Authors: Quan Li, Dongcai Shen, Zhengting Xiao, Xin Liu, Xiang Xu, Mingrui Wu, Wentai Wang, Licheng Liu, Qin Li, Xianguo Li
Published: 2025-02-07
Source: Full article
AbstractElectrocatalytic nitrogen oxidation (NOR) provides a promising alternative strategy for synthesizing nitric acid from widespread N2, which overcomes the disadvantages of Haber‐Bosch‐Ostwald process. However, the NOR process suffers from the limitation of high N≡N bonding energy, sluggish kinetics, and low efficiency. It is prerequisite to develop more efficient NOR electrocatalysts. Herein, dual‐shelled CeO2 hollow spheres (D‐CeO2) are synthesized and modified with Ti3C2 MXene quantum dots (MQDs) for NOR, which exhibited a NO3− yield rate of 71.25 µg h−1 mgcat−1 and Faradic Efficiency (FE) of 31.80% at 1.7 V versus RHE. The unique quantum size effect and abundant edge active sites lead to more effective capture of nitrogen. Moreover, the dual‐shelled hollow structure will gather intermediate products in the interlayer of the core‐shell to facilitate N2 fixation. The in situ Fourier transform infrared (FTIR) spectroscopy confirmed the formation of *NO and NO3− species during the NOR, and the kinetics and possible pathways of NOR are calculated by density functional theory (DFT). In addition, a Zn‐N2 reaction device is assembled with D‐CeO2/MQDs as anode and Zn plate as cathode, obtaining an extremely high NO3− yield rate of 104.57 µg h−1 mgcat−1 at 1 mA cm−2.