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Title: Understanding the breathing phenomena in nano-ZIF-7 upon gas adsorption

Abstract

For this research, synchrotron X-ray diffraction and inelastic neutron scattering measurements have been applied to evaluate the breathing phenomena in small nanocrystals of ZIF-7 upon gas adsorption. The experimental results show that an extended solvent exchange process with methanol is crucial to get a solvent-free narrow pore structure. Under these conditions, nano-ZIF-7 is indeed able to adsorb N 2 with a total BET surface area of around 380 m 2 g -1, in close agreement with theoretical predictions. The breathing phenomenon upon nitrogen adsorption is accompanied by a phase-to-phase transition, from a narrow-pore (phase II) to a large-pore (phase I) structure and a suppression of the cooperative deformation of the framework involving mainly the flapping motion of the benzimidazolate (bIm) ligand with the 4- and 6-membered rings. Whereas nitrogen requires temperature and pressure conditions close to condensation (close to 1 bar and 77 K) to induce the breathing in ZIF-7, CO 2 can do it under milder conditions (at room temperature and low relative pressures). These results reflect that the nature of the adsorptive probe and the gas–framework interactions, rather than the molecular diameter and/or shape, play a crucial role in defining the pressure and temperature conditions required to inducemore » the breathing. Lastly, the presence of two different cavities in ZIF-7 as suggested by theoretical predictions, one with a window diameter of below 0.4 nm (cavity A) and the other with a pore size of around 0.6 nm (cavity B), has been confirmed experimentally using immersion calorimetry.« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [3];  [3]; ORCiD logo [3]; ORCiD logo [1]
  1. Universidad de Alicante (Spain). Laboratorio de Materiales Avanzados, Departamento de Quimica Inorganica, Instituto Universitario de Materiales
  2. CELLS-ALBA Synchrotron, Barcelona (Spain)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1422567
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 39; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cuadrado-Collados, Carlos, Fernández-Català, Javier, Fauth, François, Cheng, Yongqiang Q., Daemen, Luke L., Ramirez-Cuesta, Anibal J., and Silvestre-Albero, Joaquín. Understanding the breathing phenomena in nano-ZIF-7 upon gas adsorption. United States: N. p., 2017. Web. doi:10.1039/C7TA05922A.
Cuadrado-Collados, Carlos, Fernández-Català, Javier, Fauth, François, Cheng, Yongqiang Q., Daemen, Luke L., Ramirez-Cuesta, Anibal J., & Silvestre-Albero, Joaquín. Understanding the breathing phenomena in nano-ZIF-7 upon gas adsorption. United States. doi:10.1039/C7TA05922A.
Cuadrado-Collados, Carlos, Fernández-Català, Javier, Fauth, François, Cheng, Yongqiang Q., Daemen, Luke L., Ramirez-Cuesta, Anibal J., and Silvestre-Albero, Joaquín. Mon . "Understanding the breathing phenomena in nano-ZIF-7 upon gas adsorption". United States. doi:10.1039/C7TA05922A. https://www.osti.gov/servlets/purl/1422567.
@article{osti_1422567,
title = {Understanding the breathing phenomena in nano-ZIF-7 upon gas adsorption},
author = {Cuadrado-Collados, Carlos and Fernández-Català, Javier and Fauth, François and Cheng, Yongqiang Q. and Daemen, Luke L. and Ramirez-Cuesta, Anibal J. and Silvestre-Albero, Joaquín},
abstractNote = {For this research, synchrotron X-ray diffraction and inelastic neutron scattering measurements have been applied to evaluate the breathing phenomena in small nanocrystals of ZIF-7 upon gas adsorption. The experimental results show that an extended solvent exchange process with methanol is crucial to get a solvent-free narrow pore structure. Under these conditions, nano-ZIF-7 is indeed able to adsorb N2 with a total BET surface area of around 380 m2 g-1, in close agreement with theoretical predictions. The breathing phenomenon upon nitrogen adsorption is accompanied by a phase-to-phase transition, from a narrow-pore (phase II) to a large-pore (phase I) structure and a suppression of the cooperative deformation of the framework involving mainly the flapping motion of the benzimidazolate (bIm) ligand with the 4- and 6-membered rings. Whereas nitrogen requires temperature and pressure conditions close to condensation (close to 1 bar and 77 K) to induce the breathing in ZIF-7, CO2 can do it under milder conditions (at room temperature and low relative pressures). These results reflect that the nature of the adsorptive probe and the gas–framework interactions, rather than the molecular diameter and/or shape, play a crucial role in defining the pressure and temperature conditions required to induce the breathing. Lastly, the presence of two different cavities in ZIF-7 as suggested by theoretical predictions, one with a window diameter of below 0.4 nm (cavity A) and the other with a pore size of around 0.6 nm (cavity B), has been confirmed experimentally using immersion calorimetry.},
doi = {10.1039/C7TA05922A},
journal = {Journal of Materials Chemistry. A},
number = 39,
volume = 5,
place = {United States},
year = {2017},
month = {9}
}

