Charge-Assisted Hydrogen-Bonded Organic Frameworks with Inorganic Ammonium Regulated Switchable Open Polar Sites

被引:9
|
作者
Ding, Xiaojun [1 ]
Luo, Yilin [1 ]
Wang, Wei [1 ]
Hu, Tongyang [1 ]
Chen, Jing [1 ]
Ye, Gang [1 ]
机构
[1] Tsinghua Univ, Inst Nucl & New Energy Technol, Collaborat Innovat Ctr Adv Nucl Energy Technol, Beijing 100084, Peoples R China
基金
中国国家自然科学基金;
关键词
ammonium cations; charge-assisted hydrogen bond; CO2; sequestration; hydrogen-bonded organic frameworks; open polar sites; CARBON-DIOXIDE; MOLECULES; NETWORKS; CAPTURE;
D O I
10.1002/smll.202207771
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Surface open polar sites within the voids of porous molecular crystals define the localized physicochemical environment for critical functions such as gas separation and molecular recognition. This study presents a new charge-assisted hydrogen bonding (H-bonding) motif, by exploiting inorganic ammonium (NH4+) cations as H-bond donors, to regulate the assembly of C-2-symmetric carboxylic tectons for building robust H-bonded frameworks with permanent ultra-micropores and open oxygen sites. Diverse building blocks are bridged by tetrahedral NH4+ to expand distinctive H-bonded networks with varied pore architectures. Particularly, the open polar oxygen sites can be switched by altering NH4+ sources to tune the deprotonation of carboxyl-containing tectons. The activated porous PTBA center dot NH4 center dot DMF preserves the pore architecture and open polar oxygen sites, exhibiting remarkably selective sorption of CO2 (107.8 cm(3) g(-1),195 K) over N-2 (11.2 cm(3) g(-1), 77 K) and H-2 (1.4 cm(3) g(-1), 77 K).
引用
收藏
页数:8
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