采用恒电位法, 以石墨箔为工作电极, 通过聚苯胺(PANI)和二氧化铈(CeO2)的电化学共沉积, 制备了PANI/CeO2复合膜. 利用SEM, TEM和电子衍射(EDP)观测了PANI/CeO2复合膜的形貌和结构, 利用Fourier变换红外光谱(FTIR)研究了 PANI/CeO2复合膜的组成, 利用循环伏安法研究了PANI/CeO2复合膜的电化学行为. 研究了电化学沉积条件对PANI/CeO2复合膜形貌的影响. 结果表明, 在1.1 V (vs SCE) 进行PANI与CeO2的电化学共沉积时, 由于苯胺电化学聚合和CeO2电化学沉积过程中均释放一定量的H+, PANI/CeO2复合膜以“羊角”形貌存在; 而0.8 V电化学沉积的复合膜则以纳米颗粒形式存在. “羊角”形的PANI/CeO2复合膜上形成很多上部宽大、底部稍窄的楔形空间, 有利于客体粒子进入复合膜深处与活性组分充分接触, 提高性能. 复合膜的FTIR谱上出现了PANI的典型振动吸收, 循环伏安测试结果表明复合膜主要呈现PANI的电化学性能.
Composite materials consisting of conducting polymers and inorganic particles have attracted considerable attention as they combine the advantages of both components and have potential applications in many fields. Electrodeposition is an attractive method for the preparation of thin films since it offers the advantages of low processing temperature, normal handling pressure, high purity of deposition, and controlled thickness of the film. Polyaniline/CeO2 (PANI/CeO2) composite with “horn--like” morphology was prepared by potentiostatic electrodeposition method in 0.05 mol/L Ce(NO3)3 containing 0.05 mol/L CH3COOH and 0.025 mol/L aniline (An) at 1.1 V (vs SCE) (pH=5.5). The morphology and composition of the PANI/CeO2composite were characterized by SEM and TEM. The results indicated that the PANI/CeO2 composite had “horn--like” morphology. Characteristic vibrations of PANI were observed on the Fourier transform infrared spectrum (FTIR) of PANI/CeO2 composite. The PANI/CeO2 composite displayed characteristic electrochemical behaviors of PANI in phosphate buffer (pH=6.9), based on cyclic voltammetric experiments. The influences of electrodeposition conditions on the morphology of the composite were investigated by changing the reaction time and the potentiostatic potential. The results showed that potential is the key factor for the formation of “horn--like” PANI/CeO2 composite. PANI/CeO2 composite obtained at 0.8 V existed in nanoparticles. No “horn-like” composite was observed at this lower potential, even after prolonged reaction time. More protons were released during the electrochemical polymerization of aniline and the electrochemical deposition of CeO2 at higher potential. One--dimensional growth of PANI was promoted due to the effect control of secondary growth of PANI at lower pH media, resulting in nanofibrous composite. More PANI and CeO2 were formed along with the electrodeposition and so more protons were released. Thus the nanofiber changed thinner and “horn-like” PANI/CeO2 was formed.
[1] Zhang X, Wang J, Chen L. Acta Metall Sin, 2009; 45: 1135
(张霞, 王晶, 陈莉. 金属学报, 2009; 45: 1135)
[2] Peng X Y, Liu X X, Hua P J, Diamond D, Lau K T. J Solid State Electrochem, 2010; 14: 1
[3] Bian L J, Zhang J H, Qi J, Liu X X, Dermot D, Lau K T. Sens Actuators, 2010; 147B: 73
[4] Wan M X, Zhou W X, Li J C. Synth Met, 1996; 78: 27
[5] Wei Y, Li M G, Fang B. Chin J Chem, 2007; 25: 1622
[6] Ansari A A, Solanki P R, Malhotra B D. Appl Phys Lett,2008; 92: 263901
[7] Bene R, Pinter Z, Perczel I V, Fleischer M, Reti F. Vacuum,2001; 61: 275
[8] Parvatikar N, Jain S, Bhoraskar S V, Prasad M V N A. J Appl Polym Sci, 2006; 102: 5533
[9] Diaz D J, Greenletch N, Solanki A, Karakoti A, Seal S. Catal Lett, 2007; 119: 319
[10] Xu H, Hou X. Int J Hydrogen Energy, 2007; 32: 4397
[11] Zhitomirsky I, Petric A. Ceram Int, 2001; 27: 149
[12] Kamada K, Higashikawa K, Inada M, Enomoto N, Hojo J. J Phys Chem, 2007; 111C: 14508
[13] Iwuoha E I, de Villaverde D S, Garcia N P, Smyth M R, Pingarron J M. Biosens Bioelectron, 1997; 12: 749
[14] Ates M, Sarac A S. Prog Org Coat, 2009; 66: 337
[15] Xia L, Wei Z, Wan M. J Colloid Interface Sci, 2010; 341: 1
[16] Chen L, Sun L J, Luan F, Liang Y, Li Y, Liu X X. J Power Sources, 2010; 195: 3742
[17] Nicolas-Debarnot D, Poncin-Epaillard F. Anal Chim Acta,2003; 475: 1
[18] Liu X X, Zhang L, Li Y B, Bian L J, Su Z, Zhang L J. J Mater Sci, 2005; 40: 4511
[19] Jiang H F, Liu X X. Electrochim Acta, 2010; 55: 7175
[20] Huang J X, Kaner R B. Chem Commun, 2006; 4: 367
[21] Liu X X, Dou Y Q, Wu J, Peng X Y. Electrochim Acta,2008; 53: 4693
[22] Peng X Y, Luan F, Liu X X, Diamond D, Lau K T. Electrochim Acta,2009; 54: 6172
[23] Zou B X, Liu X X, Diamond D, Lau K T. Electrochim Acta,2010; 55: 3915
[24] Liu X X, Zhang L, Li Y B, Bian L J, Huo Y Q, Su Z. Polym Bulletin, 2006; 57: 825
[25] Cummings C Y, Stott S J, Bonne M J, Edler K J, King P M, Mortimer R J,Marken F. J Solid State Electrochem, 2008; 12: 1541
[26] Liu X X, Bian L J, Zhang L, Zhang L J. J Solid State Electrochem, 2007; 11: 1279
