assigned tothe degradation and decomposition of PANI with differentdegrees of polymerization The weight reduction of CNTsobserved at temperatures less than 100∘C and between 150and 300∘C was consistent with the degradation of absorbedwater and oxygen functional groups respectively ThesendashCOOH groups on the walls of the CNTs not only enhancedthe dispersibility but also could anchor PANI to the surfaceFor the composite the gradual degradation below 280∘C wasattributed to the evaporation of absorbed solvent and thedecomposition of oxygen groups on the CNT surface Theweight loss at approximately 300∘C was consistent with thedegradation and decomposition of PANI TGA suggestedthat the CNTPANI composite has higher and slightly lowerthermal stability pure PANI This might be because of thestrong interactions between CNT and PANI which imposea restriction on the decomposition of the ndashCOOH groupsremaining on the CNT surface These interactions can result


C 1s

5

10

15

20

25

30

35

40

45

50

Cou

nts

292 290 288 286 284 282 280

Binding energy (eV)

CndashC

CndashNC=N

120587-120587lowast

Pure PANItimes10

2

(a)

N 1s

ndashN=

ndashNHndash

ndashN+

Cou

nts

Binding energy (eV)

12

14

16

18

20

22

408 406 404 402 400 398 396 394 392 390

Pure PANItimes10

2

(b)

5

10

15

20

25

30

35

40

45

291 288 285 282

times102

Cou

nts

Binding energy (eV)

C 1s

CndashN

CndashC

CndashO

OndashC=O

CNTPANI

(c)

20

25

30

35

40

406 404 402 400 398

ndashN+

times102

Cou

nts

Binding energy (eV)

N 1s

ndashN=

ndashNHndash

CNTPANI

(d)

Figure 5 XPS survey spectra of pure PANI and the CNTPANI composites prepared in HCl medium at core-levels of C 1s and N 1s

in homogeneous heating and the avoidance of heat concen-trations [18]

Figure 5 shows the XPS spectrum of the N 1s core level ofpure PANI which is composed of three subpeaks centeredat 3978 eV (ndashN=) 3990 eV (ndashNHndash) and 4001 eV (ndashN+ndash)When combined with CNTs the N+ peak (4045 eV) of theCNTndashPANI composite had a higher binding energy thanpure PANI The highest binding energy peak was assignedto the protonated amine units Figure 5 also shows the C1s spectrum of pure PANI The lowest binding energy fea-ture (2831 eV) was assigned to the CndashC group in the aromaticring The second peak was attributed to the CndashN bonds(2841 eV) The feature at 2849 eV can be attributed to C=NAn additional component centered at 2862 eVwas attributedto the 120587-120587lowast ldquoshake-uprdquo satellite Compared to the C 1s

spectrum of the CNTndashPANI composite these C 1s spectrashowed asymmetric characteristics indicating the presenceof structural defects These C 1s spectra can be separated intofour peaks which were centered at approximately 2857 (CndashC) 2874 (CndashN) 2887 (CndashO) and 2897 eV (OndashC=O) Asa result XPS showed that the CNTndashPANI composites hadbeen doped successfully with CNT whichmay result in betterelectrochemical properties of the composite

Figure 6 presents the UV-vis absorption spectra of purePANI functionalized CNT and CNTPANI dispersed inethanol Dispersed individual CNTs are active in the UVndashvis region and exhibit characteristic bands at approximately250 nm corresponding to additional absorption due to the 1DvanHove singularities [19] (Figure 5(a))The PANI spectrumrevealed a sharp peak at 209 nm which was assigned to


200 300 400 500 600 700

(d)

(c)(b)

Inte

nsity

(au

)

Wavenumber (nm)

(a)

Figure 6 UV-visible spectra of the CNT-COOH (a) CNTPANI composite prepared in HCl (b) and HNO3(c) medium and pure PANI (d)

in ethanol

00 01 02 03 04 05 06minus40

minus20

0

20

40

60

Curr

ent (

mA

)

Potential (V versus SCE)

CNTPANI (using HNO3)CNTPANI (using HCl)

Bare CNT-COOHPure PANI

(a)

0 20 40 60 80 100 120 140

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)

CNTPANI (using HNO3)CNTPANI (using HCl) Bare CNT-COOH

Pure PANI

(b)

Figure 7 (a) CV curves of pure PANI bare CNT-COOH and CNTPANI composites at scan rate of 10V sminus1 (b) galvanostatic dischargecurves of pure PANI bare CNT-COOH and CNTPANI composites at a current density of 2A gminus1

the 120587-120587lowast transition in molecular conjugation A weak peak at265 nm and broad peak at approximately 415 nm originatedfrom the charged cationic species called polarons [20] Forthe CNTPANI composites prepared in both HCl and HNO

