, ) 1977,Heeger, MacDiarmid ,,,, 10 3 SPcm, PPy, 1980, PPy. PPy. PPy. PPy PPy. PPy. PPy

Transcription

1 4 51 (, ) : 1995 ( : ), : ; ; ; ; 1977,Heeger, MacDiarmid, 10 3 SPcm,,,, 1979, IBM Diaz 100 SPcm (PPy) [1 ],,, 1980, PPy, PPy PPy,, 017V( vs. SCE),,, PPy PPy,, PPy, PPy, PPy PPy PPy PPy 1995, PPy 1 PPy, PPy (, ) PPy [2 ] ( ),

2 PPy ( 1) [3 ] ph,,ph > 4, ph 2 F ph F 315 [4 ],,011 molpl 012 molpl ( TsOH) 10 2 SPcm, 118 GPa 50 MPa 100 cm 2 [5 ] 3 1 Table 1 Effect of electrolyte anions on the conductivity and density of as2prepared PPy films P(S cm - 1 ) P(g cm - 3 ) P(g cm - 3 ) HClO NaBF KPF TsOH TsONa NaNO H 2 SO Na 2 SO , (1), PPy [6 ], OP10 PPy 127 MPa [6a], PPy ; (2), (DN), PPy ( 2) [7 ] DN 20 2 DN Table 2 Effect of solvent donor number of the electrolyte on the conductivity of the as2prepared PPy films DN 3 (PPy) P(S cm - 1 ) PPy(BF - 4 ) PPy(ClO - 4 ) PPy(NO - 3 ) PPy(TsO - ) DMSO DMF TBP TMP THF H 2 O PC CH 3 NO DN :Doner Number, DN,,, 43 SPcm [8 ] 2 [9, ],,

3 4 53,, ph H +, H + 2, 52 ph > 7, H + [4a] ph, PPy, [10 ], [11, ], ( Py) (Py + ) (A - ) ( Py + A - ),,,,, [11 ] : i = K[ Py ][ A - ] 1 + Kp[ Py ] + K A [ A - ] i ( ),[ Py ] [ A - ], K, K p K A, K K p K A [A - ] (1 + K P [ P y ]), (1) i = K[ Py ] [ A - ]P(1 + K P [ Py ]), ; K A [ A - ] (1 + K p [ Py]), (1) i = K [ Py]PK A,, (1) 3 [ PPy(NO - 3 ) ], ph 2, PPy, ( 1) [12 ], 2C,, 1 PPy 4 5 (a) ; (b) [13 ] PPy Figure 1 Two doping structures of conducting polypyrrole (a) the counter2anion doping structure with the oxidation of [14, ] PPy the conjugated chain ; (b) proton2acid doping structure., OH - [15 ] PPy (Thermopower), (VRH) [16 ] PPy [17, ] [18 PPy, ] (1) K A

4 PPy,,, PPy PPy p2,,ppy p2 ( ) ( ), : PPy + ( A - ) + e - PPy o + A - (2) p2 PPy + (A - ) A - ( p2),ppy o ( ) ( EQCM), PPy PPy 411, PPy ph [12a,19 ], NO - 3 Cl - ClO - 4,, (2) 2 (b), V vs. SCE, V vs. SCE, 2 (a) [12a] EQCM [19b] PPy, PPy 2 PPy(NO - 3 ) 015 molpl NaNO 3, (2),, : (a) (ph7) ; (b) (ph3) ; PPy + ( A - ) + e - + M + PPy o ( M + A - ) (3) 20mVPs,PPy Figure 2 Cyclic voltammograms of PPy(NO - 3 ), in 015 molpl NaNO 3 aqueous solution 3 [12a], 013V V,530nm (a) in neutral solution ; (b) in ph3 acidic solution. Potential scan rate : 20mVPs, - 013V,530 nm PPy,PPy(Cl - ) ph = 3, 015molPL KCl,011V vs. SCE 1115mAPcm 2, PPy cm 2 Ps [20 ], PPy, OH -, OH - [15,19b],,, PPy, 015 V vs. SCE PPy,pH,, ph ( ), [21 PPy ] 412 PPy,

5 4 55 PPy, ( PC),, - 016V vs. SCE, - 018V,, ( 4) [22 ] PPy, [22 ] PPy,, PPy,,, (3), PPy,, 3 PPy(NO - 3 ) ph = 3, 015molPL NaNO 3 Figure 3 In2situ absorption spectra of PPy(NO - 3 ) in ph = 3, 5 015molPL NaNO 3 aqueous solution at different potentials PPy, PPy Cl -, NO - 3 ClO - 4, Cl - NO - 3, [23 PPy ] PPy ph [24 ], PPy(NO 3 - ) ph = 2, 1 molpl NaNO V vs. SCE, ph, 240 mvpph, Nernst ph - 4 PPy(ClO - 4 ) 015 molpl NaClO 4 PC PPy, PPy, Figure 4 Cyclic voltammograms of PPy(ClO 4 - ) ;,PPy in 015 molpl NaClO 4 PC solution, ;, the numbers in the figure indicate the OH -, 4 sequence of the potential scan PPy, PPy, [25, PPy ] 6 PPy, PPy,,, PPy, P,

