Interspersed Bi Promoting Hot Electron Transfer of Covalent Organic Frameworks Boosts Nitrogen Reduction to ammonia

Seeking highly-efficient, non-pollutant, and chemically robust photocatalysts for visible-light-driven ammonia production still remained challenging, especially in pure water. The key bottle-necks closely correlate to the nitrogen activation, water oxidization, and hydrogen evolution reaction (HER) processes. In this study, a novel Bi decorated imine-linked COF-TaTp (Bi/COF-TaTp) through N–Bi–O coordination is reasonably designed to achieve a boosting solar-to-ammonia conversion of 61 µmol −1 g −1 h −1 in the sacrificial-free system. On basis of serial characterizations and DFT calculations, the incorporated Bi is conducive to the acceleration of charge carriers transfer and N 2 activation through the donation and back-donation mode. The N 2 adsorption energy of 5% Bi/COF-TaTp is calculated to be −0.19 eV in comparison with −0.09 eV of the pure COF-TaTp and the electron exchange between N 2 and the modified catalyst is much more intensive. Moreover, the accompanied hydrogen production process is effectively inhibited by Bi modification, demonstrated by the higher energy barrier for HER over Bi/COF-TaTp (2.62 eV) than the pure COF-TaTp (2.31 eV) when using H binding free energy (Δ G H* ) as a descriptor. This work supplies novel insights for the design of photocatalysts for N 2 reduction and intensifies the understanding of N 2 adsorption and activation over covalent organic frameworks-based materials.