3

media two peaks were observed at 207 and 268 nm due toa 120587-120587 interaction between the PANI chains and CNTs in thecomposite Compared to PANI the peak shift from 415 nm to372 nm indicated that PANI is protonated in the synthesizedcomposite The UV-vis absorption results confirmed thestrong interaction between the PANI polymer and carbontubes

The electrochemical performance of the CNTPANIcomposites as active supercapacitor electrodes was examined

by cyclic voltammetry (CV) electrochemical impedancespectroscopy (EIS) and chronopotentiometry (CP) carriedout in a three-electrode system using a SCE and platinum foilas the reference and counter electrode (Figures 7 and 8) Atthe same scan rate of 50mV sminus1 (Figure 7(a)) the CNTPANIcomposites exhibited a much higher resulting current anda more rectangular shape than those of the bare CNT-COOH and the pure PANI Interestingly the CNTPANI(prepared in a HNO

3solution) electrode exhibited a much

higher current than those of the CNTPANI (prepared ina HCl solution) electrode suggesting that the compositedoped with H+ from HNO

3had higher electron trans-

port (Figures 8(a) and 8(b)) The improved electrochemical


minus01 00 01 02 03 04 05 06 07minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(a)

minus01 00 01 02 03 04 05 06 07

minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(b)

0 20 40 60 80 100

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)

2A gminus135A gminus1

5A gminus1


(c)

0 20 40 60 80 100

00

01

02

03

04

05Po

tent

ial (

V v

ersu

s SCE

)

Time (s)

2

35

5

75

15

A gminus1

A gminus1

A gminus1

A gminus1A gminus1

(d)

0 50 100 150 200 250 300 350

0

100

200

300

400

500

600

700

0 2 4 6 8 1002468

10

Bare CNT-COOH

Pure PANI

minusZ998400998400

(Ohm

)

minusZ998400998400

(Ohm

)

Z998400 (Ohm)

Z998400 (Ohm)

CNTPANI(using HCl)

CNTPANI(using HNO3)

(e)

0 2 4 6 8 10 12 14 16

Current density (A gminus1)

0

100

200

300

400

500

Spec

ific c

apac

itanc

e (F

gminus1)


Bare CNT-COOH

Pure PANI

(f)

Figure 8 CV curves of the CNTPANI composite prepared in HCl (a) and HNO3(b) in a 1M KOH solution at different scan rates

galvanostatic discharge curves of the CNTPANI composites prepared in HCl (a) and HNO3(b) at different current densities (e) Nyquist

plots of the pure PANI bare CNT-COOH and CNTPANI composites (f) the specific capacitance of the pure PANI bare CNT-COOH andCNTPANI composite electrodes at different current densities


performance was also confirmed by galvanostatic charge-discharge tests performed under the same current density forpure PANI bare CNT-COOH and CNTPANI (Figure 7(b))and at different current densities (Figures 8(c) and 8(d)) Inparticular two composite electrodes showed excellent rateperformance in comparison to that of pure PANI and bareCNT-COOH Moreover a pair of smaller platforms with thestarting and ending potentials close to those in the CV curves(Figures 8(a) and 8(b)) are shown in the discharge curves(Figures 8(c) and 8(d)) which is a typical characteristic ofthe existence of redox reactions during the charge-dischargeprocess In addition all discharge curves showed a verysmall IR drop which indicated the low internal resistanceof the electrodes Figure 8(e) presents the impedance curvesfor the pure PANI bare CNT-COOH and CNTPANIelectrodes measured in a 1M KOH electrolyte solution Themore vertical line in the low and high frequency regionsindicated the more capacitive behavior of the electrodesFigure 8(f) summarizes the specific capacitance at differentcurrent densities calculated from the discharge curves TheCNTPANI composites yielded much enhanced capacitanceperformance compared to that of the pure PANI and bareCNT-COOH In the other hand the CNTPANI (preparedin HNO

3solution) electrode exhibited enhanced capacitance

performance with an approximate 8 increase in specificcapacitance compared to that of CNTPANI (prepared inHCl solution) electrode What is more the specific capaci-tance obtained in our work is considerable compared withthe other morphologies that have been reported in litera-tures such as SWCNTPANI (350ndash485 F gminus1) [21ndash23] porouscarbonPANI (160ndash180 F gminus1) [24 25] MWCNTPANI (322ndash606 F gminus1) [26ndash29] activated carbonPANI (380ndash500 F gminus1)[30 31] and carbon nanofiberPANI (264 F gminus1) [32]

4 Conclusions

CNTPANI composites were prepared efficiently in an IL-water system via the typical interfacial polymerization of ananiline monomer XRD confirmed the highly ordered chainstructure of pure PANI and PANI in the composite SEMand TEM indicated that the polymer layer almost completelycovered the carbon tubes The resulting CNTPAN compos-ite showed higher thermal stability than pure PANI Theelectrochemical performance of the as-prepared CNTPANIcomposites as active supercapacitor material electrodes wasevaluated The CNTPANI (prepared in HNO

