Tailoring activity of iron phthalocyanine by edge-nitrogen sites induced electronic delocalization

Sun, Qi; Wang, Zhaoyang; Zhou, Min; Li, Jiantao; Lu, Ruihu; Wang, Yuhan; Liao, Xiaobin; Zhao, Yan

doi:10.1016/j.apsusc.2023.157154

Tailoring activity of iron phthalocyanine by edge-nitrogen sites induced electronic delocalization

Journal Article · Thu Mar 30 00:00:00 EDT 2023 · Applied Surface Science

DOI:https://doi.org/10.1016/j.apsusc.2023.157154· OSTI ID:2423685

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Wuhan Univ. of Technology (China)
Wuhan Univ. of Technology (China); Hubei Engineering Univ., Xiaogan (China)
Wuhan Univ. of Technology (China); Univ. of Auckland (New Zealand)
Wuhan Univ. of Technology (China); Wuhan Univ. (China); Sichuan Univ., Chengdu (China)

Fe-N-C catalysts have been recognized as the most satisfactory candidates alternatively to Pt-based catalysts for oxygen reduction reaction (ORR). However, fine-tailoring of their intrinsic ORR catalytic activity still remains a great challenge due to the inferior accessibility and intrinsic activity of FeN_x moieties. Herein, one order of magnitude activity enhancement of pristine Fe-N-C through cooperating with nitrogen-doped carbon micro-flower is achieved. The axial coordination effect between Fe active center and nitrogen atoms in support can break the electronic distribution symmetry of FeN_x moieties and induce the electron delocalization on Fe active center and the electron localization on N, respectively, which favor the adsorption behavior of *OH intermediate. As a result, the catalyst exhibits a remarkable half-wave potential of 0.9 V and a high kinetic current density of 74.04 mA cm^-2 at 0.85 V. In addition, when utilized as a cathode catalyst of liquid Zn-air batteries (ZABs), it possesses excellent electrochemical performance, for example, a high open circuit voltage (OCV) and peak power density of 1.59 V and 170.09 mW cm^-2, respectively. In conclusion, this work provides a new understanding into the activity enhancement mechanism of Fe-N-C catalysts, and inspires electronic delocalization of active sites for adjusting catalytic activity.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: China Postdoctoral Science Foundation; Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory; National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2423685

Journal Information:: Applied Surface Science, Journal Name: Applied Surface Science Journal Issue: C Vol. 624; ISSN 0169-4332

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Tailoring activity of iron phthalocyanine by edge-nitrogen sites induced electronic delocalization

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