کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
6614180 | 459623 | 2014 | 9 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Effect of amine substituted at ortho and para positions on the electrochemical and electrocatalytic properties of cobalt porphyrins self-assembled on glassy carbon surface
ترجمه فارسی عنوان
اثر آمین در جایگاه های ارتو و پارا جایگزین شده در خواص الکتروشیمیایی و الکتریکی کاتالیستی پورفیرین کبالت خودمختار بر روی سطح کربن شیشه ای
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
مهندسی شیمی
مهندسی شیمی (عمومی)
چکیده انگلیسی
This work addresses the influence of amine group substituted at para and ortho positions of the phenyl groups on the electrochemical and electrocatalytic properties of cobalt porphyrins self-assembled on glassy carbon electrode (GCE). We have synthesized meso-tetra(para-aminophenyl)porphyrinatocobalt(II) (Co(II)MTpAP) and meso-tetra(ortho-aminophenyl)porphyrinatocobalt(II) (Co(II)MToAP) and were self-assembled on GCE through Michael addition of nucleophilic amine with olefinic GCE surface. Cyclic voltammetry, reflectance spectroscopy and X-ray photoelectron spectroscopy (XPS) techniques were employed to confirm the formation of the self-assembled monolayers (SAMs) of Co(II)MTpAP and Co(II)MToAP on GCEs. Interestingly, the SAM of Co(II)MTpAP in 0.1Â M H2SO4 shows two redox waves at 0.37 and 0.60Â V whereas the SAM of Co(II)MToAP shows a single redox wave at 0.32Â V, indicating the influence of amine group position in the phenyl ring on the redox chemistry of porphyrin. In contrary, the SAMs of the corresponding free base porphyrins prepared under identical conditions show a single redox wave around 0.36Â V. Thus, we have assigned the redox wave at 0.37Â V to Co(II)Por1â/Co(II)Por2â and 0.60Â V to CoIII/II redox couples for the SAM of Co(II)MTpAP. In the case of Co(II)MToAP, we have assigned the redox wave at 0.32Â V due to both Co(II)Por1â/Co(II)Por2â and CoIII/II. The surface coverage estimated from the charge consumed for the oxidation of CoIII/II was used to study the thermodynamics and kinetics of Co(II)MTpAP and Co(II)MToAP self-assembled on GCE. Further, the electrochemical reduction of dioxygen was studied at the SAMs of Co(II)MTpAP and Co(II)MToAP in 0.1Â M H2SO4. The dioxygen reduction potential was shifted to less positive potential with enhanced current at both the SAMs of Co(II)MTpAP and Co(II)MToAP when compared to bare GCE. Among the two SAMs, Co(II)MTpAP significantly reduced the overpotential of dioxygen reduction (65Â mV) when compared to Co(II)MToAP.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Electrochimica Acta - Volume 115, 1 January 2014, Pages 197-205
Journal: Electrochimica Acta - Volume 115, 1 January 2014, Pages 197-205
نویسندگان
Palanisamy Muthukumar, S. Abraham John,