3solution)

electrode showed enhanced capacitance performancewith anapproximate 8 increase in specific capacitance comparedto that of the CNTPANI (prepared in a HCl solution)electrode This experimental method is a facile efficient andgreen route that can be used to develop other PANI-basedcomposites

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

This research was supported by the Priority Research Cen-ters Program through the National Research Foundationof Korea (NRF) funded by the Ministry of Education(2014R1A6A1031189)

References

[1] A P Alivisatos ldquoSemiconductor clusters nanocrystals andquantum dotsrdquo Science vol 271 no 5251 pp 933ndash937 1996

[2] C Dhand M Das M Datta and B D Malhotra ldquoRecentadvances in polyaniline based biosensorsrdquo Biosensors and Bio-electronics vol 26 no 6 pp 2811ndash2821 2011

[3] S Bhadra D Khastgir N K Singha and J H Lee ldquoProgressin preparation processing and applications of polyanilinerdquoProgress in Polymer Science vol 34 no 8 pp 783ndash810 2009

[4] T A Sergeyeva N V Lavrik S A Piletsky A E Rachkov andA V Elrsquoskaya ldquoPolyaniline label-based conductometric sensorfor IgG detectionrdquo Sensors and Actuators B Chemical vol 34no 1ndash3 pp 283ndash288 1996

[5] Y C Luo and J S Do ldquoUrea biosensor based on PANi(urease)-NafionAu composite electroderdquo Biosensors and Bioelectronicsvol 20 no 1 pp 15ndash23 2004

[6] V H Nguyen and J-J Shim ldquoFacile synthesis and character-ization of carbon nanotubessilver nanohybrids coated withpolyanilinerdquo SyntheticMetals vol 161 no 19-20 pp 2078ndash20822011

[7] V H Nguyen and J-J Shima ldquoSupercritical fluid-assistedsynthesis of a carbon nanotubes-grafted biocompatible polymercompositerdquo Composite Interfaces vol 20 no 2 pp 155ndash1622013

[8] M S Shamsudin A B Suriani S Abdullah S Y S Yahyaand M Rusop ldquoImpact of thermal annealing under nitrogenambient on structural micro-Raman and thermogravimetricanalyses of camphoric-CNTrdquo Journal of Spectroscopy vol 2013Article ID 167357 6 pages 2013

[9] C Oueiny S Berlioz and F-X Perrin ldquoCarbon nanotube-polyaniline compositesrdquo Progress in Polymer Science vol 39 no4 pp 707ndash748 2014

[10] P Gajendran and R Saraswathi ldquoPolyaniline-carbon nanotubecompositesrdquo Pure and Applied Chemistry vol 80 no 11 pp2377ndash2395 2008

[11] J-H Pang X Liu M Wu Y-Y Wu X-M Zhang and R-CSun ldquoFabrication and characterization of regenerated cellulosefilms using different ionic liquidsrdquo Journal of Spectroscopy vol2014 Article ID 214057 8 pages 2014

[12] V H Nguyen Y P Ren Y R Lee D Tuma B K Min andJ J Shim ldquoMicrowave-assisted synthesis of carbon nanotube-TiO2nanocomposites in ionic liquid for the photocatalytic

degradation of methylene bluerdquo Synthesis and Reactivity inInorganic Metal-Organic and Nano-Metal Chemistry vol 42no 2 pp 296ndash301 2012

[13] V H Nguyen Y Haldorai Q L Pham S K Noh W SLyoo and J-J Shim ldquoPreparation of poly(vinyl pivalate) micro-spheres by dispersion polymerization in an ionic liquid andsaponification for the preparation of poly(vinyl alcohol) withhigh syndiotacticityrdquo European Polymer Journal vol 46 no 11pp 2190ndash2198 2010

[14] V H Nguyen L Tang and J-J Shim ldquoElectrochemical prop-erty of graphene oxidepolyaniline composite prepared by in


situ interfacial polymerizationrdquo Colloid and Polymer Sciencevol 291 no 9 pp 2237ndash2243 2013

[15] V H Nguyen and J-J Shim ldquoIonic liquid mediated synthesis ofgraphene-TiO

2hybrid and its photocatalytic activityrdquoMaterials

Science and Engineering B vol 180 no 1 pp 38ndash45 2014[16] J P Pouget M E Jozefowicz A J Epstein X Tang and A G

MacDiarmid ldquoX-ray structure of polyanilinerdquoMacromoleculesvol 24 no 3 pp 779ndash789 1991

