Rational design of microporous MOFs with anionic boron cluster functionality and cooperative dihydrogen binding sites for highly selective capture of acetylene.

Separation of acetylene (C 2 H 2 ) from carbon dioxide (CO 2 ) or ethylene (C 2 H 4 ) is important in industry but challenged by the low capacity and selectivity due to their similar molecular sizes and physical properties. Herein, we report two novel dodecaborate-hybrid metal organic frameworks, MB 12 H 12 (dpb) 2 (termed as BSF-3 and BSF-3-Co for M = Cu and Co), for highly selective capture of C 2 H 2 . The high C 2 H 2 capacity and remarkable C 2 H 2 /CO 2 selectivity resulted from the unique anionic boron cluster functionality as well as the suitable pore size with cooperative proton-hydride dihydrogen bonding sites (B-H δ- ···H δ+ -C≡C-H δ+ ···H δ- -B). This new type of C 2 H 2 -specific functional sites represents a fresh paradigm distinct from those in previous leading materials based on open metal sites, strong electrostatics or hydrogen bonding.

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