Redox chemistry of N4-Fe 2+ in iron phthalocyanines for oxygen reduction reaction

doi:10.1016/S1872-2067(20)63731-7

Chinese Journal of Catalysis ›› 2021, Vol. 42 ›› Issue (8): 1404-1412.DOI: 10.1016/S1872-2067(20)63731-7

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Redox chemistry of N₄-Fe ²⁺ in iron phthalocyanines for oxygen reduction reaction

Anuj Kumar^a^,^b, Ying Zhang^c, Yin Jia^a, Wen Liu^a^,^#(), Xiaoming Sun^a^,^*()

^aState Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
^bDepartment of Chemistry, Institute of Humanities and Applied Science, GLA University, Mathura 281406, India
^cSchool of Chemistry, Monash University, Wellington Road, Clayton 3800, VIC, Australia

Received:2020-08-09 Accepted:2020-08-09 Online:2021-08-18 Published:2020-12-10
Contact: Wen Liu,Xiaoming Sun
About author:^#. E-mail: wenliu@mail.buct.edu.cn
^*. Tel/Fax: +86-10-64448751; E-mail: sunxm@mail.buct.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China(21675007);This work was supported by the National Natural Science Foundation of China(21676015);This work was supported by the National Natural Science Foundation of China(21520102002);This work was supported by the National Natural Science Foundation of China(91622116);Beijing University of Chemical Technology(buctrc201901);National Natural Science Foundation of China and Ministry of Foreign Affairs and International Cooperation, Italy(NSFC-MAECI 51861135202);the National Key Research and Development Project(2018YFB1502401);the National Key Research and Development Project(2018YFA0702002);the Royal Society and the Newton Fund through the Newton Advanced Fellowship award(NAF\R1\191294);the Program for Changjiang Scholars and Innovation Research Team in the University(IRT1205);the Fundamental Research Funds for the Central Universities, and the long-term subsidy mechanism from the Ministry of Finance and the Ministry of Education of PRC

Abstract

Abstract:

A precise understanding of the redox chemistry of N_m-M ⁿ⁺ (like N₄-Fe ²⁺) systems is essential for fundamental studies and rational design of N_m-M ⁿ⁺-based electrocatalysts for the oxygen reduction reaction (ORR). Herein, three different iron phthalocyanines (FePcs) adsorbed on carbon nanotubes ((NH₂)₄FePc@CNTs, (t-Bu)₄FePc@CNTs, and FePc@CNTs) were evaluated to demonstrate the effect of the electron donating power of the substituents on the Fe ³⁺/Fe ²⁺redox potential of FePc@CNTs and the role of these composites as ORR mediators in alkaline media. The Fe ³⁺/Fe ²⁺redox potential of the FePcs was found to shift towards the cathodic region upon substitution with electron-donating groups. This up-field shift in the e_g-orbital leads to a lower overlap between the onset potential of the Fe ³⁺/Fe ²⁺ redox couple and that of the ORR, and thus, the ORR activity decreased in the following order based on the substitution of FePc: ‒H > ‒t-Bu > ‒NH₂.

Key words: Iron phthalocyanines, Substitution effect, Oxygen reduction reaction, Carbon nanotubes, Activity descriptor

Anuj Kumar, Ying Zhang, Yin Jia, Wen Liu, Xiaoming Sun. Redox chemistry of N₄-Fe ²⁺ in iron phthalocyanines for oxygen reduction reaction[J]. Chinese Journal of Catalysis, 2021, 42(8): 1404-1412.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63731-7

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Figures/Tables 5

Scheme 1. Schematic representation of synthesis of FePc@CNTs composite via microwave-assisted strategy.

Fig. 1. TEM images of CNTs (a) and enlarged view of selected CNTs (b), FePc@CNTs (c) and enlarged view of selected FePc@CNTs (d).

Fig. 2. (a) FT-IR spectra of CNTs and FePcs@CNTs; (b) UV-visible spectra of CNTs, unsupported FePcs, and FePcs@CNTs; (c) XRD pattern of FePcs@CNTs; (d) Expanded view of XRD pattern of (t-Bu)4FePc@CNTs.

Fig. 3. (a) CVs of (NH2)4FePc@CNTs, (t-Bu)4FePc@CNTs, and FePc@CNTs recorded in 0.1 M KOH under O2/N2 environment at 50 mV s-1 scan rate; (b) LSV curves for FePc@CNTs, (NH2)4FePc@CNTs, (t-Bu)4FePc@CNTs, and 20% Pt/C, recorded in 0.1 M KOH in presence of O2 at 5 mV s-1 with 1600 rpm rotation rate; (c) Comparison of ORR activity in terms of Fe2+/Fe3+ redox potential vs. ORR formal potential; (d) LSV curves of FePc@CNTs before and after dipping in thiocyanate anion (SCN?) at 5 mV s-1 scan rate with 1600 r/min rotation rate.

Fig. 4. Representation of up-shift in the eg-orbital with strongly electron donating groups (relative hardness of Fe-O2 adduct).

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Redox chemistry of N₄-Fe ²⁺ in iron phthalocyanines for oxygen reduction reaction

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