[17] M A Atieh O Y Bakather B Al-Tawbini A A Bukhari FA Abuilaiwi and M B Fettouhi ldquoEffect of carboxylic func-tional group functionalized on carbon nanotubes surface onthe removal of lead from waterrdquo Bioinorganic Chemistry andApplications vol 2010 Article ID 603978 9 pages 2010

[18] H Wang Q Hao X Yang L Lu and X Wang ldquoEffectof graphene oxide on the properties of its composite withpolyanilinerdquo ACS Applied Materials and Interfaces vol 2 no 3pp 821ndash828 2010

[19] J Yu N Grossiord C E Koning and J Loos ldquoControllingthe dispersion of multi-wall carbon nanotubes in aqueoussurfactant solutionrdquo Carbon vol 45 no 3 pp 618ndash623 2007

[20] J Stejskal P Kratochvıl and N Radhakrishnan ldquoPolyanilinedispersions 2 UVmdashVis absorption spectrardquo Synthetic Metalsvol 61 no 3 pp 225ndash231 1993

[21] V Gupta and N Miura ldquoPolyanilinesingle-wall carbon nan-otube (PANISWCNT) composites for high performancesupercapacitorsrdquo Electrochimica Acta vol 52 no 4 pp 1721ndash1726 2006

[22] V Gupta and N Miura ldquoInfluence of the microstructure onthe supercapacitive behavior of polyanilinesingle-wall carbonnanotube compositesrdquo Journal of Power Sources vol 157 no 1pp 616ndash620 2006

[23] Y-K Zhou B-L HeW-J Zhou andH-L Li ldquoPreparation andelectrochemistry of SWNTPANI composite films for electro-chemical capacitorsrdquo Journal of the Electrochemical Society vol151 no 7 pp A1052ndashA1057 2004

[24] W-C Chen and T-C Wen ldquoElectrochemical and capacitiveproperties of polyaniline-implanted porous carbon electrodefor supercapacitorsrdquo Journal of Power Sources vol 117 no 1-2pp 273ndash282 2003

[25] W-C Chen T-C Wen and H S Teng ldquoPolyaniline-depositedporous carbon electrode for supercapacitorrdquo ElectrochimicaActa vol 48 no 6 pp 641ndash649 2003

[26] S R Sivakkumar W J Kim J-A Choi D R MacFarlaneM Forsyth and D-W Kim ldquoElectrochemical performanceof polyaniline nanofibres and polyanilinemulti-walled carbonnanotube composite as an electrode material for aqueous redoxsupercapacitorsrdquo Journal of Power Sources vol 171 no 2 pp1062ndash1068 2007

[27] H Y Mi X G Zhang S Y An X G Ye and S D YangldquoMicrowave-assisted synthesis and electrochemical capacitanceof polyanilinemulti-wall carbon nanotubes compositerdquo Elec-trochemistry Communications vol 9 no 12 pp 2859ndash28622007

[28] Y Zhou Z-Y Qin L Li et al ldquoPolyanilinemulti-walled carbonnanotube composites with corendashshell structures as supercapac-itor electrode materialsrdquo Electrochimica Acta vol 55 no 12 pp3904ndash3908 2010

[29] B Dong B-L He C-L Xu and H-L Li ldquoPreparation andelectrochemical characterization of polyanilinemulti-walledcarbon nanotubes composites for supercapacitorrdquo MaterialsScience and Engineering B Solid-State Materials for AdvancedTechnology vol 143 no 1ndash3 pp 7ndash13 2007

[30] J H Park and O O Park ldquoHybrid electrochemical capacitorsbased on polyaniline and activated carbon electrodesrdquo Journalof Power Sources vol 111 no 1 pp 185ndash190 2002

[31] M J Bleda-Martınez C Peng S Zhang G Z Chen EMorallon and D Cazorla-Amoros ldquoElectrochemical methodsto enhance the capacitance in activated carbonpolyanilinecompositesrdquo Journal of the Electrochemical Society vol 155 no9 pp A672ndashA678 2008

[32] J Jang J Bae M Choi and S-H Yoon ldquoFabrication andcharacterization of polyaniline coated carbon nanofiber forsupercapacitorrdquo Carbon vol 43 no 13 pp 2730ndash2736 2005

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


absorbing ability [11 12] Previous studies successfully pre-pared polymers and nanocomposites in ILs [12ndash15]

In the present study CNTPANI nanocomposites wereprepared by in situ interfacial polymerization using two greensolvents water and [bmim][BF

4]Thismethodminimizes the

use of toxic organic solvents The products obtained werecharacterized using standard techniques The compositeswere also used to modify the nickel foam electrodes for char-acterization of the electrochemical properties

2 Experimental

21 Materials MWNTs (gt90 Aldrich) have a diameterand length of 10ndash50 nm and 01ndash10 120583m respectively Aniline(99 Aldrich) was distilled under reduced pressure priorto use [Bmim][BF

