通过脱水进行超微孔工程以实现均苯三甲酸钙对氢的分子筛作用
Ultramicropore Engineering by Dehydration to Enable Molecular Sieving of H by Calcium Trimesate.
作者信息
Mukherjee Soumya, Chen Shoushun, Bezrukov Andrey A, Mostrom Matthew, Terskikh Victor V, Franz Douglas, Wang Shi-Qiang, Kumar Amrit, Chen Mansheng, Space Brian, Huang Yining, Zaworotko Michael J
机构信息
Bernal Institute, Department of Chemical Sciences, University of Limerick, Limerick, V94 T9PX, Republic of Ireland.
Department of Chemistry, University of Western Ontario, London, Ontario, N6A 5B7, Canada.
出版信息
Angew Chem Int Ed Engl. 2020 Sep 7;59(37):16188-16194. doi: 10.1002/anie.202006414. Epub 2020 Jun 29.
The high energy footprint of commodity gas purification and increasing demand for gases require new approaches to gas separation. Kinetic separation of gas mixtures through molecular sieving can enable separation by molecular size or shape exclusion. Physisorbents must exhibit the right pore diameter to enable separation, but the 0.3-0.4 nm range relevant to small gas molecules is hard to control. Herein, dehydration of the ultramicroporous metal-organic framework Ca-trimesate, Ca(HBTC)⋅H O (H BTC=trimesic acid), bnn-1-Ca-H O, affords a narrow pore variant, Ca(HBTC), bnn-1-Ca. Whereas bnn-1-Ca-H O (pore diameter 0.34 nm) exhibits ultra-high CO /N , CO /CH , and C H /C H binary selectivity, bnn-1-Ca (pore diameter 0.31 nm) offers ideal selectivity for H /CO and H /N under cryogenic conditions. Ca-trimesate, the first physisorbent to exhibit H sieving under cryogenic conditions, could be a prototype for a general approach to exert precise control over pore diameter in physisorbents.
商品气体净化的高能量足迹以及对气体不断增长的需求，需要新的气体分离方法。通过分子筛对气体混合物进行动力学分离能够实现基于分子大小或形状排阻的分离。物理吸附剂必须具有合适的孔径才能实现分离，但与小气体分子相关的0.3 - 0.4纳米范围很难控制。在此，对超微孔金属有机骨架Ca - 均苯三甲酸酯Ca(HBTC)·H₂O（H₃BTC = 均苯三甲酸）bnn - 1 - Ca - H₂O进行脱水处理，得到了一种窄孔变体Ca(HBTC)，即bnn - 1 - Ca。虽然bnn - 1 - Ca - H₂O（孔径0.34纳米）表现出超高的CO₂/N₂、CO₂/CH₄以及C₂H₄/C₂H₆二元选择性，但bnn - 1 - Ca（孔径0.31纳米）在低温条件下对H₂/CO和H₂/N₂具有理想的选择性。Ca - 均苯三甲酸酯作为第一种在低温条件下表现出H₂筛分性能的物理吸附剂，可能成为一种对物理吸附剂孔径进行精确控制的通用方法的原型。
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