Understanding Hysteresis in Carbon Dioxide Sorption in Porous Metal-Organic Frameworks

Sergey A. Sapchenko; Marina O. Barsukova; Rodion V. Belosludov; Konstantin A. Kovalenko; Denis G. Samsonenko; Artem S. Poryvaev; Alena M. Sheveleva; Matvey V. Fedin; Artem S. Bogomyakov; Danil N. Dybtsev; Martin Schröder; Vladimir P. Fedin

doi:10.1021/acs.inorgchem.9b00016

Understanding Hysteresis in Carbon Dioxide Sorption in Porous Metal-Organic Frameworks

Sergey A. Sapchenko^*, Marina O. Barsukova, Rodion V. Belosludov, Konstantin A. Kovalenko, Denis G. Samsonenko, Artem S. Poryvaev, Alena M. Sheveleva, Matvey V. Fedin, Artem S. Bogomyakov, Danil N. Dybtsev, Martin Schröder, Vladimir P. Fedin

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

25 Scopus citations

Abstract

Two new isostructural microporous coordination frameworks [Mn₃(Hpdc)₂(pdc)₂] (1) and [Mg₃(Hpdc)₂(pdc)₂] (2) (pdc^2- = pyridine-2,4-dicarboxylate) showing primitive cubic (pcu) topology have been prepared and characterized. The pore aperture of the channels is too narrow for the efficient adsorption of N₂; however, both compounds demonstrate substantially higher uptake of CO₂ (119.9 mL·g^-1 for 1 and 102.5 mL·g^-1 for 2 at 195 K, 1 bar). Despite of their structural similarities, 2 shows a typical reversible type I isotherm for adsorption/desorption of CO₂, while 1 features a two-step adsorption process with a very broad hysteresis between the adsorption and desorption curves. This behavior can be explained by a combination of density functional theory calculations, sorption, and X-ray diffraction analysis and gives insights into the further development of new sorbents showing adsorption/desorption hysteresis.

Original language	English (US)
Pages (from-to)	6811-6820
Number of pages	10
Journal	Inorganic chemistry
Volume	58
Issue number	10
DOIs	https://doi.org/10.1021/acs.inorgchem.9b00016
State	Published - May 20 2019

Bibliographical note

Funding Information:
The reported study was funded by RFBR according to Research Project No. 18-29-04001. R.V.B. is grateful to the crew of Center for Computational Materials Science and E-IMR Center at the Institute for Materials Research, Tohoku University, for continuous support and also is thankful to the Ministry of Education, Culture, Sports, Science, and Technology of Japan (Grant No. 17H03122) for financial support. EPR studies were supported by FASO (0333-2017-0002). A.M.S. acknowledges RF President’s Grant MK-3272.2017.3 and FASO (0333-2017-0002). M.S. acknowledges support from the ERC (AdG 742041).

Publisher Copyright:
© 2019 American Chemical Society.

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.9b00016

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Sapchenko, S. A., Barsukova, M. O., Belosludov, R. V., Kovalenko, K. A., Samsonenko, D. G., Poryvaev, A. S., Sheveleva, A. M., Fedin, M. V., Bogomyakov, A. S., Dybtsev, D. N., Schröder, M., & Fedin, V. P. (2019). Understanding Hysteresis in Carbon Dioxide Sorption in Porous Metal-Organic Frameworks. Inorganic chemistry, 58(10), 6811-6820. https://doi.org/10.1021/acs.inorgchem.9b00016

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title = "Understanding Hysteresis in Carbon Dioxide Sorption in Porous Metal-Organic Frameworks",

abstract = "Two new isostructural microporous coordination frameworks [Mn3(Hpdc)2(pdc)2] (1) and [Mg3(Hpdc)2(pdc)2] (2) (pdc2- = pyridine-2,4-dicarboxylate) showing primitive cubic (pcu) topology have been prepared and characterized. The pore aperture of the channels is too narrow for the efficient adsorption of N2; however, both compounds demonstrate substantially higher uptake of CO2 (119.9 mL·g-1 for 1 and 102.5 mL·g-1 for 2 at 195 K, 1 bar). Despite of their structural similarities, 2 shows a typical reversible type I isotherm for adsorption/desorption of CO2, while 1 features a two-step adsorption process with a very broad hysteresis between the adsorption and desorption curves. This behavior can be explained by a combination of density functional theory calculations, sorption, and X-ray diffraction analysis and gives insights into the further development of new sorbents showing adsorption/desorption hysteresis.",