4] (gt98 Ionic Liquids Tech Germany)

was kept in a vacuum oven at 100∘C for 24 h to removethe volatile impurities prior to use Potassium persulfate(KPS) and the other reagents were of analytical grade andused as received Water was deionized in the laboratory Thecarboxylic acid-functionalized CNTs (CNT-COOH) wereobtained by sonication in a mixture of concentrated H

2SO4

and HNO3(3 1 vv) at 50∘C for 10 hours followed by

centrifugation of 15000 rpm and washing with deionizedwater until the decanted solution was neutral

22 Synthesis of CNTPANIComposite TheCNTPANI com-posites were prepared using a methodology reported else-where [14] In a typical experiment 05 g anilinewas dissolvedin 10mL IL and 50mg CNT-COOH was dispersed in 10mLDI water which was followed by the addition of 05mLhydrochloric acid (1M HCl) or nitric acid (1M HNO

3) and

29 g of KPS The KPS to aniline molar ratio was 2 1 Thetwo solutions were transferred carefully to a vial and aninterface was formed between the aqueous phase and the ILphase Green PANI that formed at the interface was thendiffused gradually into the aqueous phase After 3 h the entirewater phase was filled homogeneously with a dark-greenCNTPANI nanocomposite The aqueous phase was thencollected and washed with ethanol and water to remove theunreacted chemicals and aniline oligomers The CNTPANIcomposite obtained was dried in a vacuum oven at 40∘C for24 h

23 Characterization The samples were characterized byscanning electronmicroscopy (SEM Hitachi S-4200) trans-mission electron microscopy (TEM Philips CM-200) atan acceleration voltage of 200 kV X-ray diffraction (XRDPANalytical XrsquoPert-PRO MPD) using Cu K120572 radiation andX-ray photoelectron spectroscopy (XPSULVAC-PHIQuan-tera SXM) using an Al X-ray source The Fourier transforminfrared (FTIR Nicolet iS10 Thermo Scientific) spectra wererecorded over 500ndash4000 cmminus1 at a resolution of 16 cmminus1within 32 scans using a diamond ATR attachment Theultraviolet-visible (UV-vis) spectra were recorded over 200ndash800 nm using a UV-Vis-NIR spectrophotometer (Cary 5000Varian) Thermogravimetric analysis (TGA) was performedon a simultaneous TGAdifferential scanning calorimetry

(DSC) analyzer (SDT Q600 TA Instrument) from 25 to600∘C at a heating rate of 10∘Cmin under a nitrogen atmos-phere

All electrochemical experiments were performed on aVersaSTAT 3 AMETEKModel (Princeton Applied ResearchUSA) in a three-electrode configuration Platinum foil anda saturated calomel electrode were used as the counter andreference electrodes respectively The working electrodeswere fabricated by mixing the as-prepared powder (3mg80wt ) with 15 wt acetylene black and 5wt pol-ytetrafluorene-ethylene (PTFE) binder and pressed ontonickel foam current-collectors (10 cm times 10 cm) The mea-surements were carried out in a 1MKOH aqueous electrolyteat room temperature The specific capacitance (119862

119904) of the

electrode was calculated using the following equation

119862 =

119868119905

119898Δ119881

(1)

where 119862 119868 119905 119898 and Δ119881 are the specific capacitance(F gminus1) discharging current (A) discharging time (s) massof active materials (g) and discharging potential range (V)respectively

3 Results and Discussion

Scheme 1 presents the preparation process of the CNTPANIcomposites The aniline monomer was dissolved in[bmim][BF

4] and the functionalized CNTs were dispersed

in an aqueous acid solution with the oxidant KPS Thewater layer was spread carefully onto an equal volume ofIL forming a waterIL interface After approximately 1mingreen PANI formed at the interface and migrated graduallyto the aqueous phase Finally the entire water phase was filledhomogeneously with a dark-green CNTPANI compositewhereas the IL phase showed a red-orange color possiblydue to the formation of aniline oligomers The compositewas collected and purified Scheme 1 also presents typicalsnapshots of the synthetic process of CNTPANI compositesin the waterIL system

The surface morphology of the as-prepared compositeswas examined by SEM and TEM Figure 1 presents SEMand TEM images of the CNTPANI composites prepared intwo different media HCl and HNO

3aqueous solution The

surfaces of the CNTs were covered completely with PANIlayers On the other hand themorphology of the PANI layerswas different nanosheet-like for the HCl medium and nano-particle-like for the HNO

3medium The crystal structure of

conducting PANI has a considerable effect on its electricalconductivity A previous study reported that strong elec-trical conductivity could be induced by the highly orderedchain structure of conducting polymers [16] Figure 2 showsthe XRD pattern of the modified CNTs pure PANI andCNTPANI compositesTheCNT spectrum has a very strongpeak at 265∘ 2120579 Pure PANI showed a typical crystallinepattern which was similar to that of the CNTPANI compos-ites The main diffraction peaks at 2126∘ 2982∘ and 3089∘2120579 with hkl values of (100) (211) and (020) respectivelyrepresent emeraldine PANI [16] The peaks centered at 2126∘


