Manipulating the Adjacent Microenvironment of Atomically Dispersed FeN<sub>4</sub> Sites via Cross-Link-Induced 3D Carbon Nest for Efficient Oxygen Reduction
Electronic perturbation induced by the microenvironment regulation adjacent to the FeN4 sites anchored on metal–N–C materials will accelerate its oxygen reduction reaction (ORR) kinetics. Herein, we report a fine-tuning in the charge configuration of FeN4 sites through a defect-rich N/S-doped carbon nest derived from the chemically cross-linked pyrrole/thiophene copolymer (CCPPT) with a sp3-hybridized cross-linker. Compared with the pyrrole/thiophene copolymer (PPT) without the cross-linker, CCPPT with a knitted three-dimensional (3D) network delivers higher defect density and ∼2-fold sulfur retention after pyrolysis. The structural characterizations combined with theoretical calculations suggest that adjacent vacancy defects (Cvd) and FeN4/S2 moiety together induce the charge redistribution of the FeN4 sites on the resultant CC-Fe1/NSC from CCPPT, reducing the adsorption strength of the oxygen-containing intermediates and the energy barrier of ORR. As expected, CC-Fe1/NSC shows an impressive half-wave potential of ∼0.91 V vs reversible hydrogen electrode (RHE), surpassing both the PPT-derived Fe1/NSC (0.88 V) and the commercial Pt/C (0.86 V). This work provides a distinctive path to manipulate the adjacent microenvironment of the single-atom catalysts toward ORR or even beyond.
Authors
- Tingting Chao
- Yun Lu (ORCID: https://orcid.org/0000-0002-5182-7839)
- Mingxing Gong
- Zedong Zhang (ORCID: https://orcid.org/0009-0003-9312-8387)
- Tonghui Zhao
- Dingsheng S. Wang (ORCID: https://orcid.org/0000-0003-0074-7633)
- Yanmin Hu (ORCID: https://orcid.org/0000-0003-0630-5342)
- Huile Jin (ORCID: https://orcid.org/0000-0002-2899-0515)
- Wei Chen (ORCID: https://orcid.org/0000-0002-7774-7685)
- Yadong Li (ORCID: https://orcid.org/0000-0003-1544-1127)
- Yapeng Li (ORCID: https://orcid.org/0000-0002-7704-4787)
- Tao Shen (ORCID: https://orcid.org/0009-0000-1656-9486)
- Deli Wang (ORCID: https://orcid.org/0000-0003-2023-6478)
- Dongdong Xiao (ORCID: https://orcid.org/0000-0001-8467-3066)
- Guangjin Wang (ORCID: https://orcid.org/0000-0002-1063-5179)
- Min Young Song (ORCID: https://orcid.org/0000-0003-4980-2023)
Institutions
- University of Science and Technology of China (CN)
- Wenzhou University (CN)
- Foshan University (CN)
- Chinese Academy of Sciences (CN)
- Hefei National Center for Physical Sciences at Nanoscale (CN)
- FZU ‒ Institute of Physics of the Academy of Sciences of the Czech Republic (CZ)
- Institute of Physics (CN)
- National Laboratory for Superconductivity (CN)
- Nano Carbon (Poland) (PL)
- Huazhong University of Science and Technology (CN)
- Tsinghua University (CN)
Publication Details
- Journal
- ACS Catalysis
- Published
- 2025-01-09
- DOI
- https://doi.org/10.1021/acscatal.4c06546
- Citations
- 7
- Primary Topic
- Electrocatalysts for Energy Conversion
- Type
- article
- Field-Weighted Citation Impact
- 2.54
Funders
- National Natural Science Foundation of China
- China Postdoctoral Science Foundation
- Wenzhou Municipal Science and Technology Bureau
- Department of Education of Guangdong Province
- Basic and Applied Basic Research Foundation of Guangdong Province