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

Mild-condition nitrogen fixation using "green" solar energy, merely requiring a solar-to-NH 3 (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 th...

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Published inGreen chemistry : an international journal and green chemistry resource : GC Vol. 21; no. 11; pp. 2852 - 2867
Main Authors Mao, Chengliang, Wang, Jiaxian, Zou, Yunjie, Li, Hao, Zhan, Guangming, Li, Jie, Zhao, Jincai, Zhang, Lizhi
Format Journal Article
LanguageEnglish
Published Cambridge Royal Society of Chemistry 04.06.2019
Subjects
activation energy
adsorption
Ammonia
Anions
Catalysts
chemical bonding
Chemical bonds
Clean energy
Electron density
electrons
Green chemistry
Metal ions
Molecular orbitals
Nitrogen
Nitrogen fixation
Nitrogenase
Photocatalysis
Solar energy
Transition metals
Vacancies
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Summary:Mild-condition nitrogen fixation using "green" solar energy, merely requiring a solar-to-NH 3 (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 N 2 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, N 2 adsorption and activation energies, and kinetic pathways, and finally propose the future challenges and prospects of this emerging area. Mild-condition nitrogen fixation using "green" solar energy, merely requiring a solar-to-NH 3 (STA) efficiency of 0.1% for potential use, is a promising alternative to the Haber-Bosch process but remains a great challenge.
Bibliography:Chengliang Mao is a Ph.D. student in physical chemistry at the Central China Normal University (CCNU) under the supervision of Professor Jincai Zhao and Professor Lizhi Zhang. His research interests focus on plasmonic-based photothermal ammonia synthesis.
Lizhi Zhang received his Ph.D. degree in environmental science from the Chinese University of Hong Kong, China in 2003. After his postdoctoral research at the department of chemistry, Chinese University of Hong Kong, he joined the College of Chemistry, CCNU as a full professor of chemistry in 2005. He worked at the Max-Planck Institute of Colloids and Interfaces as an Alexander von Humboldt Scholar from 2006 to 2007. His research interests include developing photocatalysts for nitrogen fixation, and utilizing the iron cycle for pollution control and environmental remediation. He won the National Natural Science Funds for Distinguished Young Scholars of China in 2014, and was appointed as the Changjiang Scholar Distinguished Professor of the Ministry of Education of China in 2015.
Jiaxian Wang is a graduate student in physical chemistry at the Central China Normal University (CCNU) under the supervision of Professor Lizhi Zhang. His research interests focus on photothermal ammonia synthesis.
Jincai Zhao obtained his Ph.D. degree in 1994 from Meisei University (Japan). Currently, he is a full professor at the Institute of Chemistry, Chinese Academy of Sciences (China). He was elected as an academician of the Chinese Academy of Sciences in 2011 and academician of the Academy of Sciences for the Developing World in 2014. He is a member of the editorial and advisory boards of eight international scientific journals, including Environmental Science & Technology and Energy & Environmental Science.
Yunjie Zou is an undergraduate student in chemistry at the Central China Normal University (CCNU) under the supervision of Professor Lizhi Zhang. His research interests focus on photothermal ammonia synthesis.
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ISSN:1463-9262
1463-9270
1463-9270
DOI:10.1039/c9gc01010f