Oxidation

Water

[Bmim][BF4]


ANI KPSHCl or HNO3



(3 1)


(a)

CNT

PANI

100nm

(b)

(c)

PANI

CNT

100nm

(d)



10 20 30 40 50 60 70 80

(020

)(211

)

(d)

(c)

(b)

Inte

nsity

(au

)

2120579 (deg)

(a)

(100

)



3500 3000 2500 2000 1500 1000

1565

15621490

1493

1092

3224

Inte

nsity

(au

)

3224 1289

12861085

3440

(b)

(c)

(d)

2359

(a)

173629291636

1125





0 100 200 300 400 500 60050

60

70

80

90

100

(d)

(c)(b)

Wei

ght (

)

(a)

Temperature (∘C)




atmosphere




C 1s

5

10

15

20

25

30

35

40

45

50

Cou

nts

292 290 288 286 284 282 280

Binding energy (eV)

CndashC

CndashNC=N

120587-120587lowast

Pure PANItimes10

2

(a)

N 1s

ndashN=

ndashNHndash

ndashN+

Cou

nts

Binding energy (eV)

12

14

16

18

20

22

408 406 404 402 400 398 396 394 392 390

Pure PANItimes10

2

(b)

5

10

15

20

25

30

35

40

45

291 288 285 282

times102

Cou

nts

Binding energy (eV)

C 1s

CndashN

CndashC

CndashO

OndashC=O

CNTPANI

(c)

20

25

30

35

40

406 404 402 400 398

ndashN+

times102

Cou

nts

Binding energy (eV)

N 1s

ndashN=

ndashNHndash

CNTPANI

(d)







200 300 400 500 600 700

(d)

(c)(b)

Inte

nsity

(au

)

Wavenumber (nm)

(a)


in ethanol

00 01 02 03 04 05 06minus40

minus20

0

20

40

60

Curr

ent (

mA

)




(a)

0 20 40 60 80 100 120 140

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)


Pure PANI

(b)



3









minus01 00 01 02 03 04 05 06 07minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(a)

minus01 00 01 02 03 04 05 06 07

minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(b)

0 20 40 60 80 100

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)


5A gminus1


(c)

0 20 40 60 80 100

00

01

02

03

04

05Po

tent

ial (

V v

ersu

s SCE

)

Time (s)

2

35

5

75

15

A gminus1

A gminus1

A gminus1

A gminus1A gminus1

(d)

0 50 100 150 200 250 300 350

0

100

200

300

400

500

600

700

0 2 4 6 8 1002468

10

Bare CNT-COOH

Pure PANI

minusZ998400998400

(Ohm

)

minusZ998400998400

(Ohm

)

Z998400 (Ohm)

Z998400 (Ohm)

CNTPANI(using HCl)

CNTPANI(using HNO3)

(e)

0 2 4 6 8 10 12 14 16


0

100

200

300

400

500

Spec

ific c

apac

itanc

e (F

gminus1)


Bare CNT-COOH

Pure PANI

(f)








4 Conclusions


3solution)




Acknowledgment


References















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Oxidation

Water

[Bmim][BF4]


ANI KPSHCl or HNO3



(3 1)


(a)

CNT

PANI

100nm

(b)

(c)

PANI

CNT

100nm

(d)



10 20 30 40 50 60 70 80

(020

)(211

)

(d)

(c)

(b)

Inte

nsity

(au

)

2120579 (deg)

(a)

(100

)



3500 3000 2500 2000 1500 1000

1565

15621490

1493

1092

3224

Inte

nsity

(au

)

3224 1289

12861085

3440

(b)

(c)

(d)

2359

(a)

173629291636

1125





0 100 200 300 400 500 60050

60

70

80

90

100

(d)

(c)(b)

Wei

ght (

)

(a)

Temperature (∘C)




atmosphere




C 1s

5

10

15

20

25

30

35

40

45

50

Cou

nts

292 290 288 286 284 282 280

Binding energy (eV)

CndashC

CndashNC=N

120587-120587lowast

Pure PANItimes10

2

(a)

N 1s

ndashN=

ndashNHndash

ndashN+

Cou

nts

Binding energy (eV)

12

14

16

18

20

22

408 406 404 402 400 398 396 394 392 390

Pure PANItimes10

2

(b)

5

10

15

20

25

30

35

40

45

291 288 285 282

times102

Cou

nts

Binding energy (eV)

C 1s

CndashN

CndashC

CndashO

OndashC=O

CNTPANI

(c)

