Wang Haifan, Yuan Menglei, Zhang Jingxian, Bai Yiling, Zhang Ke, Li Bin, Zhang Guangjin
CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China; Northwestern Polytechnical University, Xian 710000, China.
J Colloid Interface Sci. 2023 Nov;649:166-174. doi: 10.1016/j.jcis.2023.06.097. Epub 2023 Jun 17.
Ammonia (NH) synthesis at mild conditions by electrocatalytic nitrogen reduction (eNRR) has received more attention and has been regarded as a promising alternative to the traditional Haber-Bosch process. Lewis acid-base pairs (LPs) can chemisorb and react with nitrogen by electronic interaction, while the tuning of the microenvironment near electrode can hinder hydrogen evolution reaction (HER) thus improving the selectivity of the eNRR. Herein, the FeOOH nanorod coupled with LPs on the surface (i.e., Fe, Fe-O) was synthesized, which could effectively drive eNRR. Meanwhile, polyethylene glycol (PEG) was introduced to serve as a local non-aqueous electrolyte system to inhibit HER. The prepared FeOOH-150 catalyst achieved outstanding eNRR performance with an NH yield rate of 118.07 μg hmg and a Faradaic efficiency of 51.4 % at -0.6 V vs. RHE in 0.1 M LiClO + 20 % PEG. Both the experiment and DFT calculations revealed that the interaction of PEG with Lewis base sites could optimize nitrogen adsorption configuration and activation.
通过电催化氮还原（eNRR）在温和条件下合成氨（NH₃）受到了更多关注，并被视为传统哈伯-博施法的一种有前景的替代方法。路易斯酸碱对（LPs）可以通过电子相互作用化学吸附氮并与之反应，而电极附近微环境的调节可以阻碍析氢反应（HER），从而提高eNRR的选择性。在此，合成了表面耦合有LPs（即Fe、Fe-O）的FeOOH纳米棒，其能够有效驱动eNRR。同时，引入聚乙二醇（PEG）作为局部非水电解质体系来抑制HER。制备的FeOOH-150催化剂在0.1 M LiClO₄ + 20% PEG中，相对于可逆氢电极（RHE）在-0.6 V时实现了出色的eNRR性能，NH₃产率为118.07 μg h⁻¹ mg⁻¹，法拉第效率为51.4%。实验和密度泛函理论（DFT）计算均表明，PEG与路易斯碱位点的相互作用可以优化氮的吸附构型和活化。
