de Souza Carolino Adriano, Moraes Biondo Matheus, Ţălu Ştefan, da Fonseca Filho Henrique Duarte, Campelo Pedro Henrique, Bezerra Jaqueline de Araújo, Mota Cicero, da Frota Hidembergue Ordozgoith, Bagnato Vanderlei Salvador, Inada Natalia Mayumi, Sanches Edgar Aparecido
Laboratory of Nanostructured Polymers (NANOPOL), Federal University of Amazonas (UFAM), Manaus 69067-005, AM, Brazil.
Graduate Program in Physics (PPGFIS), Federal University of Amazonas (UFAM), Manaus 69067-005, AM, Brazil.
Molecules. 2022 Jul 31;27(15):4905. doi: 10.3390/molecules27154905.
The development of conjugated polymer-based nanocomposites by adding metallic particles into the polymerization medium allows the proposition of novel materials presenting improved electrical and optical properties. Polyaniline Emeraldine-salt form (ES-PANI) has been extensively studied due to its controllable electrical conductivity and oxidation states. On the other hand, tungsten oxide (WO) and its di-hydrated phases, such as WO·2HO, have been reported as important materials in photocatalysis and sensors. Herein, the WO·2HO phase was directly obtained during the in-situ polymerization of aniline hydrochloride from metallic tungsten (W), allowing the formation of hybrid nanocomposites based on its full oxidation into WO·2HO. The developed ES-PANI-WO·2HO nanocomposites were successfully characterized using experimental techniques combined with Density Functional Theory (DFT). The formation of WO·2HO was clearly verified after two hours of synthesis (PW nanocomposite), allowing the confirmation of purely physical interaction between matrix and reinforcement. As a result, increased electrical conductivity was verified in the PW nanocomposite: the DFT calculations revealed a charge transfer from the -orbitals of the polymeric phase to the -orbitals of the oxide phase, resulting in higher conductivity when compared to the pure ES-PANI.
通过在聚合介质中添加金属颗粒来制备共轭聚合物基纳米复合材料，这使得新型材料得以提出，这些材料具有改善的电学和光学性能。聚苯胺翡翠盐形式（ES-PANI）因其可控的电导率和氧化态而受到广泛研究。另一方面，氧化钨（WO）及其二水合物相，如WO·2H₂O，已被报道为光催化和传感器领域的重要材料。在此，在盐酸苯胺从金属钨（W）原位聚合过程中直接获得了WO·2H₂O相，这使得基于其完全氧化成WO·2H₂O形成了杂化纳米复合材料。所制备的ES-PANI-WO·2H₂O纳米复合材料通过结合密度泛函理论（DFT）的实验技术成功进行了表征。在合成两小时后（PW纳米复合材料），WO·2H₂O的形成得到了明确验证，从而证实了基体与增强体之间纯粹的物理相互作用。结果，在PW纳米复合材料中验证了电导率的提高：DFT计算表明电荷从聚合物相的π轨道转移到氧化物相的π*轨道，与纯ES-PANI相比，导致更高的电导率。
