Selective carbon dioxide sorption and heterogeneous catalysis by a new 3D Zn-MOF with nitrogen-rich 1D channels

Hyun Chul Kim, Seong Huh, Sung Jin Kim, Youngmee Kim

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21 Scopus citations


We prepared a new C 2h-symmetric bridging ligand, 3,3′-(pyrazine-2,5-diyl)dibenzoic acid (3,3′-PDBA), through a Suzuki coupling reaction. 3,3′-PDBA contains a central pyrazine ring instead of the phenyl ring of 3,3′-terphenyldicarboxylic acid (3,3′-TPDC). Despite the geometrical similarity of the two bridging ligands, the reaction between Zn(NO3)2·6H2O and 3,3′-PDBA in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) yielded a structurally different Zn-based metal-organic framework (Zn-MOF). The Zn-MOF, [Zn2(3,3′-PDBA)2(DABCO)1.5]·2DMF·H2O, had two-dimensional (2D) layers, and the interlocked 2D layers formed a porous 3D framework. Interestingly, one of the two available N atoms of DABCO remained intact. The uncoordinated N atoms of the dangling DABCO ligand and the pyrazinyl N atoms of the 3,3′-PDBA bridging ligand were fully exposed toward the 1D channels. Therefore, the 1D channels represented a highly nitrogen-rich environment. Gas sorption analysis indicated that the Zn-MOF was selective for adsorption of CO2 at 196 K over N2 (77 K) and H2 (77 K). The exceptionally high zero surface coverage heat of CO2 adsorption (Q st = 79.5 kJ mol-1) was attributable to the openly accessible multiple Lewis basic sites in the nitrogen-rich 1D channels. Zn-MOF also showed good Lewis base catalytic activities in three model aldol-type reactions with good recyclability due to chemically accessible 3° amine sites.

Original languageEnglish
Article number17185
JournalScientific Reports
Issue number1
StatePublished - 1 Dec 2017

Bibliographical note

Funding Information:
This work was supported by the Basic Science Research Program of the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2015R1D1A1A01058136) and by the Ministry of Science, ICT & Future Planning (2015R1C1A2A01053025). This work was supported by the Hankuk University of Foreign Studies Research Fund of 2017.

Publisher Copyright:
© 2017 The Author(s).


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