Construction of Coordination Spaces with Narrow Pore Windows in Co-Based Metal-Organic Frameworks toward CO2/N2 Separation

Da-Shuai Zhang; Zhen-Wei Zhang; Fan-Cui Li; Hongliang Huang; Hui Hu; Yong-Zheng Zhang; Longlong Geng; Rongmin Wei; Xiuling Zhang; Wei Li; Yun-Wu Li

doi:10.1021/acs.inorgchem.4c02251

Construction of Coordination Spaces with Narrow Pore Windows in Co-Based Metal-Organic Frameworks toward CO₂/N₂ Separation

Inorg Chem. 2024 Aug 26;63(34):15915-15923. doi: 10.1021/acs.inorgchem.4c02251. Epub 2024 Aug 9.

Authors

Da-Shuai Zhang^{1

2}, Zhen-Wei Zhang^{1

2}, Fan-Cui Li¹, Hongliang Huang³, Hui Hu¹, Yong-Zheng Zhang¹, Longlong Geng^{1

2}, Rongmin Wei¹, Xiuling Zhang^{1

2}, Wei Li⁴, Yun-Wu Li⁵

Affiliations

¹ Shandong Provincial Key Laboratory of Monocrystalline Silicon Semiconductor Materials and Technology, Shandong Universities Engineering Research Center of Integrated Circuits Functional Materials and Expanded Applications, College of Chemistry and Chemical Engineering, Dezhou University, Dezhou 253023, P. R. China.
² School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo 255000, P. R. China.
³ State Key Laboratory of Separation Membranes and Membrane Processes, School of Chemical Engineering and Technology, Tiangong University, Tianjin 300387, P. R. China.
⁴ School of Materials Science and Engineering, Nankai University, Tianjin 443000, P. R. China.
⁵ Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, and School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252000, P. R. China.

PMID: 39121364
DOI: 10.1021/acs.inorgchem.4c02251

Abstract

Carbon emission reduction is an important measure to mitigate the greenhouse effect, which has become a hotspot in global climate change research. To contribute to this, here, we fabricated two Co-based metal-organic frameworks (Co-MOFs), namely, {[Co₃(NTB)₂(bib)]·(DMA)₂·(H₂O)₄}_n (DZU-211) and {[Co₃(NTB)₂(bmip)]·(DMA)₂}_n (DZU-212) (H₃NTB = 4,4',4″-nitrilotribenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane, bmip = 1,3-bis(2-methyl-1H-imidazol-1-yl)propane) to realize efficient CO₂/N₂ separation by dividing coordination spaces into suitable pores with narrow windows. DZU-211 reveals a 3D open porous framework, while DZU-212 exhibits a 3D double-fold interpenetrated structure. The two MOFs both possess large coordination spaces and small open pore sizes, via the bib ligand insertion and framework interpenetration, respectively. Comparatively, DZU-211 reveals superior selective CO₂ uptake properties due to its more suitable pore characteristics. Gas sorption experiments show that DZU-211 has a CO₂ uptake of 52.6 cm³ g^-1 with a high simulated CO₂/N₂ selectivity of 101.7 (298 K, 1 atm) and a moderate initial adsorption heat of 38.1 kJ mol^-1. Moreover, dynamic breakthrough experiments confirm the potential application of DZU-211 as a CO₂ separation material from postcombustion flue gases.