化学
反键分子轨道
铀
催化作用
离解(化学)
法拉第效率
电化学
无机化学
氮气
金属
物理化学
原子轨道
电子
电极
量子力学
物理
有机化学
生物化学
冶金
材料科学
作者
Wenkun Zhu,Hanwu Dong,Tong Liu,Li Zhou,Dengjiang Fu,Beibei Pang,Jie Lian,Tao Ding,Wei Zhang,Rong He,Wenkun Zhu
标识
DOI:10.1021/acs.inorgchem.3c00637
摘要
Uranium-based catalysts have been regarded as promising candidates for N2 fixation owing to the low-valent uranium metal active sites possessing the ability to enhance the electron back-donating to the π* antibonding orbitals of N2 for N≡N dissociation. Herein, we report a directional half-wave rectified alternating current electrochemical method to confine oxygen-rich uranium precursors over ultrathin 2D GO nanosheets. The as-prepared uranium catalysts exhibit a considerable Faradaic efficiency of 12.7% for NH3 and the NH3 yield rate of 18.7 μg h-1 mg-1 for N2 electroreduction. Operando XAS and isotope-labeling FTIR further unravel the preferred nitrogen adsorption reaction intermediate N-(2Oax-1 U-4Oeq) and confirm the key *N2Hy intermediate species derived from the fed N2 gas. Theoretical simulations demonstrate that the U-O atomic interface originated from U 5f-O 2p orbital hybridization can accumulate partial charge from GO, which can facilitate the N≡N dissociation and lower the thermodynamic energy barrier of the first hydrogenation step.
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