JACS领衔！国仪量子EPR助力27项高水平研究成果发表

Vanadium-Catalyzed Dinitrogen Reduction to Ammonia via a [V]═NNH₂ Intermediate.Journal of the American Chemical Society（2023）

摘要

地球大气中含有丰富的N₂（78%），但由于其化学惰性，氮气的活化和转化一直是一项具有挑战性的任务。合成氨工业中使用高温高压条件将N₂和H₂在固体催化剂表面转化为NH₃。在环境条件下，某些微生物可以通过基于Fe（Mo/V）的固氮酶与N₂结合并转化为NH₃，尽管在固氮酶的结构和中间体方面取得了巨大进展，但N₂与活性位点结合的性质和N₂还原的详细机制仍不确定。

为了更好地理解反应机理并开发温和条件下氨合成催化剂，已经开展关于用过渡金属配合物活化N₂的各种研究。但是目前为止，过渡金属配合物对N₂到NH₃的催化转化仍是一个挑战。尽管钒在生物固氮中起着至关重要的作用，但能够催化N₂转化为NH₃的明确钒络合物却很少。特别是，从配位N₂的质子/电子转移反应中得到的V(NxHy)中间物仍然是未知的。在此，本文报道了钒金属配合物催化氮气还原为氨气，并首次从氮气活化体系分离和表征了中性酰肼配合物中间体（[V]=NNH₂），通过还原质子化钒的氨基配合物（[V]-NH₂）得到双氮化合物并释放氨气模拟了循环转化过程，结合理论计算阐明了在该催化体系中氮气可能经过端位反应途径（distal pathway）转化为氨气，这些发现为与FeV固氮酶有关的N₂还原机制提供了前所未有的见解。

北京师范大学胡少伟课题组致力于发展过渡金属配合物活化惰性小分子的研究，近日与崔刚龙教授课题组合作，通过理论计算和实验研究相结合的方式报道了钒金属配合物催化氮气还原为氨气。相关研究结果发表在Journal of the American Chemical Society，黄文双（硕士研究生）和彭灵雅（博士研究生）为本文的共同第一作者，分别从事实验和理论计算的相关工作，该研究也得到了北京师范大学方维海院士、北京林业大学宋国勇教授和中国科学技术大学苏吉虎教授的大力支持。

钒金属配合物催化剂合成

EPR

配合物5b固氮反应机理图

结论

研究结果表明，带有POCOP和芳氧基辅助配体的过渡金属钒配合物可稳定活性含氮物种（NHy）并促进N2到NH3的催化转化，从而为生物固氮机理，特别是为FeV固氮酶有关的N2还原机制提供了更多的视角，为设计出更为高效的合成氨催化剂提供了新的思路。

1.Vanadium-Catalyzed Dinitrogen Reduction to Ammonia via a [V]═NNH₂ Intermediate.Journal of the American Chemical Society（2023）

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