Sequencing of metals in multivariate metal-organic frameworks

Ji, Z. and Li, T. and Yaghi, O.M.

Volume: 369 Pages: 674-680
DOI: 10.1126/science.aaz4304
Published: 2020

We mapped the metal sequences within crystals of metal-oxide rods in multivariate metal-organic framework-74 containing mixed combinations of cobalt (Co), cadmium (Cd), lead (Pb), and manganese (Mn). Atom probe tomography of these crystals revealed the presence of heterogeneous spatial sequences of metal ions that we describe, depending on the metal and synthesis temperature used, as random (Co, Cd, 120°C), short duplicates (Co, Cd, 85°C), long duplicates (Co, Pb, 85°C), and insertions (Co, Mn, 85°C). Three crystals were examined for each sequence type, and the molar fraction of Co among all 12 samples was observed to vary from 0.4 to 0.9, without changing the sequence type. Compared with metal oxides, metal-organic frameworks have high tolerance for coexistence of different metal sizes in their rods and therefore assume various metal sequences. © 2020 American Association for the Advancement of Science. All rights reserved.

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