Vol 33 No 11 2012 11 CHEMICAL JOURNAL OF CHINESE UNIVERSITIES 2501 ~ 2508 2 1 1 2 1 361005 2 350004 CSA PANI SEM TEM - UV-Vis CD PANI ζ PANI PANI PANI PANI / O646 A doi 10 7503 /cjcu20120239 PANI 1 Martin 2 3 4 PANI 5 AAO PANI 6 PANI PANI Kaner 7 PANI PANI PANI PANI 8 9 10 PANI PANI Yang 11 PANI Li 12 CSA PANI Yan 13 SEM CSA PANI PANI 14 ~ 18 Li 14 CSA PANI PANI PANI / PANI 19 PANI CSA PANI 2012-03-19 21021002 2011J05023 2010BS006 E-mail jzzhou@ xmu edu cn
2502 Vol 33 PANI 1 1 1 1S - + - -10- D-CSA 1R - - - -10- L-CSA Alfa Aesar ITO 25 ~ 35 Ω /cm 2 Millipore CHI630B ITO Pt SCE Hitachi S-4800 Philips FEI Technai 30 Varian Cary 5000 - JASCO Corporation J-810 spectropolarimeter CD Brookhaven Zeta 1 2 1 2 1 CSA PANI 1 ml 0 1 mol /L ANI + 1 mol /L D-CSA 0 2 mol /L ANI + 1 mol /L D-CSA 0 5 mol /L ANI + 1 mol /L D-CSA 1 h 1 ml 20 h D-CSA PANI SEM 1 2 2 PANI CSA 0 1 mol /L ANI + 1 mol /L D- CSA 0 2 mol /L ANI + 1 mol /L D-CSA 0 5 mol /L ANI + 1 mol /L D-CSA 0 1 mol /L ANI + 1 mol /L L- CSA ITO 0 75 0 80 0 85 V 300 s CSA PANI D-CSA PANI PANI D-PANI L-CSA PANI PANI L-PANI PANI - 0 2 ~ 0 9 V 100 mv /s 1 0 9 V 1 6 mc /cm 2 2 h 1 2 3 PANI D-PANI 0 1 mol /L HCl 0 1 mol /L - UV-Vis CD 0 1 mol /L HCl 0 9-0 2 0 45 V vs SCE 2 2 1 PANI 1 D-CSA L-CSA 1 mol /L 0 1 ~ 0 5 mol /L PANI SEM PANI PANI 50 ~ 100 nm SEM 1 B D F H PANI CSA PANI 19 D-CSA PANI L-CSA CSA PANI 13 20 CSA SO 3 H C 10 H 15 O CSA CSA - /HAn + CSA CSA - /HAn + CSA - CSA / An CSA / An < 1 CSA / An 13 > 5 20 CSA / An > 20 PANI 13 CSA PANI PANI
No 11 2503 Fig 1 SEM images A C E G and high resolution of images B D F H of D-PANI A F and L-PANI G H A B 0 1 mol /L ANI + 1 mol /L D-CSA solution C D 0 2 mol /L ANI + 1 mol /L D-CSA solution E F 0 5 mol /L ANI + 1 mol /L D-CSA solution G H 0 1 mol /L ANI + 1 mol /L L-CSA solution The potential was set at 0 9 V vs SCE CSA CSA / An 1 CSA 1 mol /L CSA PANI CSA 2 mol /L 2 Fig 2 SEM images A C E G and high resolution of images B D F H of potentiostatic electropolymerization D-PANI A F and L-PANI G H A B 0 1 mol /L ANI + 2 mol /L D-CSA solution C D 0 2 mol /L ANI + 2 mol /L D-CSA solution E 0 05 mol /L ANI + 2 mol /L D-CSA solution F 0 5 mol /L ANI + 2 mol /L D-CSA solution G H 0 1 mol /L ANI + 2 mol /L L-CSA solution The potential was set at 0 9 V vs SCE CSA PANI 3 CSA / An 3 A 3 B Fig 3 SEM images of D-PANI nanofibers prepared from 0 1 mol /L ANI + 1 mol /L D-CSA solution A 0 2 mol / L ANI + 1 mol /L D-CSA solution B and 0 5 mol /L ANI + 1 mol /L D-CSA solution C with chemical method
2504 Vol 33 C 13 CSA PANI CSA / An CSA 1 1 2 mol /L CSA 0 1 mol /L ζ CSA 2 mol /L -CSA Table 1 Average diameter of micelles and ζ-potential of 1 mol /L CSA 2 different solutions ζ CSA - /HAn + CSA 2 mol /L ζ PANI Solution Diameter / nm ζ potential / mv 0 1 mol /L aniline + 2 mol /L D-CSA 3176-1 05 2 mol /L D-CSA 71 77 0 1 mol /L aniline + 1 mol /L D-CSA 1400-14 55 1 mol /L D-CSA 75 91 13 19 CSA 1 mol /L ζ PANI 4 CSA 1 mol /L 0 75 V PANI > 0 75 V PANI 0 75 0 80 0 85 0 90 V PANI 5 0 9 V PANI Fig 4 Cyclic voltammograms of ITO electrode in 0 1 mol /L ANI + 1 mol /L D-CSA solution scan rate = 100 mv /s A and anodic current as a function of deposition time for PANI growth at 0 9 V B Fig 5 SEM images of electrodeposited D-PANI nanofibers from different solutions of 0 1 mol /L ANI + 1 mol /L D-CSA A1 A3 0 2 mol /L ANI + 1 mol /L D-CSA B1 B3 and 0 5 mol /L ANI + 1 mol /L D-CSA C1 C3 at different set potentials at 0 75 V A1 C1 0 80 V A2 C2 and 0 85 V A3 C3
