Anaerobic ammonium oxidation (anammox)—the biological process that activates ammonium with nitrite—is responsible for a significant fraction of N₂ production in marine environments. Despite decades of biochemical research, however, no synthetic models capable of anammox have been identified. Here we report that a copper sulfide mineral replicates the entire biological anammox pathway catalysed by three metalloenzymes. We identified a copper–nitrosonium {CuNO}¹⁰ complex, formed by nitrite reduction, as the oxidant for ammonium oxidation that leads to heterolytic N–N bond formation from nitrite and ammonium. Similar to the biological process, N₂ production was mediated by the highly reactive intermediate hydrazine, one of the most potent reductants in nature. We also found another pathway involving N–N bond heterocoupling for the formation of hybrid N₂O, a potent greenhouse gas with a unique isotope composition. Our study represents a rare example of non-enzymatic anammox reaction that interconnects six redox states in the abiotic nitrogen cycle.

厌氧铵态氮氧化 （anammox） 是用亚硝酸盐活化铵态氮的生物过程，是海洋环境中产生 N₂ 的很大一部分的原因。然而，尽管进行了数十年的生化研究，但尚未发现能够产生厌氧氨氧化的合成模型。在这里，我们报道了一种硫化铜矿物复制了由三种金属酶催化的整个生物厌氧氨氧化途径。我们鉴定了由亚硝酸盐还原形成的铜-亚硝基 {CuNO}¹⁰ 络合物，作为铵态氮氧化的氧化剂，导致亚硝酸盐和铵态形成异质 N-N 键。与生物过程类似，N₂ 的产生是由高反应性中间肼介导的，肼是自然界中最有效的还原剂之一。我们还发现了另一种涉及 N-N 键异质偶联的途径，用于形成杂化 N₂O，这是一种具有独特同位素组成的强效温室气体。我们的研究代表了非酶促厌氧氨氧化反应的一个罕见例子，它将非生物氮循环中的六种氧化还原状态相互关联。