TY - JOUR
T1 - Delicate Softness in a Temperature-Responsive Porous Crystal for Accelerated Sieving of Propylene/Propane
AU - Huang, Yuhang
AU - Wan, Jingmeng
AU - Pan, Ting
AU - Ge, Kai
AU - Guo, Yanan
AU - Duan, Jingui
AU - Bai, Junfeng
AU - Jin, Wanqin
AU - Kitagawa, Susumu
N1 - Publisher Copyright:
© 2023 American Chemical Society
PY - 2023/11/8
Y1 - 2023/11/8
N2 - Soft nanoporous crystals with structural dynamics are among the most exciting recently discovered materials. However, designing or controlling a porous system with delicate softness that can recognize similar gas pairs, particularly for the promoted ability at increased temperature, remains a challenge. Here, we report a soft crystal (NTU-68) with a one-dimensional (1D) channel that expands and contracts delicately around 4 Å at elevated temperature. The completely different adsorption processes of propane (C3H8: kinetic dominance) and propylene (C3H6: thermodynamic preference) allow the crystal to show a sieving separation of this mixtures (9.9 min·g-1) at 273 K, and the performance increases more than 2-fold (20.4 min·g-1) at 298 K. This phenomenon is contrary to the general observation for adsorption separation: the higher the temperature, the lower the efficiency. Gas-loaded in situ powder X-ray analysis and modeling calculations reveal that slight pore expansion caused by the increased temperature provides plausible nanochannel for adsorption of the relatively smaller C3H6 while maintaining constriction on the larger C3H8. In addition, the separation process remains unaffected by the general impurities, demonstrating its true potential as an alternative sorbent for practical applications. Moving forward, the delicate crystal dynamics and promoted capability for molecular recognition provide a new route for the design of next-generation sieve materials.
AB - Soft nanoporous crystals with structural dynamics are among the most exciting recently discovered materials. However, designing or controlling a porous system with delicate softness that can recognize similar gas pairs, particularly for the promoted ability at increased temperature, remains a challenge. Here, we report a soft crystal (NTU-68) with a one-dimensional (1D) channel that expands and contracts delicately around 4 Å at elevated temperature. The completely different adsorption processes of propane (C3H8: kinetic dominance) and propylene (C3H6: thermodynamic preference) allow the crystal to show a sieving separation of this mixtures (9.9 min·g-1) at 273 K, and the performance increases more than 2-fold (20.4 min·g-1) at 298 K. This phenomenon is contrary to the general observation for adsorption separation: the higher the temperature, the lower the efficiency. Gas-loaded in situ powder X-ray analysis and modeling calculations reveal that slight pore expansion caused by the increased temperature provides plausible nanochannel for adsorption of the relatively smaller C3H6 while maintaining constriction on the larger C3H8. In addition, the separation process remains unaffected by the general impurities, demonstrating its true potential as an alternative sorbent for practical applications. Moving forward, the delicate crystal dynamics and promoted capability for molecular recognition provide a new route for the design of next-generation sieve materials.
UR - http://www.scopus.com/inward/record.url?scp=85176508518&partnerID=8YFLogxK
U2 - 10.1021/jacs.3c10277
DO - 10.1021/jacs.3c10277
M3 - 文章
C2 - 37880205
AN - SCOPUS:85176508518
SN - 0002-7863
VL - 145
SP - 24425
EP - 24432
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 44
ER -