Wen Lulu, Chang Qingfang, Zhang Xilin, Li Xinyang, Zhong Shichuan, Zeng Pan, Shah Syed Shoaib Ahmad, Hu Xiaoye, Cai Weiping, Li Yue
Key Lab of Materials Physics, Anhui Key Lab of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei, Anhui, 230031, P. R. China.
School of Physics, Henan Key Laboratory of Photovoltaic Materials, Henan Normal University, Xinxiang, Henan, 453000, P. R. China.
Small. 2024 Dec;20(50):e2407594. doi: 10.1002/smll.202407594. Epub 2024 Sep 30.
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 is tailored based on a metal and nonmetal dual-doping strategy (denoted Fe, F-WS) to lower the d-band center of W in order to optimize the adsorption of nitrogen intermediates. The obtained Fe, F-WS nanosheet catalyst presents a high Faradic efficiency (FE) of 22.42% with a NH yield rate of 91.46 µg h mg . 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 NH 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.
调节氮中间体的吸附能并降低反应能垒对于加速氮还原反应（NRR）的动力学至关重要，但仍然是一个巨大的挑战。在此，基于金属和非金属双掺杂策略（表示为Fe，F-WS）对WS的电子结构进行了调整，以降低W的d带中心，从而优化氮中间体的吸附。所制备的Fe，F-WS纳米片催化剂具有22.42%的高法拉第效率（FE），NH产率为91.46 μg h mg 。原位表征和DFT模拟一致表明，活性增强归因于d带中心的下移，这有助于第二步质子化形成NH关键中间体的速率决定步骤，从而提高整体氮电催化反应动力学。这项工作通过调节催化金属中心的电子结构和周围微环境，为增强电催化开辟了一条新途径。
