ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Figure 1Loading Img

High H2 Sorption Energetics in Zeolitic Imidazolate Frameworks

View Author Information
Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, CHE205, Tampa, Florida 33620-5250, United States
Department of Chemistry, Materials Sciences Division, Lawrence Berkeley National Laboratory, University of California, Berkeley, Berkeley, California 94720, United States
§ Helmholtz-Zentrum Berlin für Materialien und Energie, Lise-Meitner Campus, Hahn-Meitner-Platz 1, 14109 Berlin, Germany
Department of Structural Chemistry, University of Milan, 21 Via G. Venezian, I-20133 Milan, Italy
Faculty of Chemistry and Pharmacy, University of Sofia, 1 James Bourchier Blvd., Sofia 1164, Bulgaria
*E-mail: [email protected] (B.S.).
*E-mail: [email protected] (J.E.).
Cite this: J. Phys. Chem. C 2017, 121, 3, 1723–1733
Publication Date (Web):December 29, 2016
Copyright © 2016 American Chemical Society

    Article Views





    Read OnlinePDF (5 MB)
    Supporting Info (1)»


    Abstract Image

    A combined experimental and theoretical study of H2 sorption was carried out on two isostructural zeolitic imidazolate frameworks (ZIFs), namely ZIF-68 and ZIF-69. The former consists of Zn2+ ions that are coordinated to two 2-nitroimidazolate and two benzimidazolate linkers in a tetrahedral fashion, while 5-chlorobenzimidazolate is used in place of benzimidazolate in the latter compound. H2 sorption measurements showed that the two ZIFs display similar isotherms and isosteric heats of adsorption (Qst). The experimental initial H2Qst value for both ZIFs was determined to be 8.1 kJ mol–1, which is quite high for materials that do not contain exposed metal centers. Molecular simulations of H2 sorption in ZIF-68 and ZIF-69 confirmed the similar H2 sorption properties between the two ZIFs, but also suggest that H2 sorption is slightly favored in ZIF-68 with regards to uptake at 77 K/1.0 atm. This work also presents inelastic neutron scattering (INS) spectra for H2 sorbed in ZIFs for the first time. The spectra for ZIF-68 and ZIF-69 show a broad range of intensities starting from about 4 meV. The most favorable H2 sorption site in both ZIFs corresponds to a confined region between two adjacent 2-nitroimidazolate linkers. Two-dimensional quantum rotation calculations for H2 sorbed at this site in ZIF-68 and ZIF-69 produced rotational transitions that are in accord with the lowest energy peak observed in the INS spectrum for the respective ZIFs. We found that the primary binding site for H2 in the two ZIFs generates high barriers to rotation for the adsorbed H2, which are greater than those in several metal–organic frameworks (MOFs) which possess open-metal sites. H2 sorption was also observed for both ZIFs in the vicinity of the nitro groups of the 2-nitroimidazolate linkers. This study highlights the constructive interplay of experiment and theory to elucidate critical details of the H2 sorption mechanism in these two isostructural ZIFs.

    Supporting Information

    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.6b11466.

    • Details of electronic structure calculations, grand canonical Monte Carlo methods, and quantum rotation calculations, pictures of ZIF fragments, tables of properties, and simulated H2 sorption results (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 13 publications.

