Li Haoyue, Wang Tie, Wang Shifu, Li Xuning, Huang Yanqiang, Yan Ning
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou, China.
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Singapore.
Nat Commun. 2025 Jan 2;16(1):257. doi: 10.1038/s41467-024-55511-4.
Amines are commonly synthesized through the amination of organooxygenates using ammonia, frequently involving the use of noble metal catalysts. In this study, we present an alternative route to make amines using iron nitride (FeN) as the nitrogen source. Without any additional catalyst, FeN reacts with a range of alcohols at 250 °C under 1 or 10 bar H to produce amines as major products. Mechanistic investigations indicate that hydrogen activates the nitrogen species within iron nitride, converting them into surface NH and NH groups that then react with alcohols to form amines. Building on this foundation, we further demonstrate an iron nitride-mediated chemical looping pathway that utilizes N as the nitrogen source to synthesize octylamines. In this process, N first reacts with iron to form FeN by a ball-milling method at ambient temperature and 6 bar N. The as-prepared FeN subsequently reacts with alcohols to yield amines, transferring over 80% of the nitrogen to organic compounds. This looping process proves stable across four cycles.
胺类化合物通常通过使用氨对有机含氧化合物进行胺化反应来合成,这一过程常常涉及使用贵金属催化剂。在本研究中,我们提出了一种以氮化铁(FeN)作为氮源来制备胺类化合物的替代路线。在没有任何额外催化剂的情况下,FeN在250 °C、1或10 bar氢气压力下与一系列醇类反应,以胺类作为主要产物。机理研究表明,氢气激活了氮化铁中的氮物种,将它们转化为表面NH和NH基团,然后这些基团与醇类反应形成胺类。在此基础上,我们进一步展示了一种以氮化铁为媒介的化学循环途径,该途径利用N作为氮源来合成辛胺。在这个过程中,N首先在环境温度和6 bar氮气压力下通过球磨法与铁反应形成FeN。制备好的FeN随后与醇类反应生成胺类,将超过80%的氮转移到有机化合物中。这个循环过程在四个循环中都证明是稳定的。