Understanding Aerobic Nitrogen Photooxidation on Titania through In Situ Time‐Resolved Spectroscopy

Nitrate is an important raw material for chemical fertilizers, but it is industrially manufactured in multiple steps at high temperature and pressure, urgently motivating the design of a green and sustainable strategy for nitrate production. We report the photosynthesis of nitrate from N2 and O2 on...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-12, Vol.61 (51), p.e202211469-n/a
Main Authors: Zhang, Shuai, Zhao, Yunxuan, Miao, Yingxuan, Xu, Yanjun, Ran, Jingrun, Wang, Zhuan, Weng, Yuxiang, Zhang, Tierui
Format: Article
Language:English
Subjects:
Absorption spectroscopy
Aerobic Nitrogen Photooxidation
Agrochemicals
Electron paramagnetic resonance
Electron spin resonance
Energy conversion
Energy conversion efficiency
Fertilizers
Fourier transforms
High temperature
Infrared spectroscopy
Nitrate Synthesis
Nitrates
Nitrogen
Oxidation
Oxygen
Photocatalysis
Photooxidation
Photosynthesis
Raw materials
Solar energy
Time-Resolved Spectroscopy
Titanium dioxide
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Summary:Nitrate is an important raw material for chemical fertilizers, but it is industrially manufactured in multiple steps at high temperature and pressure, urgently motivating the design of a green and sustainable strategy for nitrate production. We report the photosynthesis of nitrate from N2 and O2 on commercial TiO2 in a flow reactor under ambient conditions. The TiO2 photocatalyst offered a high nitrate yield of 1.85 μmol h−1 as well as a solar‐to‐nitrate energy conversion efficiency up to 0.13 %. We combined reactivity and in situ Fourier transform infrared spectroscopy to elucidate the mechanism of nitrate formation and unveil the special role of O2 in N≡N bond dissociation. The mechanistic insight into charge‐involved N2 oxidation was further demonstrated by in situ transient absorption spectroscopy and electron paramagnetic resonance. This work exhibits the mechanistic origin of N2 photooxidation and initiates a potential method for triggering inert catalytic reactions. In situ and ultrafast time‐resolved spectroscopic characterization and computational simulations were employed to elucidate the role of O2 in promoting N2 dissociation through a low‐energy pathway evolving from *OxNy to an *ON intermediate. A TiO2 photocatalyst exhibited outstanding N2 photofixation performance with a solar‐to‐nitrate energy conversion efficiency up to 0.13 %.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202211469