author = "Sapchenko, {Sergey A.} and Barsukova, {Marina O.} and Belosludov, {Rodion V.} and Kovalenko, {Konstantin A.} and Samsonenko, {Denis G.} and Poryvaev, {Artem S.} and Sheveleva, {Alena M.} and Fedin, {Matvey V.} and Bogomyakov, {Artem S.} and Dybtsev, {Danil N.} and Martin Schr{\"o}der and Fedin, {Vladimir P.}",

note = "Funding Information: The reported study was funded by RFBR according to Research Project No. 18-29-04001. R.V.B. is grateful to the crew of Center for Computational Materials Science and E-IMR Center at the Institute for Materials Research, Tohoku University, for continuous support and also is thankful to the Ministry of Education, Culture, Sports, Science, and Technology of Japan (Grant No. 17H03122) for financial support. EPR studies were supported by FASO (0333-2017-0002). A.M.S. acknowledges RF President{\textquoteright}s Grant MK-3272.2017.3 and FASO (0333-2017-0002). M.S. acknowledges support from the ERC (AdG 742041). Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

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AU - Sapchenko, Sergey A.

AU - Barsukova, Marina O.

AU - Belosludov, Rodion V.

AU - Kovalenko, Konstantin A.

AU - Samsonenko, Denis G.

AU - Poryvaev, Artem S.

AU - Sheveleva, Alena M.

AU - Fedin, Matvey V.

AU - Bogomyakov, Artem S.

AU - Dybtsev, Danil N.

AU - Schröder, Martin

AU - Fedin, Vladimir P.

N1 - Funding Information: The reported study was funded by RFBR according to Research Project No. 18-29-04001. R.V.B. is grateful to the crew of Center for Computational Materials Science and E-IMR Center at the Institute for Materials Research, Tohoku University, for continuous support and also is thankful to the Ministry of Education, Culture, Sports, Science, and Technology of Japan (Grant No. 17H03122) for financial support. EPR studies were supported by FASO (0333-2017-0002). A.M.S. acknowledges RF President’s Grant MK-3272.2017.3 and FASO (0333-2017-0002). M.S. acknowledges support from the ERC (AdG 742041). Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/5/20

Y1 - 2019/5/20

N2 - Two new isostructural microporous coordination frameworks [Mn3(Hpdc)2(pdc)2] (1) and [Mg3(Hpdc)2(pdc)2] (2) (pdc2- = pyridine-2,4-dicarboxylate) showing primitive cubic (pcu) topology have been prepared and characterized. The pore aperture of the channels is too narrow for the efficient adsorption of N2; however, both compounds demonstrate substantially higher uptake of CO2 (119.9 mL·g-1 for 1 and 102.5 mL·g-1 for 2 at 195 K, 1 bar). Despite of their structural similarities, 2 shows a typical reversible type I isotherm for adsorption/desorption of CO2, while 1 features a two-step adsorption process with a very broad hysteresis between the adsorption and desorption curves. This behavior can be explained by a combination of density functional theory calculations, sorption, and X-ray diffraction analysis and gives insights into the further development of new sorbents showing adsorption/desorption hysteresis.

AB - Two new isostructural microporous coordination frameworks [Mn3(Hpdc)2(pdc)2] (1) and [Mg3(Hpdc)2(pdc)2] (2) (pdc2- = pyridine-2,4-dicarboxylate) showing primitive cubic (pcu) topology have been prepared and characterized. The pore aperture of the channels is too narrow for the efficient adsorption of N2; however, both compounds demonstrate substantially higher uptake of CO2 (119.9 mL·g-1 for 1 and 102.5 mL·g-1 for 2 at 195 K, 1 bar). Despite of their structural similarities, 2 shows a typical reversible type I isotherm for adsorption/desorption of CO2, while 1 features a two-step adsorption process with a very broad hysteresis between the adsorption and desorption curves. This behavior can be explained by a combination of density functional theory calculations, sorption, and X-ray diffraction analysis and gives insights into the further development of new sorbents showing adsorption/desorption hysteresis.

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ER -

Understanding Hysteresis in Carbon Dioxide Sorption in Porous Metal-Organic Frameworks

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