No 11 2505 4 B CSA CSA - /HAn + CSA - /HAn + π- CSA PANI 2 2 PANI 6 0 1 ~ 1 mol /L CSA D-PANI L-PANI CD UV-Vis PANI Fig 6 CD A and UV-Vis B spectra of D-PANI dash dot line and L-PANI solid line prepared from 0 1 mol /L ANI + 1 mol /L D-CSA and 0 1 mol /L ANI + 1 mol /L L-CSA respectively PANI UV-Vis 340 nm π-π * 450 800 nm PANI 6 A D-PANI L-PANI 300 nm D-CSA L-CSA 290 nm 7 D-PANI L-PANI PANI D-PANI 340 nm Cotton 460 nm Cotton 700 nm Cotton L-PANI 19 PANI 10 580 mdeg Fig 7 CD spectra of D-CSA a and L-CSA b in aqueous solution 0 01 mol /L 13 19 PANI CSA 12 TEM PANI 8 D-PANI L-PANI PANI CSA - PANI 12 PANI 13 Fig 8 TEM images of D-PANI A prepared from 0 1 mol /L ANI + 1 mol /L D-CSA solution and L-PANI B prepared from 0 1 mol /L ANI + 1 mol /L L-CSA solution
2506 Vol 33 PANI 9 1 mol /L D-CSA D-PANI CD D-PANI D-PANI 460 nm CD D-PANI 0 5 mol /L 0 2 0 1 mol /L CSA PANI Fig 9 CD spectra of D-PANI prepared in 1 mol /L 9 16 17 PANI D-CSA with different aniline concentrations a 0 5 mol /L b 0 1 mol /L c 0 2 mol /L PANI - 10 0 1 mol /L D-PANI UV-Vis CD PANI 0 1 mol /L 0 1 mol /L HCl PANI PANI UV-Vis CD 10 A UV-Vis D-PANI 0 1 mol /L Emeraldine base EB PANI 350 660 nm 21 CD 10 B 330 400 530 770 nm UV-Vis PANI PANI PANI CSA PANI D-PANI HCl D-PANI 10 Fig 10 UV-Vis A and CD B spectra of as-prepared D-PANI a dedoped D-PANI b by 0 1 mol /L ammonia and redoped D-PANI c by 0 1 mol /L HCl D-PANI prepared from 0 1 mol /L ANI + 1 mol /L D-CSA solution a Original b redoped c dedoped 11 D-PANI 0 1 mol /L HCl CD UV-Vis 11 A D-PANI D-PANI UV-Vis 11 B 430 790 nm 325 590 nm PANI CD 11 A 462 680 nm CD 22 360 510 nm 315 720 nm UV-Vis 23 D-PANI UV-Vis 11 B π-π * 350 nm 450 nm PANI 24 25 11 A D-PANI 340 390 450 nm CD 340 390 nm PANI 350 nm π-π *
No 11 2507 Fig 11 CD A and UV-Vis B spectra of different oxidized state D-PANI prepared from 0 1 mol /L ANI + 1 mol /L D-CSA solution a Mid-oxided b oxided c reduced 22 CD 23 PANI CD 3 PANI CSA 1 mol /L PANI CSA / PANI PANI PANI 1 Li D Huang J X Kaner R B Acc Chem Res J 2009 42 1 135 145 2 Parthasarathy R V Martin C R Nature J 1994 369 298 301 3 Liang W Martin C R J Am Chem Soc J 1990 112 26 9666 9668 4 WENG Shao-Huang ZHOU Jian-Zhang WEN Li QI Li CAI Cheng-Dong YAO Guang- Hua LIN Zhong-Hua Chem J Chinese Universities J 2006 27 11 2179 2181 5 QI Li ZHOU Jian-Zhang CAI Cheng-Dong YAO Guang-Hua LIN Zhong-Hua Chem J Chinese Universities J 2007 28 3 562 564 6 Wan M X Macromol Rapid Commun J 2009 30 12 963 975 7 Li D Kaner R B J Am Chem Soc J 2006 128 3 968 975 8 Yashima E Maeda K Macromolecules J 2008 41 1 3 12 9 Huang J Y Wei Z X Chen J C Sens Actuators B J 2008 134 2 573 578 10 Huang J X Egan V M Guo H L Yoon J Y Briseno A