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Research Article | Open Access

Tailoring the d-band electronic structure of FePc by direct oxygen bridge on ZIF-8 derived ultrathin carbon shell to improve the oxygen reduction performance

Xilin Zhang1,3, Shan Wang1, Zhiyi Sun2, Zhongjun Ma3, Huixuan Wang1, Zongxian Yang1(), Qingfang Chang1(), Wenxing Chen2()
School of Physics, Henan Normal University, Xinxiang 453007, China
Energy & Catalysis Center, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
Key Laboratory of Yellow River and Huai River Water Environmental and Pollution Control, Ministry of Education, School of Environment, Henan Normal University, Xinxiang 453007, China
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A novel molecular electrocatalyst featuring with a direct oxygen atom bridging the iron phthalocyanine (FePc) and an ultrathin carbon substrate derived from ZIF-8, namely FePc/TAONG-N, was designed and synthesized. This direct connection with oxygen bridge significantly enhances the interaction between the FePc molecule and the carbon substrate, facilitating electron transfer and leading to an improved durability and activity in oxygen reduction reactions.

Abstract

Molecular catalysts with well-defined single atom sites and coordination environments exhibit significant potential as oxygen reduction electrocatalysts, but suffering from the activity and stability issues. Herein, the ultrathin carbon shell supported FePc molecule electrocatalysts (FePc/TA-ONG-N), featuring with a direct oxygen bridging between FePc and carbon substrate, were designed and synthesized. The direct connection with oxygen atom on carbon substrate, certified by the Fourier transform infrared spectroscopy (FTIR) and extended X-ray absorption fine structure (EXAFS), can remarkably enhance the interaction and facilitate electron transfer from Fe, leading to an improved activity by reducing adsorption strength of intermediate species through lowering the d-band center position. The resultant half-wave potential of 0.902 V together with a Tafel slope of 23.64 mV·dec−1 is superior to Pt/C and control samples. Such catalyst holds a promise as air-cathode electrocatalyst in Zn-air battery with excellent operation stability exceeding 80 h. The density functional theory (DFT) calculations and molecular dynamic simulations unveiled that the O-bridge can effectively stabilize the FePc molecule and function as electron buffer to donate/gain electrons to/from Fe atom during the adsorption of oxygenates. The current findings are insightful for developing molecular catalysts with high performance through substrate engineering and axial coordination.

Keywords

metal-organic frameworkaxial coordinationinterfacial electron transferiron phthalocyanineoxygen reduction reaction

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Nano Research
Volume 18 Issue 3,
March 2025
Article number: 94907235
DOI: 10.26599/NR.2025.94907235
Cite this article:
Zhang X, Wang S, Sun Z, et al. Tailoring the d-band electronic structure of FePc by direct oxygen bridge on ZIF-8 derived ultrathin carbon shell to improve the oxygen reduction performance. Nano Research, 2025, 18(3): 94907235. https://doi.org/10.26599/NR.2025.94907235
Topics:
Oxygen evolution reaction
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