Tailoring the <i>d</i>‐Band Center of WS<sub>2</sub> by Metal and Nonmetal Dual‐Doping for Enhanced Electrocatalytic Nitrogen Reduction
Tuning the adsorption energy of nitrogen intermediates and lowering the reaction energy barrier is essential to accelerate the kinetics of nitrogen reduction reaction (NRR), yet remains a great challenge. Herein, the electronic structure of WS<sub>2</sub> is tailored based on a metal and nonmetal dual-doping strategy (denoted Fe, F-WS<sub>2</sub>) to lower the d-band center of W in order to optimize the adsorption of nitrogen intermediates. The obtained Fe, F-WS<sub>2</sub> nanosheet catalyst presents a high Faradic efficiency (FE) of 22.42% with a NH<sub>3</sub> yield rate of 91.46 µg h<sup>-1</sup> mg<sub>cat.</sub> <sup>-1</sup>. The in situ characterizations and DFT simulations consistently show the enhanced activity is attributed to the downshift of the d-band center, which contributes to the rate-determining step of the second protonation to form N<sub>2</sub>H<sub>2</sub> <sup>*</sup> key intermediates, thereby boosting the overall nitrogen electrocatalysis reaction kinetics. This work opens a new avenue to enhanced electrocatalysis by modulating the electronic structure and surrounding microenvironment of the catalytic metal centers.
Authors
- Qingfang Chang
- Xiaoye Hu
- Syed Shoaib Ahmad Shah (ORCID: https://orcid.org/0000-0003-1741-6048)
- Shichuan Zhong (ORCID: https://orcid.org/0000-0001-9261-3944)
- Lulu Wen (ORCID: https://orcid.org/0000-0001-6720-556X)
- Xinyang Li (ORCID: https://orcid.org/0000-0002-7816-4262)
- Yue Li (ORCID: https://orcid.org/0000-0002-1202-4224)
- Pan Zeng (ORCID: https://orcid.org/0000-0003-4632-6279)
- Xilin Zhang (ORCID: https://orcid.org/0000-0002-7141-5700)
- Weiping Cai (ORCID: https://orcid.org/0000-0002-4515-6098)
Institutions
- University of Science and Technology of China (CN)
- Tiangong University (CN)
- Chinese Academy of Sciences (CN)
- Hefei Institutes of Physical Science (CN)
- Institute of Solid State Physics (CN)
- Henan Normal University (CN)
- National University of Sciences and Technology (PK)
Publication Details
- Journal
- Small
- Published
- 2024-09-30
- DOI
- https://doi.org/10.1002/smll.202407594
- Citations
- 9
- Primary Topic
- Ammonia Synthesis and Nitrogen Reduction
- Type
- article
- Field-Weighted Citation Impact
- 0.96
Funders
- Henan Normal University
- Salt Science Research Foundation
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- China Postdoctoral Science Foundation
- National Science Fund for Distinguished Young Scholars
- High Magnetic Field Laboratory, Chinese Academy of Sciences