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Anion (O, N, C, and S) vacancies promoted photocatalytic nitrogen fixation

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Abstract

Mild-condition nitrogen fixation using “green” solar energy, merely requiring a solar-to-NH3 (STA) efficiency of 0.1% for potential use, is a promising alternative to the Haber–Bosch process but remains a great challenge. The bottleneck lies in the ultra-low efficiency originating from the sluggish surface reaction involving 6e/6H+, specifically, the rate-limiting reductive activation of nitrogen. To meet this challenge, a common approach adopted by natural nitrogenase or artificial catalysts is to craft an active center (transition metal) of electron-rich nature, thus enriching the LUMO (lowest unoccupied molecular orbital) electron density of N2 via the e → π*-orbital (N) transition to facilitate the molecular nitrogen activation. Recent progress suggests that anion vacancies such as O, C, N, and S vacancies, which inherently bear excess electrons and coordinatively unsaturated metal ions, could be explored in promoting the molecular nitrogen activation in photocatalysis. In this review, we summarize the in depth anion vacancy-dominated nitrogen photo-fixation systems, and then focus on the mechanical understanding of how an anion vacancy kinetically affects the nitrogen reductive activation including N–N triple bond weakening, N2 adsorption and activation energies, and kinetic pathways, and finally propose the future challenges and prospects of this emerging area.

Graphical abstract: Anion (O, N, C, and S) vacancies promoted photocatalytic nitrogen fixation

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Publication details

The article was received on 27 Mar 2019, accepted on 07 May 2019 and first published on 07 May 2019


Article type: Critical Review
DOI: 10.1039/C9GC01010F
Green Chem., 2019, Advance Article

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    Anion (O, N, C, and S) vacancies promoted photocatalytic nitrogen fixation

    C. Mao, J. Wang, Y. Zou, H. Li, G. Zhan, J. Li, J. Zhao and L. Zhang, Green Chem., 2019, Advance Article , DOI: 10.1039/C9GC01010F

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