New insights into the breathing phenomenon in ZIF-4

Jesus Gandara-Loe; Alexander Missyul; François Fauth; Luke L. Daemen; Yongqiang Q. Cheng; Anibal J. Ramirez-Cuesta; Peter I. Ravikovitch; Joaquin Silvestre-Albero

doi:10.1039/c8ta09713e

New insights into the breathing phenomenon in ZIF-4

Jesus Gandara-Loe, Alexander Missyul, François Fauth, Luke L. Daemen, Yongqiang Q. Cheng, Anibal J. Ramirez-Cuesta, Peter I. Ravikovitch, Joaquin Silvestre-Albero

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

15 Scopus citations

Abstract

Structural changes in ZIFs upon adsorption remain a paradigm due to the sensitivity of the adsorption mechanism to the nature of the organic ligands and gas probe molecules. Synchrotron X-ray diffraction under operando conditions clearly demonstrates for the first time that ZIF-4 exhibits a structural reorientation from a narrow-pore (np) to a new expanded-pore (ep) structure upon N₂ adsorption, while it does not do so for CO₂ adsorption. The existence of an expanded-pore structure of ZIF-4 has also been predicted by molecular simulations. In simulations the expanded structure was stabilized by entropy at high temperatures and by strong adsorption of N₂ at low temperatures. These results are in perfect agreement with manometric adsorption measurements for N₂ at 77 K that show the threshold pressure for breathing at ∼30 kPa. Inelastic neutron scattering (INS) measurements show that CO₂ is also able to promote structural changes but, in this specific case, only at cryogenic temperatures (5 K).

Original language	English
Pages (from-to)	14552-14558
Number of pages	7
Journal	Journal of Materials Chemistry A
Volume	7
Issue number	24
DOIs	https://doi.org/10.1039/c8ta09713e
State	Published - 2019
Externally published	Yes

Funding

The authors would like to acknowledge nancial support from the MINECO (MAT2016-80285-p), Generalitat Valenciana (PROMETEOII/2014/004), H2020 (MSCA-RISE-2016/NanoMed Project), Spanish ALBA synchrotron (Projects AV-2017021985 and IH-2018012591) and Oak Ridge beam time availability (Project IPTS-20843.1). JSA and JGL acknowledge nancial support from UA (ACIE17-15) to cover all the expenses for INS measurements at Oak Ridge. JGL acknowledges GV (GRISOLIAP/2016/089) for the research contract. The computing resources were made available through the VirtuES and the ICE-MAN projects, funded by the Laboratory Directed Research and Development program at ORNL.

Funders	Funder number
Oak Ridge National Laboratory
Laboratory Directed Research and Development
Horizon 2020 Framework Programme	AV-2017021985, MSCA-RISE-2016, IH-2018012591, 734641, IPTS-20843.1, GRISOLIAP/2016/089
Ministerio de Economía y Competitividad
Generalitat Valenciana	PROMETEOII/2014/004

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title = "New insights into the breathing phenomenon in ZIF-4",

abstract = "Structural changes in ZIFs upon adsorption remain a paradigm due to the sensitivity of the adsorption mechanism to the nature of the organic ligands and gas probe molecules. Synchrotron X-ray diffraction under operando conditions clearly demonstrates for the first time that ZIF-4 exhibits a structural reorientation from a narrow-pore (np) to a new expanded-pore (ep) structure upon N2 adsorption, while it does not do so for CO2 adsorption. The existence of an expanded-pore structure of ZIF-4 has also been predicted by molecular simulations. In simulations the expanded structure was stabilized by entropy at high temperatures and by strong adsorption of N2 at low temperatures. These results are in perfect agreement with manometric adsorption measurements for N2 at 77 K that show the threshold pressure for breathing at ∼30 kPa. Inelastic neutron scattering (INS) measurements show that CO2 is also able to promote structural changes but, in this specific case, only at cryogenic temperatures (5 K).",

author = "Jesus Gandara-Loe and Alexander Missyul and Fran{\c c}ois Fauth and Daemen, {Luke L.} and Cheng, {Yongqiang Q.} and Ramirez-Cuesta, {Anibal J.} and Ravikovitch, {Peter I.} and Joaquin Silvestre-Albero",

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doi = "10.1039/c8ta09713e",

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T1 - New insights into the breathing phenomenon in ZIF-4

AU - Gandara-Loe, Jesus

AU - Missyul, Alexander

AU - Fauth, François

AU - Daemen, Luke L.

AU - Cheng, Yongqiang Q.

AU - Ramirez-Cuesta, Anibal J.

AU - Ravikovitch, Peter I.

AU - Silvestre-Albero, Joaquin

PY - 2019

Y1 - 2019

N2 - Structural changes in ZIFs upon adsorption remain a paradigm due to the sensitivity of the adsorption mechanism to the nature of the organic ligands and gas probe molecules. Synchrotron X-ray diffraction under operando conditions clearly demonstrates for the first time that ZIF-4 exhibits a structural reorientation from a narrow-pore (np) to a new expanded-pore (ep) structure upon N2 adsorption, while it does not do so for CO2 adsorption. The existence of an expanded-pore structure of ZIF-4 has also been predicted by molecular simulations. In simulations the expanded structure was stabilized by entropy at high temperatures and by strong adsorption of N2 at low temperatures. These results are in perfect agreement with manometric adsorption measurements for N2 at 77 K that show the threshold pressure for breathing at ∼30 kPa. Inelastic neutron scattering (INS) measurements show that CO2 is also able to promote structural changes but, in this specific case, only at cryogenic temperatures (5 K).

AB - Structural changes in ZIFs upon adsorption remain a paradigm due to the sensitivity of the adsorption mechanism to the nature of the organic ligands and gas probe molecules. Synchrotron X-ray diffraction under operando conditions clearly demonstrates for the first time that ZIF-4 exhibits a structural reorientation from a narrow-pore (np) to a new expanded-pore (ep) structure upon N2 adsorption, while it does not do so for CO2 adsorption. The existence of an expanded-pore structure of ZIF-4 has also been predicted by molecular simulations. In simulations the expanded structure was stabilized by entropy at high temperatures and by strong adsorption of N2 at low temperatures. These results are in perfect agreement with manometric adsorption measurements for N2 at 77 K that show the threshold pressure for breathing at ∼30 kPa. Inelastic neutron scattering (INS) measurements show that CO2 is also able to promote structural changes but, in this specific case, only at cryogenic temperatures (5 K).

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New insights into the breathing phenomenon in ZIF-4

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