TY - JOUR
T1 - Ultramicropore Engineering by Dehydration to Enable Molecular Sieving of H2 by Calcium Trimesate
AU - Mukherjee, Soumya
AU - Chen, Shoushun
AU - Bezrukov, Andrey A.
AU - Mostrom, Matthew
AU - Terskikh, Victor V.
AU - Franz, Douglas
AU - Wang, Shi Qiang
AU - Kumar, Amrit
AU - Chen, Mansheng
AU - Space, Brian
AU - Huang, Yining
AU - Zaworotko, Michael J.
N1 - Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/9/7
Y1 - 2020/9/7
N2 - 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)⋅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 selectivity, bnn-1-Ca (pore diameter 0.31 nm) offers ideal selectivity for H2/CO2 and H2/N2 under cryogenic conditions. Ca-trimesate, the first physisorbent to exhibit H2 sieving under cryogenic conditions, could be a prototype for a general approach to exert precise control over pore diameter in physisorbents.
AB - 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)⋅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 selectivity, bnn-1-Ca (pore diameter 0.31 nm) offers ideal selectivity for H2/CO2 and H2/N2 under cryogenic conditions. Ca-trimesate, the first physisorbent to exhibit H2 sieving under cryogenic conditions, could be a prototype for a general approach to exert precise control over pore diameter in physisorbents.
KW - crystal engineering
KW - hydrogen
KW - physisorption
KW - porous materials
KW - size-sieving
UR - http://www.scopus.com/inward/record.url?scp=85087179268&partnerID=8YFLogxK
U2 - 10.1002/anie.202006414
DO - 10.1002/anie.202006414
M3 - Article
C2 - 32449818
AN - SCOPUS:85087179268
SN - 1433-7851
VL - 59
SP - 16188
EP - 16194
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 37
ER -