A zero-dimensional nickel, iron–metal–organic framework (MOF) for synergistic N2 electrofixation,Journal of Materials Chemistry A

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A zero-dimensional nickel, iron–metal–organic framework (MOF) for synergistic N2 electrofixation
Journal of Materials Chemistry A ( IF 10.7 ) Pub Date : 2020-08-13 , DOI: 10.1039/d0ta05010e
Jingjing Duan _{1,

2,

3,

4} , Yuntong Sun _{5,

6,

7,

8,

9} , Sheng Chen _{1,

2,

3,

4,

5} , Xianjue Chen _{1,

2,

3,

4} , Chuan Zhao _{1,

2,

3,

4}

Affiliation

Metal–organic frameworks (MOFs) can electrochemically reduce nitrogen and thus can be considered as a potential electrocatalyst for converting atmospheric N₂ into useful ammonia. In this work, we fabricate a class of zero-dimensional (0D), bimetallic nickel, iron–MOFs with greatly promoted activity for the nitrogen electroreduction reaction, affording a faradaic efficiency of 11.5% and ammonia yield rate of 9.3 mg h⁻¹ mg_cat⁻¹ at −345 mV versus the reversible hydrogen electrode (RHE). Mechanistic investigations through density functional theory (DFT) calculations highlight the iron doping effect (3.1 wt% of Fe) that can suppress the energy barrier of the first ammonia release step with significantly decreased Gibbs free energy. Further, a combination of experimental studies underline the downsizing of the MOF that contributes to the optimal electronic structures of metal active sites for N [triple bond, length as m-dash]

N activation, in addition to enlarged porosity for facilitating reaction kinetics at electrode/electrolyte interfaces. This new emerging class of 0D, bimetallic MOF catalysts with remarkable electronic and structural features would not only constitute a very promising candidate for low-cost, efficient nitrogen fixation, but also holds great potential for many other technical applications.

中文翻译：

零维镍铁金属有机框架（MOF），用于N2协同电固定

金属有机骨架（MOF）可以电化学还原氮，因此可以视为将大气中的N ₂转化为有用的氨的潜在电催化剂。在这项工作中，我们制造了一类零维（0D），双金属镍，铁-MOF，其对氮电还原反应的活性大大提高，法拉第效率为11.5％，氨水产率为9.3 mg h ^-1 mg _cat^-1在-345 mV与可逆氢电极（RHE）。通过密度泛函理论（DFT）计算进行的机械研究表明，铁掺杂效应（Fe的3.1 wt％）可以抑制Gibbs自由能明显降低的第一个氨释放步骤的能垒。此外，一系列实验研究突显了MOF的小型化，这有助于N的金属活性位点的最佳电子结构 [三重键，长度为m-破折号]