共价有机骨架
氨生产
材料科学
催化作用
吸附
电子转移
化学工程
共价键
金属有机骨架
氨
氢
光化学
化学物理
纳米技术
物理化学
化学
有机化学
工程类
作者
Mingfei Yu,Yueling Chen,Ming Gao,Guocheng Huang,Qiaoshan Chen,Jinhong Bi
出处
期刊:Small
[Wiley]
日期:2022-12-04
卷期号:19 (7)
被引量:9
标识
DOI:10.1002/smll.202206407
摘要
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 N2 activation through the donation and back-donation mode. The N2 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 N2 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 (ΔGH* ) as a descriptor. This work supplies novel insights for the design of photocatalysts for N2 reduction and intensifies the understanding of N2 adsorption and activation over covalent organic frameworks-based materials.
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