本論文主要探討當混入不同材料與聚苯胺形成複合物時，聚苯胺的電化學活性是否會因而產生變化。並將材料的種類分三部份舉例來討論，第一部份：用高分子酸(如：聚(磺酸苯乙烯))與聚苯胺形成複合物、第二部份：用非酸型高分子(如：聚(乙烯醇))與聚苯胺形成複合物；第三部份：用金屬奈米粒子(如：金奈米粒子)與聚苯胺形成複合物。本研究發現，當混入不同材料與聚苯胺形成複合物時，將對聚苯胺的電化學活性造成不同的影響。分述如下：
(1) 以聚(磺酸苯乙烯)為複合材
　　此研究利用聚(磺酸苯乙烯)摻雜去質子化的聚苯胺來合成聚苯胺-聚(磺酸苯乙烯)複合材料。發現此摻雜程序遵守費克質傳定律，於80oC時的聚(磺酸苯乙烯)在聚苯胺高分子膜中的質傳表觀係數為(0.37×10-16 cm2/s)，使得能夠快速地於20分鐘內製備此複合物；由於此值比在25oC的質傳係數(0.28×10-18 cm2/s)大上132倍，導致於25oC的電化學應用過程中，聚(磺酸苯乙烯)仍能穩定地存在於聚苯胺高分子膜中。其提供一個酸性的環境，讓聚苯胺能在中性液裡應用時，依然能夠再質子化，並保持其電化學活性。且於再質子化時，又能作為陽離子自由基的穩定劑，使聚苯胺能有更快的電子傳送速率。
(2) 以聚(乙烯醇)為複合材
　　此研究利用聚苯胺奈米纖維與聚(乙烯醇)混摻來合成聚苯胺-聚(乙烯醇)奈米複合材料。發現聚苯胺奈米纖維混以25wt%聚(乙烯醇)後，所形成的複合材料具有多孔隙結構與高電化學活性。更發現聚苯胺奈米纖維與聚(乙烯醇)之間的氫鍵作用力，可保護聚苯胺奈米纖維上的雙偏質子，使其免於被水分子所攻擊而產生水解反應，可提升聚苯胺電化學活性的穩定度。此外，此研究亦發現，對此奈米複合材料進行熱處理後，聚苯胺主鏈上的苯環將會與聚(乙烯醇)的醇基進行反應生成酯鍵結，造成聚苯胺的電化學活性與其穩定性大幅下降。
(3) 以金奈米粒子為複合材
　　此研究利用聚苯胺奈米纖維還原四氯金酸來合成聚苯胺-金的奈米複合材料。發現四氯金離子傾向與聚苯胺上被質子化的亞胺基進行錯合，並逐漸地電子轉移；在聚苯胺奈米纖維表面上，均勻地還原出超微小的奈米金粒子(2nm)。於此此研究亦提出其可能的形成機構。此外，此研究發現聚苯胺奈米纖維與金奈米粒子間的作用力，會提升其各別的電化學活性與電催化活性。將此奈米複合材料應用在過氧化氫的感測上時，其製成之感應器可擁有高敏感度(8.34 mA/M)與快速應答(3秒)的特性。

This study investigated the effect of the interaction between polyaniline (PANI) and its composite materials on electroactivity of PANI. The composite materials are classified into polyacids (e.g. poly(styrene sulfonic acid), PSS), non-polyacids (e.g. poly(vinyl alcohol), PVA), and metals (e.g. gold nanoparticles, AuNPs). We found that different kinds of interaction between the materials really influenced the electroactivity of PANI.
(1) incorporating PSS with PANI as the composite material
PANI-PSS was prepared by redoping de-protonated PANI with PSS. Through the kinetic study, we found that the apparent diffusion coefficient (D) value of PSS in PANI film was 0.37 × 10-16 cm2/s at 80 °C and the redoping process obeys the Fickian diffusion kinetics, hence, the redoping process could be fast finished in 1200 seconds. The reason of the good electro-stability of PANI-PSS under a disgusting electrochemical process can be attributed to the low D value of PSS (0.28 × 10-18 cm2/s) in PANI film that prevented the release of PSS form PANI film. PSS given PANI an acidic environmental for re-protonated its nitrogen sites under electrochemical sweeping in neutral solution. Furthermore, the PSS act as a stabilizer for re-protonated nitrogen sites on PANI, thus PANI-PSS with a faster charge transfer rate and higher electroactivity than PANI.
(2) incorporating PVA with PANI as the composite material
PANI-PVA nanocomposite was prepared by blending Polyaniline nanofibers (PANFs) with aqueous solution of polyvinyl alcohol (PVA). We found that blended 25 wt% PVA with PANF then casting at 105 oC can obtain a high-electroactive and porous nanocomposite (PANF-PVA25). The presence of the hydrogen bonding interaction between PANF and PVA improves the electroactive stability of PANF-PVA25, due to it prevented the attack of H2O on the protonated imine sites. However, the electroactivity and electroactive stability decreased after thermal treatment of PANF-PVA25 at 200 oC for 15 min due to that causing the ether linkage between PANF and PVA polymer chain.
(3) incorporating AuNPs with PANI as the composite material
PANI-AuNPs nanocomposite was prepared by using PANFs for reducing chloroaurate anions (AuCl4-). We found that ultra-fine and uniform AuNPs (2 nm) were selectively reduced on PANFs. The water dispersible PANFs, which acted as the reductant, provided a high surface area to absorb (form complexes) and react with AuCl4-. A possible mechanism for the formation of the AuNPs-PANF nanocomposite was proposed. The strong interaction would accelerate the redox reactions for both PANFs and AuNPs, and enhanced the electroactivity of PANF and the electrocatalytic activity of AuNPs. The electrode of AuNPs-PANFs exhibited a fast response time (less than 3 s) and a high sensitivity (8.34 mA M-1) for H2O2 sensing.

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