Yamazaki Yasuomi, Endo Yoshiki, Nishibayashi Yoshiaki
Department of Applied Chemistry, School of Engineering, The University of Tokyo, Tokyo, Japan.
Nat Commun. 2025 May 22;16(1):4540. doi: 10.1038/s41467-025-59727-w.
The development of the production method for green ammonia, which is produced only from ubiquitous and clean small molecules (i.e., dinitrogen and water) using renewable energy, has been desired for a next-generation carbon-free energy carrier to build a carbon-neutral society and solve global warming. We have herein achieved visible-light-driven catalytic ammonia formation from dinitrogen and water under ambient conditions using tertiary phosphines, which are widely-used organic compounds, as an electron donor in the presence of molybdenum complexes as molecular catalysts for ammonia formation from dinitrogen and iridium complexes as photosensitizers. In this reaction system, visible light energy enables iridium photosensitizers to trigger electron relay from tertiary phosphines (RP) as weak reductants to molybdenum catalysts, and the produced radical cation (RP) activates water molecules to donate protons for ammonia formation to molybdenum catalysts via the production of a phosphine-water adducted radical cation (RP-OH).
绿色氨的生产方法仅利用无处不在的清洁小分子（即氮气和水）并使用可再生能源来生产，人们一直期望这种方法能作为下一代无碳能源载体，以构建碳中和社会并解决全球变暖问题。在此，我们利用叔膦（一种广泛使用的有机化合物）作为电子供体，在钼配合物作为氮气合成氨的分子催化剂以及铱配合物作为光敏剂的存在下，在环境条件下实现了由氮气和水可见光驱动的催化氨生成。在该反应体系中，可见光能量使铱光敏剂能够引发电子从作为弱还原剂的叔膦（RP）传递至钼催化剂，并且生成的自由基阳离子（RP）通过生成膦 - 水加合自由基阳离子（RP - OH）来活化水分子，从而向钼催化剂提供质子以用于氨的生成。
