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Instruments / Technical Area	Publication Details	Published	Actions
I11-High Resolution Powder Diffraction	Amino functionalised hybrid ultramicroporous materials that enable single‐step ethylene purification from a ternary mixture Michael Zaworotko , Soumya Mukherjee , Naveen Kumar , Andrey A. Bezrukov , Kui Tan , Tony Pham , Katherine A. Forrest , Kolade Oyekan , Omid T. Qazvini , David G. Madden , Brian Space Angewandte Chemie International Edition DOI: 10.1002/anie.202100240 Diamond Proposal Number(s): [20500] Open Access Show Abstract ▼ Abstract: Pyrazine‐linked hybrid ultramicroporous (pore size <7 Å) materials (HUMs) offer benchmark performance for trace carbon capture thanks to strong selectivity for CO2 over small gas molecules, including light hydrocarbons. That the prototypal pyrazine‐linked HUMs are amenable to crystal engineering has enabled second generation HUMs to supersede the performance of the parent HUM, SIFSIX‐3‐Zn, mainly through substitution of the metal and/or the inorganic pillar. Herein, we report that two isostructural aminopyrazine‐linked HUMs, MFSIX‐17‐Ni (17 = aminopyrazine; M = Si, Ti), which we had anticipated would offer even stronger affinity for CO2 than their pyrazine analogs, unexpectedly exhibit reduced CO2 affinity but enhanced C2H2 affinity. MFSIX‐17‐Ni are consequently the first physisorbents that enable single‐step production of polymer‐grade (>99.95% for SIFSIX‐17‐Ni) ethylene from a ternary equimolar mixture of ethylene, acetylene and CO2 thanks to coadsorption of the latter two gases. We attribute this performance to the very different binding sites in MFSIX‐17‐Ni versus SIFSIX‐3‐Zn.	Jan 2021
I11-High Resolution Powder Diffraction	Ultramicropore engineering by dehydration to enable molecular sieving of H2 by calcium trimesate Michael Zaworotko , Soumya Mukherjee , Shoushun Chen , Andrey Bezrukov , Matthew Mostrom , Victor Terskikh , Douglas Franz , Shiqiang Wang , Mansheng Chen , Amrit Kumar , Yining Huang , Brian Space Angewandte Chemie International Edition DOI: 10.1002/anie.202006414 Diamond Proposal Number(s): [20500] Show Abstract ▼ Abstract: The high energy footprint of commodity gas purification and ever‐increasing demand for gases require new approaches to gas separation. Kinetic separation of gas mixtures through molecular sieving can enable “ideal” separation through molecular size or shape exclusion. Physisorbents must exhibit just the right pore diameter to enable such ideal separation, but the 0.3‐0.4 nm range relevant to small gas molecules is hard to control with precision. Herein, we report that dehydration of the ultramicroporous metal‐organic framework Ca‐trimesate, Ca(HBTC) . H2O (H3BTC = trimesic acid), bnn‐1‐Ca‐H2O, affords a narrow pore variant, Ca(HBTC), bnn‐1‐Ca. Whereas bnn‐1‐Ca‐H2O (pore diameter 0.34 nm) exhibits ultra‐high CO2/N2, CO2/CH4 and C2H2/C2H4 binary selectivities, bnn‐1‐Ca (pore diameter 0.31 nm) offers ideal selectivities for H 2 /CO 2 and H2/N2 under cryogenic conditions. Ca‐trimesate, the first physisorbent to exhibit H2 sieving under cryogenic conditions, could be prototypal for a potentially general approach to exert precise control over pore diameter in physisorbents.	May 2020

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