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Works referenced in this record:

A Pillared-Layer Coordination Polymer with a Rotatable Pillar Acting as a Molecular Gate for Guest Molecules
journal, September 2009

  • Seo, Joobeom; Matsuda, Ryotaro; Sakamoto, Hirotoshi
  • Journal of the American Chemical Society, Vol. 131, Issue 35
  • DOI: 10.1021/ja904363b

A Combined Experimental-Computational Study on the Effect of Topology on Carbon Dioxide Adsorption in Zeolitic Imidazolate Frameworks
journal, November 2012

  • Morris, William; He, Ning; Ray, Keith G.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 45
  • DOI: 10.1021/jp307170a

Characterization of microporous solids by immersion calorimetry
journal, August 2001

  • Silvestre-Albero, J.
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 187-188, Issue 1-3
  • DOI: 10.1016/S0927-7757(01)00620-3

Opening the Gate: Framework Flexibility in ZIF-8 Explored by Experiments and Simulations
journal, June 2011

  • Fairen-Jimenez, D.; Moggach, S. A.; Wharmby, M. T.
  • Journal of the American Chemical Society, Vol. 133, Issue 23
  • DOI: 10.1021/ja202154j

Understanding Gas-Induced Structural Deformation of ZIF-8
journal, April 2012

  • Ania, Conchi O.; García-Pérez, E.; Haro, M.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 9
  • DOI: 10.1021/jz300292y

Molecular Sieve Membrane: Supported Metal-Organic Framework with High Hydrogen Selectivity
journal, November 2009

  • Li, Yan-Shuo; Liang, Fang-Yi; Bux, Helge
  • Angewandte Chemie International Edition, Vol. 49, Issue 3
  • DOI: 10.1002/anie.200905645

Understanding ZIF-8 Performance upon Gas Adsorption by Means of Inelastic Neutron Scattering
journal, March 2017

  • Casco, Mirian E.; Fernández-Catalá, Javier; Cheng, Yongqiang
  • ChemistrySelect, Vol. 2, Issue 9
  • DOI: 10.1002/slct.201700250

Direct visualisation of carbon dioxide adsorption in gate-opening zeolitic imidazolate framework ZIF-7
journal, January 2014

  • Zhao, Pu; Lampronti, Giulio I.; Lloyd, Gareth O.
  • J. Mater. Chem. A, Vol. 2, Issue 3
  • DOI: 10.1039/C3TA13981F

aCLIMAX 4.0.1, The new version of the software for analyzing and interpreting INS spectra
journal, March 2004


High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture
journal, February 2008


The crystallography stations at the Alba synchrotron
journal, August 2015

  • Fauth, François; Boer, Roeland; Gil-Ortiz, Fernando
  • The European Physical Journal Plus, Vol. 130, Issue 8
  • DOI: 10.1140/epjp/i2015-15160-y

Deformation of Microporous Carbon during Adsorption of Nitrogen, Argon, Carbon Dioxide, and Water Studied by in Situ Dilatometry
journal, November 2015