    1. Anupam Maiti, Dilip Kumar Maity, Arijit Halder, Debajyoti Ghoshal. Multidirectional Solvent-Induced Structural Transformation in Designing a Series of Polycatenated Cobalt(II) Coordination Polymers: Impact on Carbon Dioxide and Hydrogen Uptake. Inorganic Chemistry 2023, 62 (31) , 12403-12412.
    2. Siddharth Gautam, Alexander I. Kolesnikov, Gernot Rother, Sheng Dai, Zhen-An Qiao, David Cole. Effects of Confinement and Pressure on the Vibrational Behavior of Nano-Confined Propane. The Journal of Physical Chemistry A 2018, 122 (33) , 6736-6745.
    3. Tony Pham, Katherine A. Forrest, Hiroyasu Furukawa, Juergen Eckert, Brian Space. Hydrogen Adsorption in a Zeolitic Imidazolate Framework with lta Topology. The Journal of Physical Chemistry C 2018, 122 (27) , 15435-15445.
    4. Li Li, Deshuai Yang, Trevor R. Fisher, Qi Qiao, Zhen Yang, Na Hu, Xiangshu Chen, and Liangliang Huang . Molecular Dynamics Simulations for Loading-Dependent Diffusion of CO2, SO2, CH4, and Their Binary Mixtures in ZIF-10: The Role of Hydrogen Bond. Langmuir 2017, 33 (42) , 11543-11553.
    5. Tony Pham, Katherine A. Forrest, Zheng Niu, Brant Tudor, Chloe B. Starkey, Yue Wang, Mohamed Eddaoudi, Nathaniel Rosi, Gisela Orcajo, Juergen Eckert, Shengqian Ma, Brian Space. Cu-ATC vs. Cu-BTC: comparing the H 2 adsorption mechanism through experiment, molecular simulation, and inelastic neutron scattering studies. Journal of Materials Chemistry A 2023, 11 (46) , 25386-25398.
    6. Xiaoqian Peng, Jing Zhang, Xu Zhang, Xiaochan Liu, Zhiqiang Huang, Haibo Li, Xibin Yi. Efficient H 2 adsorption using a bimetallic Ni–Zn zeolite imidazole skeleton. New Journal of Chemistry 2023, 47 (44) , 20279-20285.
    7. Cheolwon Jung, Sang Beom Choi, Jaewoo Park, Minji Jung, Jonghoon Kim, Hyunchul Oh, Jaheon Kim. Porous zeolitic imidazolate frameworks assembled with highly-flattened tetrahedral copper( ii ) centres and 2-nitroimidazolates. Chemical Communications 2023, 59 (27) , 4040-4043.
    8. K.R. Maiyelvaganan, M. Janani, K. Gopalsamy, M.K. Ravva, M. Prakash, V. Subramanian. Studies on hydrogen storage in molecules, cages, clusters, and materials: A DFT study. 2023, 213-235.
    9. Minhua Zhang, Qinghua Li, Kun Gu, Yifei Chen. The modified MOF-74 with H2 dissociation function for CO2 hydrogenation: A DFT study. Materials Today Communications 2021, 27 , 102419.
    10. Vera V. Butova, Vladimir A. Polyakov, Elena A. Bulanova, Mikhail A. Soldatov, Ibrahim S. Yahia, Heba Y. Zahran, Alaa F. Abd El-Rehim, Hamed Algarni, Abdelaziz M. Aboraia, Alexander V. Soldatov. MW synthesis of ZIF-65 with a hierarchical porous structure. Microporous and Mesoporous Materials 2020, 293 , 109685.
    11. Douglas M. Franz, Jonathan L. Belof, Keith McLaughlin, Christian R. Cioce, Brant Tudor, Adam Hogan, Luciano Laratelli, Meagan Mulcair, Matthew Mostrom, Alejandro Navas, Abraham C. Stern, Katherine A. Forrest, Tony Pham, Brian Space. MPMC and MCMD: Free High‐Performance Simulation Software for Atomistic Systems. Advanced Theory and Simulations 2019, 2 (11)
    12. N. Scott Bobbitt, Randall Q. Snurr. Molecular modelling and machine learning for high-throughput screening of metal-organic frameworks for hydrogen storage. Molecular Simulation 2019, 45 (14-15) , 1069-1081.
    13. Yulia A. Pimonova, Tatiana A. Lastovina, Andriy P. Budnyk, Egor A. Kudryavtsev, Maxim N. Yapryntsev. Cobalt-based ZIF-68 and ZIF-69 as the precursors of non-platinum electrocatalysts for oxygen reduction. Mendeleev Communications 2019, 29 (5) , 544-546.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect