A zero-dimensional nickel, iron–metal–organic framework (MOF) for synergistic N2 electrofixation. Issue 36 (1st September 2020)

• Record Type: Journal Article
• Authors: Duan, Jingjing; Sun, Yuntong; Chen, Sheng; Chen, Xianjue; Zhao, Chuan
• Is Part Of: Journal of materials chemistry. Volume 8:Issue 36(2020)
• Page Start: 18810
• Page End: 18815
• Publication Date: 2020-09-01
• Subjects: Materials -- Research -- Periodicals; Chemistry, Analytic -- Periodicals; Environmental sciences -- Research -- Periodicals; 543.0284
• DOI: 10.1039/d0ta05010e
• Languages: English
• ISSNs: 2050-7488

Abstract

Abstract : A zero-dimensional metal–organic framework (MOF) has been fabricated that can electrochemically reduce atmospheric N2 into useful ammonia. Abstract : 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 mgcat −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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.