Britvin S N, Pekov I V, Yapaskurt V O, Koshlyakova N N, Göttlicher J, Krivovichev S V, Turchkova A G, Sidorov E G
Department of Crystallography, Institute of Earth Sciences, St. Petersburg State University, University Embankment 7/9, 199034, St Petersburg, Russia.
Kola Science Center of Russian Academy of Sciences, Fersman Str. 14, 184200, Apatity, Russia.
Sci Rep. 2020 Apr 14;10(1):6345. doi: 10.1038/s41598-020-63109-1.
Polyoxometalate (POM) chemistry is an important avenue of comprehensive chemical research, due to the broad chemical, topological and structural variations of multinuclear polyoxoanions that result in advanced functionality of their derivatives. The majority of compounds in the polyoxometalate kingdom are synthesized under laboratory conditions. However, Nature has its own labs with the conditions often unconceivable to the mankind. The striking example of such a unique environment is volcanic fumaroles - the natural factories of gas-transport synthesis. We herein report on the discovery of a novel class of complex polyoxocuprates grown in the hot active fumaroles of the Tolbachik volcano at the Kamchatka Peninsula, Russia. The cuboctahedral nanoclusters {MCuO} are stabilized by the core Fe(III) or Ti(IV) cations residing in the unique cubic coordination. The nanoclusters are uniformly dispersed over the anion- and cation-deficient NaCl matrix. Our discovery might have promising implications for synthetic chemistry, indicating the possibility of preparation of complex polyoxocuprates by chemical vapor transport (CVT) techniques that emulate formation of minerals in high-temperature volcanic fumaroles.
由于多核聚氧阴离子具有广泛的化学、拓扑和结构变化，从而导致其衍生物具有先进的功能，多金属氧酸盐（POM）化学是综合化学研究的一个重要领域。多金属氧酸盐领域中的大多数化合物是在实验室条件下合成的。然而，大自然有它自己的实验室，其条件往往是人类难以想象的。这种独特环境的一个显著例子是火山喷气孔——气体传输合成的天然工厂。我们在此报告在俄罗斯堪察加半岛托巴契克火山的热活动喷气孔中生长的一类新型复杂聚氧铜酸盐的发现。立方八面体纳米团簇{MCuO}由位于独特立方配位中的核心Fe(III)或Ti(IV)阳离子稳定。这些纳米团簇均匀地分散在缺乏阴离子和阳离子的NaCl基质上。我们的发现可能对合成化学具有潜在的重要意义，表明通过模拟高温火山喷气孔中矿物形成的化学气相传输（CVT）技术制备复杂聚氧铜酸盐的可能性。
