Lv Keran, Xu Mengqian, Yang Li, Wei Chenghu, Sun Jikai, Fang Xu, Yu Tie, Li Zhenyu, Deng Weiqiao
Institute of Frontier Chemistry, School of Chemistry and Chemical Engineering, Shandong University, Qingdao, China.
Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei, China.
Nat Commun. 2025 Aug 23;16(1):7887. doi: 10.1038/s41467-025-63145-3.
The Haber-Bosch process is used for industrial ammonia production worldwide, and it accounts for ~2% of the global energy consumption and 1.3% anthropogenic carbon footprint. Ammonia synthesis under ambient conditions with minimum carbon emission is highly desired, but it is still in the initial stage. Herein, we report a cobalt-based catalyst for ammonia continuous synthesis under ambient conditions via mechanochemistry. To describe mechanochemistry of ammonia synthesis, density functional theory (DFT) calculation was carried out and a transient confinement was discovered. 5 dual side models with Fe, Co, Ni, Cu, Ag have been set up and the Co dual side model exhibits the highest transient confinement effect with the maximum energy barrier reducing from 1.3 eV to 0.62 eV. The experiment confirmed cobalt powders in mechanochemical synthesis of ammonia showed the highest catalytic activity. By using the Co catalyst, up to 13.7 μmol·g·h ammonia has been achieved under ambient conditions, and the cobalt-based catalyst can maintain its activity more than 350 h without deactivation. This represents the longest lifespan for ammonia synthesis among all the various methods reported under room temperature and atmospheric pressure to the best of our knowledge, which is also 10 times longer than the recent reported FeCs catalysts via mechanocatalysis under ambient conditions. This study suggests that continuous mechano-synthesis of ammonia under ambient condition is valuable.
哈伯-博施法用于全球范围内的工业合成氨，其能耗占全球能源消耗的约2%，人为碳足迹占1.3%。人们迫切希望在环境条件下以最低的碳排放进行氨合成，但目前仍处于初始阶段。在此，我们报道了一种通过机械化学在环境条件下连续合成氨的钴基催化剂。为了描述氨合成的机械化学过程，我们进行了密度泛函理论（DFT）计算，并发现了一种瞬态限制效应。我们建立了5种分别含有Fe、Co、Ni、Cu、Ag的双侧模型，其中Co双侧模型表现出最高的瞬态限制效应，最大能垒从1.3 eV降至0.62 eV。实验证实，钴粉在氨的机械化学合成中表现出最高的催化活性。使用Co催化剂，在环境条件下可实现高达13.7 μmol·g·h的氨产量，且该钴基催化剂可保持其活性超过350小时而不失活。据我们所知，这是在室温和大气压下报道的所有各种方法中氨合成的最长寿命，也比最近报道的通过环境条件下机械催化的FeCs催化剂长10倍。这项研究表明，在环境条件下连续机械合成氨具有重要价值。