20

25

30

35

40

406 404 402 400 398

ndashN+

times102

Cou

nts

Binding energy (eV)

N 1s

ndashN=

ndashNHndash

CNTPANI

(d)







200 300 400 500 600 700

(d)

(c)(b)

Inte

nsity

(au

)

Wavenumber (nm)

(a)


in ethanol

00 01 02 03 04 05 06minus40

minus20

0

20

40

60

Curr

ent (

mA

)




(a)

0 20 40 60 80 100 120 140

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)


Pure PANI

(b)



3









minus01 00 01 02 03 04 05 06 07minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(a)

minus01 00 01 02 03 04 05 06 07

minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(b)

0 20 40 60 80 100

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)


5A gminus1


(c)

0 20 40 60 80 100

00

01

02

03

04

05Po

tent

ial (

V v

ersu

s SCE

)

Time (s)

2

35

5

75

15

A gminus1

A gminus1

A gminus1

A gminus1A gminus1

(d)

0 50 100 150 200 250 300 350

0

100

200

300

400

500

600

700

0 2 4 6 8 1002468

10

Bare CNT-COOH

Pure PANI

minusZ998400998400

(Ohm

)

minusZ998400998400

(Ohm

)

Z998400 (Ohm)

Z998400 (Ohm)

CNTPANI(using HCl)

CNTPANI(using HNO3)

(e)

0 2 4 6 8 10 12 14 16


0

100

200

300

400

500

Spec

ific c

apac

itanc

e (F

gminus1)


Bare CNT-COOH

Pure PANI

(f)








4 Conclusions


3solution)




Acknowledgment


References















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


10 20 30 40 50 60 70 80

(020

)(211

)

(d)

(c)

(b)

Inte

nsity

(au

)

2120579 (deg)

(a)

(100

)



3500 3000 2500 2000 1500 1000

1565

15621490

1493

1092

3224

Inte

nsity

(au

)

3224 1289

12861085

3440

(b)

(c)

(d)

2359

(a)

173629291636

1125





0 100 200 300 400 500 60050

60

70

80

90

100

(d)

(c)(b)

Wei

ght (

)

(a)

Temperature (∘C)




atmosphere




C 1s

5

10

15

20

25

30

35

40

45

50

Cou

nts

292 290 288 286 284 282 280

Binding energy (eV)

CndashC

CndashNC=N

120587-120587lowast

Pure PANItimes10

2

(a)

N 1s

ndashN=

ndashNHndash

ndashN+

Cou

nts

Binding energy (eV)

12

14

16

18

20

22

408 406 404 402 400 398 396 394 392 390

Pure PANItimes10

2

(b)

5

10

15

20

25

30

35

40

45

291 288 285 282

times102

Cou

nts

Binding energy (eV)

C 1s

CndashN

CndashC

CndashO

OndashC=O

CNTPANI

(c)

20

25

30

35

40

406 404 402 400 398

ndashN+

times102

Cou

nts

Binding energy (eV)

N 1s

ndashN=

ndashNHndash

CNTPANI

(d)







200 300 400 500 600 700

(d)

(c)(b)

Inte

nsity

(au

)

Wavenumber (nm)

(a)


in ethanol

00 01 02 03 04 05 06minus40

minus20

0

20

40

60

Curr

ent (

mA

)




(a)

0 20 40 60 80 100 120 140

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)


Pure PANI

(b)



3









minus01 00 01 02 03 04 05 06 07minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(a)

minus01 00 01 02 03 04 05 06 07

minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(b)

0 20 40 60 80 100

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)


5A gminus1


(c)

0 20 40 60 80 100

00

01

02

03

04

05Po

tent

ial (

V v

ersu

s SCE

)

Time (s)

2

35

5

75

15

A gminus1

A gminus1

A gminus1

A gminus1A gminus1

(d)

0 50 100 150 200 250 300 350

0

100

200

300

400

500

600

700

0 2 4 6 8 1002468

10

Bare CNT-COOH

Pure PANI

minusZ998400998400

(Ohm

)

minusZ998400998400

(Ohm

)

Z998400 (Ohm)

Z998400 (Ohm)

CNTPANI(using HCl)

CNTPANI(using HNO3)

(e)

0 2 4 6 8 10 12 14 16


0

100

200

300

400

500

Spec

ific c

apac

itanc

e (F

gminus1)


Bare CNT-COOH

Pure PANI

(f)








4 Conclusions


3solution)




Acknowledgment


References















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


C 1s

5

10

15

20

25

30

35

40

45

50

Cou

nts

292 290 288 286 284 282 280

Binding energy (eV)

CndashC

CndashNC=N

120587-120587lowast

Pure PANItimes10

2

(a)

N 1s

ndashN=

ndashNHndash

ndashN+

Cou

nts

Binding energy (eV)

