Angew. Chem. Int. Ed. - Bio-Inspired Aerobic-Hydrophobic Janus Interface on Partially Carbonized Iron Heterostructure Promotes Bifunctional Nitrogen Fixation

Wei Zong‡, Haiqi Gao‡, Yue Ouyang‡, Kaibin Chu, Hele Guo, Leiqian Zhang, Wei Zhang, Ruwei Chen, Yuhang Dai, Fei Guo, Jiexin Zhu, Zhenfang Zhang, Chumei Ye, Yue-E Miao,* Johan Hofkens, Feili Lai,* Tianxi Liu*

Angewandte Chemie 2023, DOI: 10.1002/anie.202218122

Overwhelming competition from hydrogen/oxygen evolution reactions and low solubility of N₂ in aqueous systems drain on selectivity and activity on nitrogen fixation reaction. Herein, we design an aerobic-hydrophobic Janus structure by introducing fluorinated modification on porous carbon nanofibers embedded with partially carbonized iron heterojunctions (Fe₃C/Fe@PCNF-F). The simulations prove that the Janus structure can keep the internal Fe₃C/Fe@PCNF-F away from water infiltration and endow a N₂ molecule-concentrating effect, suppressing the competing reactions and overcoming the mass-transfer limitations to build a robust "quasi-solid-gas" state micro-domain around the catalyst surface. In this proof-of-concept system, the Fe₃C/Fe@PCNF-F exhibits excellent electrocatalytic performance for nitrogen fixation (NH₃ yield rate up to 29.2 μg h^-1 mg^-1_cat. and Faraday efficiency (FE) up to 27.8% in NRR; NO₃^- yield rate up to 15.7 μg h^-1 mg^-1_cat. and FE up to 3.4 % in NOR).

Link: https://doi.org/10.1002/anie.202218122