Acid concentration, low- and high-valent sulfate anion, and solvent effects on polaronic transitions and conductivity of new poly (ortho-methoxyaniline) nanocomposites

IF 3.1 3区化学 Q2 POLYMER SCIENCE

Polymer Bulletin Pub Date : 2025-01-28 DOI:10.1007/s00289-025-05642-5

Ali Reza Modarresi-Alam, Ilnaz Shariati, Ferydoon Khamooshi, Samaneh Doraji-Bonjar

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引用次数: 0

Abstract

The aim of this research is the identification of the changes in anion- and solvent-dependent polaronic transitions and the ratio of acid to monomer during the polymerization of new poly(ortho-methoxyaniline) nanosilica-supported sulfuric acid emeraldine salt1/salt2 (POMA-NSSSA-ES1/ES2) nanocomposites. The synthesis is done by doping poly(ortho-methoxyaniline)-emeraldine base (POMA-EB) in the presence of nanosilica-supported sulfuric acid (NSSSA) under solid-state condition. The structure, size, and morphology of all samples were identified using spectroscopy methods. Effect of acid concentration (0.5, 1.5, and 2.0) and low- and high-valent sulfate anion (H₂SO₄/HSO₄⁻ Vs. HSO₄⁻/SO₄²⁻) on polaronic transitions of poly(ortho-methoxyaniline) nanocomposites in different solvents (NMP, MCR, DMSO, and MeOH), and conductivity were studied. Afterwards, changes in polaron mutations under changing conditions were analyzed. Increasing the acid concentration compared to the monomer increases the absorption number (λ_max) in the UV–Vis study along with hypsochromic effect (blueshift) and bathochromic effect (redshift) in low acid concentration for polaronic transition. The anion effect proved that by increasing the negative charge of the anion (SO₄²⁻) due to the limiting potential of the polaron and bipolaron structures, it prevents the creation of delocalized polaron structure with no change in the POMA-NSSSA-ES2 nanocomposite conductivity. Results showed that the average size of nanocomposite particle obtained by this method was a range of 40–50 nm and the morphology of nanocomposites was spherical (nanospheres). POMA-NSSSA nanocomposites were completely in a doped state and the emeraldine salt from of POMA. During this research, for the first time, the polaronic orbital energy level was determined.

Graphical abstract

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酸浓度、低价和高价硫酸盐阴离子及溶剂对新型聚邻甲氧基苯胺纳米复合材料极化跃迁和电导率的影响

本研究的目的是确定在聚（邻甲氧基苯胺）纳米硅负载的硫酸绿绿盐t1/salt2 （POMA-NSSSA-ES1/ES2）纳米复合材料聚合过程中阴离子和溶剂依赖的极性转变以及酸与单体的比例的变化。在纳米二氧化硅负载硫酸（NSSSA）的存在下，在固态条件下掺杂聚邻甲氧基苯胺祖母绿碱（POMA-EB）进行了合成。所有样品的结构、大小和形态用光谱学方法鉴定。研究了酸浓度（0.5、1.5和2.0）和低价和高价硫酸盐阴离子（H2SO4/HSO4−Vs. HSO4−/SO42−）对聚邻甲氧基苯胺纳米复合材料在不同溶剂（NMP、MCR、DMSO和MeOH）中的极性转变和电导率的影响。然后，分析了极化子突变在不同条件下的变化。与单体相比，酸浓度的增加增加了紫外-可见研究中的吸收数（λmax），并伴随着低酸浓度下的色变效应（蓝移）和显色效应（红移）。阴离子效应证明，由于极化子和双极化子结构的极限势，通过增加阴离子（SO42−）的负电荷，可以防止极化子结构的离域产生，而POMA-NSSSA-ES2纳米复合材料的电导率没有变化。结果表明，该方法制备的纳米复合材料颗粒的平均尺寸为40 ~ 50 nm，纳米复合材料的形貌为球形（纳米球）。POMA- nsssa纳米复合材料完全处于掺杂状态，其绿宝石盐来自于POMA。在本研究中，首次确定了极化子轨道能级。图形抽象

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来源期刊

Polymer Bulletin 化学-高分子科学

CiteScore

6.00

自引率

6.20%

发文量

审稿时长

5.5 months

期刊介绍： "Polymer Bulletin" is a comprehensive academic journal on polymer science founded in 1988. It was founded under the initiative of the late Mr. Wang Baoren, a famous Chinese chemist and educator. This journal is co-sponsored by the Chinese Chemical Society, the Institute of Chemistry, and the Chinese Academy of Sciences and is supervised by the China Association for Science and Technology. It is a core journal and is publicly distributed at home and abroad. "Polymer Bulletin" is a monthly magazine with multiple columns, including a project application guide, outlook, review, research papers, highlight reviews, polymer education and teaching, information sharing, interviews, polymer science popularization, etc. The journal is included in the CSCD Chinese Science Citation Database. It serves as the source journal for Chinese scientific and technological paper statistics and the source journal of Peking University's "Overview of Chinese Core Journals."