L Rauda I E Garrell R L Knobler C M Zhou F M Kaner R B Adv Mater J 2003 15 14 1158 1161 11 Yang Y S Wan M X J Mater Chem J 2002 12 897 901 12 Li W G Wang H L J Am Chem Soc J 2004 126 8 2278 2279 13 Yan Y Yu Z Huang Y W Yuan W X Wei Z X Adv Mater J 2007 19 20 3353 3357 14 Li W G Wang H L Adv Funct Mater J 2005 15 11 1793 1798 15 Majidi M R Kane-Maguire L A P Wallace G G Polymer J 1994 35 14 3113 3115 16 Norris I D Kane-Maguire L A P Wallace G G Macromolecules J 2000 33 9 3237 3243 17 Pornputtkul Y Kane-Maguire L A P Wallace G G Macromolecules J 2006 39 17 5604 5610 18 Zhang X T Song W H Polymer J 2007 48 19 5473 5479 19 Weng S H Lin Z H Chen L X Zhou J Z Electrochimica Acta J 2010 55 8 2727 2733 20 Zhang L J Wan M X Nanotechnology J 2002 13 750 755 21 Masters J G Ginder J M MacDiarmid A G Epstein A J J Chem Phys J 1992 96 6 4768 4778 22 Su S J Kuramoto N Macromolecules J 2001 34 21 7249 7256
2508 Vol 33 23 Su S J Kuramoto N Chem Mater J 2001 13 12 4787 4793 24 McCall R P Ginder J M Leng J M Ye H J Manohar S K Masters J G Asturias G E MacDiarmid A G Epstein A J Phys Rev B J 1990 41 8 5202 5213 25 ZHOU Jian-Zhang WENG Shao-Huang LIN Zhong-Hua Journal of Electrochemistry J 2009 15 3 241 244 Electrochemical Preparation of Chiral Polyaniline Nanofibers WENG Shao-Huang 2 ZHOU Jian-Zhang 1* LIN Zhong-Hua 1 LIN Xin-Hua 2 1 State Key Laboratory of Physical Chemistry of the Solid Surface Department of Chemistry College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China 2 Department of Pharmaceutical Analysis Faculty of Pharmacy Fujian Medical University Fuzhou 350004 China Abstract Chiral polyaniline PANI nanofibers were synthesized via facilely potentiostatic electropolymerization method without template in the presence of 1S - + -camphor-10-sulfonic acid D-CSA or 1R - - -camphor-10-sulfonic acid L-CSA as the dopant The morphology and optical property of chiral PANI nanofibers were characterized with scanning electron microscopy SEM transmission electron microscopy TEM UV-Vis spectrum UV-Vis and circular dichroism CD Combined with the average diameter of micelles and zeta-potential of different deposition solutions the formation mechanism and the enhanced optical activity of the optical PANI nanofibers were studied The morphology of PANI nanofibers without the helical structure was consistent with the change of the concentration of aniline in the deposition solution when the concerntion of CSA was 1 mol /L Furthermore chiral PANI nanofibers induced by different chiral CSA exhibited mirror-imaged circular dichroism spectra with high ellipticity indicating the stereochemical selectivity of the molecular structure of PANI chain in the electrodeposited process The colors and optical activities of the chiral PANI nanofibers not only can be kept with the chemical dedoping /redoping treatment but also can reversibly varied with the different oxidized forms which were controlled via electrochemical route Keywords Stereochemical selectivity Electropolymerization Polyaniline PANI nanofiber Chiral Circular dichroism spectrum Ed S Z