Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2020 Sep 24;25(19):4396.
doi: 10.3390/molecules25194396.

A Selenophene-Incorporated Metal-Organic Framework for Enhanced CO2 Uptake and Adsorption Selectivity

Pavel A Demakov  1   2 , Sergey S Volynkin  1 , Denis G Samsonenko  1   2 , Vladimir P Fedin  1   2 , Danil N Dybtsev  1   2
Affiliations

A Selenophene-Incorporated Metal-Organic Framework for Enhanced CO2 Uptake and Adsorption Selectivity

Pavel A Demakov et al. Molecules. .

Abstract

A new metal-organic coordination polymer [Zn2(sedc)2(dabco)] (1se; sedc2- = selepophene-2,5-dicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane) was synthesized and characterized by single-crystal X-ray diffraction analysis. This MOF is based on {Zn2(OOCR)4N2} paddle wheels and is isoreticular to the family of [Zn2(bdc)2(dabco)] derivatives (1b; bdc2- = 1,4-benzenedicarboxylate) with pcu topology. The gas adsorption measurements revealed that 1se shows a 15% higher CO2 volumetric uptake at 273 K and 28% higher CO2 uptake at 298 K (both at 1 bar) compared to the prototypic framework 1b. Methane and nitrogen adsorption at 273 K was also investigated, and IAST calculations demonstrated a pronounced increase in CO2/CH4 and CO2/N2 selectivity for 1se, compared with 1b. For example, the selectivity factor for the equimolar CO2/CH4 gas mixture at 1 bar = 15.1 for 1se and 11.9 for 1b. The obtained results show a remarkable effect of the presence of selenium atom on the carbon dioxide affinity in the isoreticular metal-organic frameworks with very similar geometry and porosity.

Keywords: X-ray diffraction studies; adsorption measurements; gas adsorption selectivity; porous metal–organic frameworks; selenophene.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Structural formulae of fdc2−, tdc2−, sedc2−, and bdc2− dicarboxylate linkers.
Figure 1
Figure 1
Crystal structure of 1se. A section of the structure showing dabco-bridged secondary building units {Zn2(OOCR)4} (a); 3D structure of the framework: view along c axis (b) and b axis (c). Zn atoms are shown green, N atoms—blue, O atoms—red, Se atoms—orange. H atoms and guest DMF molecules are not shown.
Figure 2
Figure 2
PXRD patterns of the theoretically simulated 1se (blue), as-synthesized 1se (black), activated 1se′ (olive), and the theoretically simulated 1se′ (red), assuming the retention of the space group P-421c.
Figure 3
Figure 3
N2 adsorption isotherm for 1se′ at 77K and pose-size distribution calculated from the isotherm.
Figure 4
Figure 4
Volumetric CO2 sorption isotherms for 1se′ and 1b′ at 273 K and 298 K.
Figure 5
Figure 5
Gravimetric CO2, CH4, and N2 sorption isotherms for 1se′ and 1b′ (b) at 273 K. Only adsorption branches are shown.
Figure 6
Figure 6
IAST selectivity factors on CO2 mole fraction in binary gas mixtures: CO2/N2 (a) and CO2/CH4 (b) at 273K and Ptotal = 1 bar.
See this image and copyright information in PMC

References

    1. Dutcher B., Fan M., Russell A.G. Amine-Based CO2 Capture Technology Development from the Beginning of 2013—A Review. ACS Appl. Mater. Interfaces. 2015;7:2137–2148. doi: 10.1021/am507465f. - DOI - PubMed
    1. Wang J., Huang L., Yang R., Zhang Z., Wu J., Gao Y., Wang Q., O’Hareb D., Zhong Z. Recent advances in solid sorbents for CO2 capture and new development trends. Energy Environ. Sci. 2014;7:3478–3518. doi: 10.1039/C4EE01647E. - DOI
    1. Bhattacharyya D., Miller D.C. Post-combustion CO2 capture technologies—A review of processes for solvent-based and sorbent-based CO2 capture. Curr. Opin. Chem. Eng. 2017;17:78–92. doi: 10.1016/j.coche.2017.06.005. - DOI
    1. Leung D.Y.C., Caramanna G., Mercedes Maroto-Valer M. An overview of current status of carbon dioxide capture and storage technologies. Renew. Sustain. Energy Rev. 2014;39:426–443. doi: 10.1016/j.rser.2014.07.093. - DOI
    1. Lin R.B., Li L., Alsalme A., Chen B. An Ultramicroporous Metal-Organic Framework for Sieving Separation of Carbon Dioxide from Methane. Small Struct. 2020 doi: 10.1002/sstr.202000022. - DOI

LinkOut - more resources