شیمى کاربردى روز

شیمى کاربردى روز

پتانسیل الکترودی الیگومرهای پیرول: رویکرد نظری و تجربی

نوع مقاله : مقاله علمی پژوهشی

نویسندگان
1 دانشکده شیمی، دانشگاه صنعتی شاهرود، سمنان، ایران
2 دانشکده شیمی، دانشگاه دامغان، سمنان، ایران
چکیده
مطالعه پتانسیل اکسایش و خواص الکترونیکی پلیمرهای رسانا برای طراحی مواد جدید با خواص بهبود یافته بسیار مهم هستند. مطالعه حاضر بر روی اطلاعات الکتروشیمیایی شامل پتانسیل الکترودی الیگومرهای پیرول (nPy: n = 2-8) و همچنین خواص ساختاری و الکترونیکی آنها متمرکز شده است. از شیمی محاسباتی بر پایه محاسبات DFT برای تعیین پتانسیل اکسیداسیون استاندارد (ox°E) گونه­های nPy در مقایسه با الکترود مرجع کالومل در محلول‌های آبی و غیر آبی استفاده شد. توافق خوبی بین پتانسیل ردوکس پیش‌بینی‌شده و مقادیر تجربی قابل دسترس با میانگین انحراف مطلق 0.16 ولت به‌دست آمد. همچنین همبستگی خطی خوبی برای مقادیر ox°E با مقادیر سطح انرژی HOMO و پتانسیل یونیزاسیون گونه­ها مشاهده شد. علاوه بر این، مقدار پتانسیل اکسایش تخمینی 0.21 ولت در مقابل الکترود مرجع SCE برای پلی­پیرول، poly(Py) ، در حلال THF به دست آمد. منحنی‌های شبیه‌سازی‌شده جریان-ولتاژ (IV) نشان داد که رسانایی زنجیره‌های الیگومری با افزایش طول زنجیر افزایش می­یابد. بر اساس بررسی مقادیر شکاف نواری حاصل از نتایج طیفی TD-DFT، افزایش سهولت حمل بار برای زنجیره­های الیگومری بلند مشاهده شد. فیلم­های پلی­پیرول از طریق الکتروشیمیایی با اکسیداسیون آندی مستقیم منومر پیرول در محلول آبی به روش ولتامتری چرخه­ای (CV) تهیه شدند. نتایج نشان داد که پتانسیل اکسایش زنجیره­های اولیگومری در حین رشد پلیمر طی فرایند الکتروپلیمریزاسیون کاهش می­یابد.
کلیدواژه‌ها
موضوعات

عنوان مقاله English

Electrode Potential for a Series of Oligo(pyrrole)s: Theoretical and Experimental Approaches

نویسندگان English

Zeynab Ashrafi 1
Hossein Nikoofard 1
Mobina Hosseini 2
1 Faculty of Chemistry, Shahrood University of Technology, Shahrood 36199-95161, Iran
2 School of Chemistry, Damghan University, Damghan 36716-41167, Iran
چکیده English

The study of oxidation potential and electronic properties of conducting polymers are very important for designing new material with improved properties. The current study focused on the electrochemical information about potential electrode of pyrrole (Py) oligomers, nPy: n = 2-8, as well as their structural and electronic properties. Computational chemistry based on DFT calculations were used to determine an accurate standard oxidation potential (E_ox^°) for the nPy with respect to the calomel reference electrode in the aqueous and non-aqueous solutions. A nice agreement between the predicted and available experimental redox potential was obtained with an average absolute deviation of 0.016 V. A good linear correlation with both the HOMO level and the ionization potential were obtained for the E_ox^° values. Additionally, an estimated E_ox^° value of 0.21 V vs. SCE was obtained for poly(Py) in THF. The simulated current-voltage (IV) curves revealed an increase in the conductivity of nPy chains as the length of oligomer increasing. Based on the analysis of the band gap from the TD-DFT spectral results, a high ease of charge transport was observed for long oligomer chains. Poly(Py) films were synthesized electro-chemically by the direct anodic oxidation of pyrrole in an aqueous solution via cyclic voltammetry (CV) technique. It was found that the oxidation potential for oligo(Py) chains decreases through the growing polymer during the electro-polymerization.

کلیدواژه‌ها English

Oligopyrrole
DFT calculations
Cyclic voltammetry
Oxidation potential
IV-curves
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