期刊
SMALL
卷 18, 期 3, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/smll.202105524
关键词
asymmetry; charge distribution; electrocatalysts; electronic structure; organic molecules
类别
资金
- National Natural Science Foundation of China [22075157, 21805148]
- Taishan Scholars Program [tsqn201909090]
- Natural Science Foundation of Shandong Province, China [ZR2019BEM016]
- Open Research Fund of State Key Laboratory of Bio-Fibers and Eco-Textiles, Qingdao University [ZKT06, GZRC202008]
- Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences [2020-02]
- Test Center of Tangshan Graphene Application Technology Public Service Platform
Organic molecular catalysts with well-controlled molecular structures have attracted attention for catalytic chemistry. By asymmetrically introducing S-heterocycles, the electronic distribution of active sites is regulated, leading to improved oxygen reduction performance. Asymmetric structure of as-BNT alters the catalytic active sites and changes the kinetics of catalytic reaction due to non-uniform charge distribution and increased dipole moment.
Organic molecular catalysts have received great attention as they have the merits of well-controlled molecular structures for the development of catalytic chemistry. Herein, the electronic distribution of active sites is regulated by asymmetrically introducing S-heterocycle on one side of the molecular core. As a result, the asymmetric as-PYT and as-BNT show higher oxygen reduction performance than their symmetric counterparts without (s-PY, s-PY2T) or with two S-heterocycle units (s-BN, s-BN2T). Density functional theory calculations reveal that the carbon atoms (site-12) at symmetric s-BN and s-BN2T are the catalytic active sites, while for asymmetric as-BNT, it has changed to amino-N atom (site-14). Due to the non-uniform charge distribution and increased dipole moment of as-BNT caused by asymmetric molecular configuration, the kinetics of catalytic reaction has changed significantly. The catalytically active sites of specific N atoms are further verified experimentally and theoretically by using sterically hindered phenyl groups. This work provides a simple but efficient method to design metal-free oxygen reduction electrocatalysts.
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