Density Functional Theory Model of Adsorption Deformation
journal, December 2006

  • Ravikovitch, Peter I.; Neimark, Alexander V.
  • Langmuir, Vol. 22, Issue 26
  • DOI: 10.1021/la061092u

Rapid room temperature syntheses of zeolitic-imidazolate framework (ZIF) nanocrystals
journal, January 2014

  • Tu, Min; Wiktor, Christian; Rösler, Christoph
  • Chem. Commun., Vol. 50, Issue 87
  • DOI: 10.1039/C4CC06491G

Phase Transitions in Zeolitic Imidazolate Framework 7: The Importance of Framework Flexibility and Guest-Induced Instability
journal, February 2014

  • Zhao, Pu; Lampronti, Giulio I.; Lloyd, Gareth O.
  • Chemistry of Materials, Vol. 26, Issue 5
  • DOI: 10.1021/cm500407f

Adsorption of n-Pentane on Mesoporous Silica and Adsorbent Deformation
journal, June 2013

  • Gor, Gennady Yu.; Paris, Oskar; Prass, Johannes
  • Langmuir, Vol. 29, Issue 27
  • DOI: 10.1021/la401513n

Ethane/Ethene Separation Turned on Its Head: Selective Ethane Adsorption on the Metal−Organic Framework ZIF-7 through a Gate-Opening Mechanism
journal, December 2010

  • Gücüyener, Canan; van den Bergh, Johan; Gascon, Jorge
  • Journal of the American Chemical Society, Vol. 132, Issue 50
  • DOI: 10.1021/ja1089765

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks
journal, June 2006

  • Park, K. S.; Ni, Z.; Cote, A. P.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 27, p. 10186-10191
  • DOI: 10.1073/pnas.0602439103

New High- and Low-Temperature Phase Changes of ZIF-7: Elucidation and Prediction of the Thermodynamics of Transitions
journal, October 2015

  • Du, Yi; Wooler, Bradley; Nines, Meghan
  • Journal of the American Chemical Society, Vol. 137, Issue 42
  • DOI: 10.1021/jacs.5b08362

Large breathing effects in three-dimensional porous hybrid matter: facts, analyses, rules and consequences
journal, January 2009

  • Férey, Gérard; Serre, Christian
  • Chemical Society Reviews, Vol. 38, Issue 5
  • DOI: 10.1039/b804302g

Unusual flexibility of mesophase pitch-derived carbon materials: An approach to the synthesis of graphene
journal, May 2017


Thermal Structural Transitions and Carbon Dioxide Adsorption Properties of Zeolitic Imidazolate Framework-7 (ZIF-7)
journal, May 2014

  • Cai, Wanxi; Lee, Taehee; Lee, Maro
  • Journal of the American Chemical Society, Vol. 136, Issue 22
  • DOI: 10.1021/ja5016298

Guest-induced gate-opening of a zeolite imidazolate framework
journal, January 2011

  • Aguado, Sonia; Bergeret, Gérard; Titus, Marc Pera
  • New J. Chem., Vol. 35, Issue 3
  • DOI: 10.1039/C0NJ00836B

Zeolitic imidazolate framework materials: recent progress in synthesis and applications
journal, January 2014

  • Chen, Binling; Yang, Zhuxian; Zhu, Yanqiu
  • Journal of Materials Chemistry A, Vol. 2, Issue 40, p. 16811-16831
  • DOI: 10.1039/C4TA02984D

Gate-opening effect in ZIF-8: the first experimental proof using inelastic neutron scattering
journal, January 2016

  • Casco, M. E.; Cheng, Y. Q.; Daemen, L. L.
  • Chemical Communications, Vol. 52, Issue 18
  • DOI: 10.1039/C5CC10222G

Guest-Induced Gate Opening and Breathing Phenomena in Soft Porous Crystals: Building Thermodynamically Consistent Isotherms
journal, January 2012

  • Pera-Titus, Marc; Farrusseng, David
  • The Journal of Physical Chemistry C, Vol. 116, Issue 2
  • DOI: 10.1021/jp210174h