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Rare minerals from Siberia found to have same structure as some man-made metal-organic frameworks

One of the hottest new materials is a class of porous solids known as metal-organic frameworks, or MOFs. These man-made materials were introduced in the 1990s, and researchers around the world are working on ways to use them as molecular sponges for applications such as hydrogen storage, carbon sequestration, or photovoltaics.

Now, a surprising discovery by scientists in Canada and Russia reveals that MOFs also exist in nature -- albeit in the form of rare minerals found so far only in Siberian coal mines.

The finding, published in the journal Science Advances, 鈥渃ompletely changes the normal view of these highly popular materials as solely artificial, 鈥榙esigner鈥� solids,鈥� says senior author Tomislav Fri拧膷i膰, an associate professor of chemistry at 麻豆AV in Montreal. 鈥淭his raises the possibility that there might be other, more abundant, MOF minerals out there.鈥�

The twisting path to the discovery began six years ago, when Fri拧膷i膰 came across a mention of the minerals stepanovite and zhemchuzhnikovite in a Canadian mineralogy journal. The crystal structure of the minerals, found in Russia between the 1940s and 1960s, hadn鈥檛 been fully determined. But the Russian mineralogists who discovered them had analyzed their chemical composition and the basic parameters of their structures, using a technique known as X-ray powder diffraction. To Fri拧膷i膰, those parameters hinted that the minerals could be structurally similar to a type of man-made MOF.

His curiosity piqued, Fri拧膷i膰 began looking for samples of the rare minerals, reaching out to experts, museums and vendors in Russia and elsewhere. After a promising lead with a mining museum in Saint Petersburg failed to pan out, Igor Huski膰, a graduate student in the Fri拧膷i膰 research group at 麻豆AV turned his attention to synthesizing analogues of the minerals in the lab 鈥� and succeeded. But a major journal last year declined to publish the team鈥檚 work, in part because the original description of the minerals had been reported in a somewhat obscure Russian mineralogical journal.

Then, the 麻豆AV chemists caught a break: with the help of a crystallographer colleague in Venezuela, they connected with two prominent Russian mineralogists: Sergey Krivovichev, a professor at Saint Petersburg State University, and Prof. Igor Pekov of Lomonosov Moscow State University.

Krivovichev and Pekov were able to obtain the original samples of the two rare minerals, which had been found decades earlier in a coal mine deep beneath the Siberian permafrost. The Russian experts were also able to determine the crystal structures of the minerals. These findings confirmed the 麻豆AV researchers鈥� initial results from their lab synthesis.

Stepanovite and zhemchuzhnikovite have the elaborate, honeycomb-like structure of MOFs, characterized at the molecular level by large voids. The two minerals aren鈥檛, however, representative of the hottest varieties of MOFs 鈥�- those that are being developed for use in hydrogen-fueled cars or to capture waste carbon dioxide.

As a result, Fri拧膷i膰 and his collaborators are now broadening their research to determine if other, more abundant minerals have porous structures that could make them suitable for uses such as hydrogen storage or even drug delivery.

In any event, the discovery of MOF structures in the two rare minerals already is 鈥減aradigm-changing鈥� Fri拧膷i膰 says. If scientists had been able to determine those structures in the 1960s, he notes, the development of MOF materials 鈥渕ight have been accelerated by 30 years.鈥�

Funding for the research was provided by the Natural Sciences and Engineering Research Council of Canada, the Fonds de recherche du Qu茅bec 鈥� Nature et technologies, and Saint Petersburg State University.

鈥淢inerals with metal-organic framework structures,鈥� Igor Huski膰, Igor V. Pekov, Sergey V. Krivovichev, Tomislav Fri拧膷i膰. Science Advances, Aug. 5, 2016. DOI: 10.1126/sciadv.1600621

Photo credits:聽

• Top:聽An aggregate of synthetic zhemchuzhnikovite -聽Igor Huski膰, Fri拧膷i膰 Research Group, 麻豆AV
• Right: Individual crystals of synthetic zhemchuzhnikovite -聽Igor Huski膰, Fri拧膷i膰 Research Group, 麻豆AV
• Left:聽Fragment of the crystal structure of the natural zhemchuzhnikovite mineral -聽Luzia Germann, Dinnebier Research Group, MPI Stuttgart and Igor Huski膰, Fri拧膷i膰 Research Group, 麻豆AV