6 [26 ] [27 ] P 66, PPy 66, PPy, 40300m, 66, 66 PPy ( ) [28 ],,,PPy, (119 SPcm) Kevlar, Kevlar PPy, 500, 7 60, 3, : 760, 10, [29 ] [30 ], :,Su2Moon Park Handbook of Organic Conductive Polymers(John Wiley & Sons Ltd., 1997, New York) :Even more interesting results were reported by Li and Qian, who identified two chemically different counter2anion doping sites formed during the doping reactions of PPy in aqueous media. These two sites are the positively charged conjugated chain ( site 1) and the protonated pyrrole units (site 2), respectively, OP10 PPy, P. Chandrasekhar Conducting Polymers, Fundamentals and Applications : A Practical Approach(Ashwin2Ushas Corp.,1999, Freehold, NJ, USA) 383 :Ouyang et al. found in recent work that the quality of PPy films can be improved greatly when pyrrole is electropolymerized from aqueous solutions containing nonaphenal polyethyleneoxy(10) ether. Properties such as the tensile strength improved from 2718 MPa to 127 MPa using this additives,,,,, : ( : , , , ) : [ 1 ] Fiaz A F, Kanazawa K K, Gardini G P, J Chem Soc, Chem Commun, 1979, 6351 [ 2 ] (a)li Y F. in Polymers and Organic Solids, ( Edited by Lianghe Shi, Daoben Zhu), Beijing : Science Press, 1997, 2281 (b) Li Y F. Current Trends in Polymer Science, 2002, Vol. 7, 1011 [ 3 ] Qian R Y, Qiu J J. Polym J, 1987, 19 : 1571 [ 4 ] (a) Qian R Y, Pei Q B, Huang Z T. Makromol Chem, 1991, 192 : 1263 ; (b) Pei Q B, Qian R Y. J Electroanal Chem, 1992, 322 : 1531 [ 5 ],.,1991, 4 :3201 [ 6 ] (a) Ouyang J Y, Li Y F. Polymer, 1997, 38 : 3997 ; (b) Li Y F, Ouyang J Y. Synth Met, 2000, 113 : 231 [ 7 ] Ouyang J Y, Li Y F. Polymer,1997, 38 :19711 [ 8 ] He C, Li Y F. Synth Met,2003, 139 : 5391 [ 9 ] Genies E M, Bidan G, Diaz A F. J Electroanal Chem, 1983, 149 :1011

7 4 57 [10 ] (a) Li Y F, Fan Y F. Synth Met, 1996, 79 : 225 ; (b) Li Y F, Yang J. J Appl Polym Sci, 1997, 65 : [11 ] Li Y F. J Electroanal Chem, 1997, 433 : 1811 [12 ] (a) Li Y F, Qian R Y. J Electroanal Chem, 1993,362 : 267 ; (b) Li Y F, Qian R Y, Imaeda K, Inokuchi H. Polym J, 1994, 26 : 535 ; (c) Li Y F, Ouyang J Y, Yang J. Synth Met, 1995, 74 : 491 (d) Li Y F, He G F. Synth Met, 1998, 94 : 1271 [13 ] Qian R Y, Li Y F, Yan B Z, Zhang H M. Synth Met, 1989, 28 : C511 [14 ] Qian R Y. On the macromolecular chain structure of conducting polypyrrole, inconjugated Polymers and Related Materials, the Interconnection of Chemical and Electronic Structure ( Edited by Salameck W R, et. al. ), Chapter 12, Oxford Science Publications, Oxford, 1993, pp [15 ] Li Y F, Qian R Y. Synth Met, 1988, 26 : 139 [16 ] Shen Y Q, Carniero K, Qian R Y, Qiu J J. Synth Met, 1987, 18 : 771 [17 ] Li Y F, Qian R Y. Synth Met, 1993, : [18 ] Ouyang J Y, Li Y F. Synth Met, 1995, 75 : 11 [19 ] (a) Li Y F, Qian R Y. Synth Met, 1989, 28 : c1271 (b) Li Y F, Liu Z F. Synth Met, 1998, 94 : 1311 [20 ] Li Y F, Qian R Y. Synth Met, 1994, 64 : 2411 [21 ] Li Y F, Qian R Y. Electrochim Acta, 2000, 45 : [22 ] Li Y F. Electrochim. Acta, 1997, 42 : 2031 [23 ] Pei Q B, Qian R Y. in Polymers and Biomaterials, ( Edited by Feng H, Han Y, Huang L. ), Elsevier Science, 1991, pp [24 ] Pei Q B, Qian R Y. Electrochim. Acta, 1992, 37 : [25 ] Li Y F, Qian R Y. Synth Met, 1993, 53 : 1491 [26 ],,,,. CN, , [27 ] Chen Y P, Qian R Y, Li G, Li Y. Polym Commun, 1991, 32 : 1891 [28 ] (a) Bi X T, Pei Q B. Synth Met, 1987, 22 : 145 ; (b),,.,1987, 376 ; (c) Bi X T, Pei Q B, Li Y F. Chin J Polym Sci, 1988, 6 : 377 ; (d) Zhang G P, Peng G, Bi X T, Synth Met, 1993, : 1123 ; (e) Bao J, Xu C, Cai W, Bi X T. J Appl Polym Sci, 1994, 52 : [29 ].,2004, 10 : 3691 [30 ].,1999,10 :1. Studies on Conducting Polypyrrole LI Yong2Fang ( CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing , China) Abstract :The main achievements of the projectstudies on Conducting Polypyrrole(which won The Second Degree National Award on the Natural Sciences in 1995) and the recent development of the research after 1995 were introduced. The related contents include the electrochemical polymerization processes and mechanism, structures, stability and electrochemical properties of conducting polypyrrole, as well as the preparation of conducting polypyrrole composite materials. Key words : Conducting polypyrrole ; Conducting polymers ; Electrochemical polymerization ; Electrochemical properties ; Doping structures