12

14

16

18

20

22

408 406 404 402 400 398 396 394 392 390

Pure PANItimes10

2

(b)

5

10

15

20

25

30

35

40

45

291 288 285 282

times102

Cou

nts

Binding energy (eV)

C 1s

CndashN

CndashC

CndashO

OndashC=O

CNTPANI

(c)

20

25

30

35

40

406 404 402 400 398

ndashN+

times102

Cou

nts

Binding energy (eV)

N 1s

ndashN=

ndashNHndash

CNTPANI

(d)







200 300 400 500 600 700

(d)

(c)(b)

Inte

nsity

(au

)

Wavenumber (nm)

(a)


in ethanol

00 01 02 03 04 05 06minus40

minus20

0

20

40

60

Curr

ent (

mA

)




(a)

0 20 40 60 80 100 120 140

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)


Pure PANI

(b)



3









minus01 00 01 02 03 04 05 06 07minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(a)

minus01 00 01 02 03 04 05 06 07

minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(b)

0 20 40 60 80 100

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)


5A gminus1


(c)

0 20 40 60 80 100

00

01

02

03

04

05Po

tent

ial (

V v

ersu

s SCE

)

Time (s)

2

35

5

75

15

A gminus1

A gminus1

A gminus1

A gminus1A gminus1

(d)

0 50 100 150 200 250 300 350

0

100

200

300

400

500

600

700

0 2 4 6 8 1002468

10

Bare CNT-COOH

Pure PANI

minusZ998400998400

(Ohm

)

minusZ998400998400

(Ohm

)

Z998400 (Ohm)

Z998400 (Ohm)

CNTPANI(using HCl)

CNTPANI(using HNO3)

(e)

0 2 4 6 8 10 12 14 16


0

100

200

300

400

500

Spec

ific c

apac

itanc

e (F

gminus1)


Bare CNT-COOH

Pure PANI

(f)








4 Conclusions


3solution)




Acknowledgment


References















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


200 300 400 500 600 700

(d)

(c)(b)

Inte

nsity

(au

)

Wavenumber (nm)

(a)


in ethanol

00 01 02 03 04 05 06minus40

minus20

0

20

40

60

Curr

ent (

mA

)




(a)

0 20 40 60 80 100 120 140

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)


Pure PANI

(b)



3









minus01 00 01 02 03 04 05 06 07minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(a)

minus01 00 01 02 03 04 05 06 07

minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(b)

0 20 40 60 80 100

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)


5A gminus1


(c)

0 20 40 60 80 100

00

01

02

03

04

05Po

tent

ial (

V v

ersu

s SCE

)

Time (s)

2

35

5

75

15

A gminus1

A gminus1

A gminus1

A gminus1A gminus1

(d)

0 50 100 150 200 250 300 350

0

100

200

300

400

500

600

700

0 2 4 6 8 1002468

10

Bare CNT-COOH

Pure PANI

minusZ998400998400

(Ohm

)

minusZ998400998400

(Ohm

)

Z998400 (Ohm)

Z998400 (Ohm)

CNTPANI(using HCl)

CNTPANI(using HNO3)

(e)

0 2 4 6 8 10 12 14 16


0

100

200

300

400

500

Spec

ific c

apac

itanc

e (F

gminus1)


Bare CNT-COOH

Pure PANI

(f)








4 Conclusions


3solution)




Acknowledgment


References















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


minus01 00 01 02 03 04 05 06 07minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(a)

minus01 00 01 02 03 04 05 06 07

minus100

minus50

0

50

100

150

Curr

ent (

mA

)


2mVs5mVs10mVs25mVs

50mVs75mVs100mVs

(b)

0 20 40 60 80 100

00

01

02

03

04

05

Pote

ntia

l (V

ver

sus S

CE)

Time (s)


5A gminus1


(c)

0 20 40 60 80 100

00

01

02

03

04

05Po

tent

ial (

V v

ersu

s SCE

)

Time (s)

2

35

5

75

15

A gminus1

A gminus1

A gminus1

A gminus1A gminus1

(d)

0 50 100 150 200 250 300 350

0

100

200

300

400

500

600

700

0 2 4 6 8 1002468

10

Bare CNT-COOH

Pure PANI

minusZ998400998400

(Ohm

)

minusZ998400998400

(Ohm

)

Z998400 (Ohm)

Z998400 (Ohm)

CNTPANI(using HCl)

CNTPANI(using HNO3)

(e)

0 2 4 6 8 10 12 14 16


0

100

200

300

400

500

Spec

ific c

apac

itanc

e (F

gminus1)


Bare CNT-COOH

Pure PANI

(f)








4 Conclusions


3solution)




Acknowledgment


References















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





4 Conclusions


3solution)




Acknowledgment


References















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of
































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Research Article Green Synthesis and Characterization of...

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