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Title: Resolving the Iron Phthalocyanine Redox Transitions for ORR Catalysis in Aqueous Media

Abstract

Metal macrocycles are among the most important catalytic systems in electrocatalysis and biocatalysis owing to their rich redox chemistry. Precise understanding of the redox behavior of metal macrocycles in operando is essential for fundamental studies and practical applications of this catalytic system. Here we present electrochemical data for the representative iron phthalocyanine (FePc) in both aqueous and nonaqueous media coupled with in situ Raman and X-ray absorption analyses to challenge the traditional notion of the redox transition of FePc at the low potential end in aqueous media by showing that it arises from the redox transition of the ring. Our data unequivocally demonstrate that the electron is shuttled to the Pc ring via the Fe(II)/Fe(I) redox center. The Fe(II)/Fe(I) redox transition of FePc in aqueous media is indiscernible by normal spectroscopic methods owing to the lack of a suitable axial ligand to stabilize the Fe(I) state.

Authors:
 [1]; ORCiD logo [2];  [2]; ORCiD logo [2];  [2]; ORCiD logo [2]
  1. Department of Chemistry and Chemical Biology, Northeastern University, Boston, Massachusetts 02115, United States; Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80200, Jeddah 21589, Saudi Arabia
  2. Department of Chemistry and Chemical Biology, Northeastern University, Boston, Massachusetts 02115, United States
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1409596
Report Number(s):
BNL-114648-2017-JA¿¿¿
Journal ID: ISSN 1948-7185
DOE Contract Number:  
SC0012704
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry Letters; Journal Volume: 8; Journal Issue: 13
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Alsudairi, Amell, Li, Jingkun, Ramaswamy, Nagappan, Mukerjee, Sanjeev, Abraham, K. M., and Jia, Qingying. Resolving the Iron Phthalocyanine Redox Transitions for ORR Catalysis in Aqueous Media. United States: N. p., 2017. Web. doi:10.1021/acs.jpclett.7b01126.
Alsudairi, Amell, Li, Jingkun, Ramaswamy, Nagappan, Mukerjee, Sanjeev, Abraham, K. M., & Jia, Qingying. Resolving the Iron Phthalocyanine Redox Transitions for ORR Catalysis in Aqueous Media. United States. doi:10.1021/acs.jpclett.7b01126.
Alsudairi, Amell, Li, Jingkun, Ramaswamy, Nagappan, Mukerjee, Sanjeev, Abraham, K. M., and Jia, Qingying. Wed . "Resolving the Iron Phthalocyanine Redox Transitions for ORR Catalysis in Aqueous Media". United States. doi:10.1021/acs.jpclett.7b01126.
@article{osti_1409596,
title = {Resolving the Iron Phthalocyanine Redox Transitions for ORR Catalysis in Aqueous Media},
author = {Alsudairi, Amell and Li, Jingkun and Ramaswamy, Nagappan and Mukerjee, Sanjeev and Abraham, K. M. and Jia, Qingying},
abstractNote = {Metal macrocycles are among the most important catalytic systems in electrocatalysis and biocatalysis owing to their rich redox chemistry. Precise understanding of the redox behavior of metal macrocycles in operando is essential for fundamental studies and practical applications of this catalytic system. Here we present electrochemical data for the representative iron phthalocyanine (FePc) in both aqueous and nonaqueous media coupled with in situ Raman and X-ray absorption analyses to challenge the traditional notion of the redox transition of FePc at the low potential end in aqueous media by showing that it arises from the redox transition of the ring. Our data unequivocally demonstrate that the electron is shuttled to the Pc ring via the Fe(II)/Fe(I) redox center. The Fe(II)/Fe(I) redox transition of FePc in aqueous media is indiscernible by normal spectroscopic methods owing to the lack of a suitable axial ligand to stabilize the Fe(I) state.},
doi = {10.1021/acs.jpclett.7b01126},
journal = {Journal of Physical Chemistry Letters},
number = 13,
volume = 8,
place = {United States},
year = {Wed Jun 14 00:00:00 EDT 2017},
month = {Wed Jun 14 00:00:00 EDT 2017}
}