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Title: Room-Temperature Synthesis of Two-Dimensional Metal–Organic Frameworks with Controllable Size and Functionality for Enhanced CO2 Sorption

Abstract

Here, two-dimensional (2D) metal-organic frameworks (MOFs), as a newly emerged member of 2D materials, have gained extensive attention due to their great potential in gas separation, sensing, and catalysis. However, it is still challenging to synthesize 2D MOFs with controllable size and functionalities using direct and scalable approaches at mild conditions (e.g., room temperature). Herein, we demonstrated onestep, room-temperature synthesis of a series of 2D MOFs based on Cu(II) paddle-wheel units, where the intrinsically anisotropic building blocks led to the anisotropic growth of 2D MOF nanoparticles, and the pillared structure led to high surface areas. The size of 2D MOFs can be adjusted by using a DMF/H2O mixed solvent. The thinnest particles were around 3 nm, and the highest aspect ratio was up to 200. The functionalization of 2D MOFs was also achieved by selecting ligands with desired functional groups. The gas sorption results revealed that amino and nitro-functionalized 2D MOFs showed higher CO2 sorption selectivity over CH4 and N2, suggesting these materials can be further applied in natural gas sweetening (CO2/CH4 separation) and carbon capture from flue gas (CO2/N2 separation).

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. The Pennsylvania State Univ., University Park, PA (United States)
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1434712
Grant/Contract Number:  
FE0026825
Resource Type:
Accepted Manuscript
Journal Name:
Crystal Growth and Design
Additional Journal Information:
Journal Volume: 18; Journal Issue: 5; Journal ID: ISSN 1528-7483
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
03 NATURAL GAS

Citation Formats

Zha, Jie, and Zhang, Xueyi. Room-Temperature Synthesis of Two-Dimensional Metal–Organic Frameworks with Controllable Size and Functionality for Enhanced CO2 Sorption. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.cgd.8b00349.
Zha, Jie, & Zhang, Xueyi. Room-Temperature Synthesis of Two-Dimensional Metal–Organic Frameworks with Controllable Size and Functionality for Enhanced CO2 Sorption. United States. https://doi.org/10.1021/acs.cgd.8b00349
Zha, Jie, and Zhang, Xueyi. Tue . "Room-Temperature Synthesis of Two-Dimensional Metal–Organic Frameworks with Controllable Size and Functionality for Enhanced CO2 Sorption". United States. https://doi.org/10.1021/acs.cgd.8b00349. https://www.osti.gov/servlets/purl/1434712.
@article{osti_1434712,
title = {Room-Temperature Synthesis of Two-Dimensional Metal–Organic Frameworks with Controllable Size and Functionality for Enhanced CO2 Sorption},
author = {Zha, Jie and Zhang, Xueyi},
abstractNote = {Here, two-dimensional (2D) metal-organic frameworks (MOFs), as a newly emerged member of 2D materials, have gained extensive attention due to their great potential in gas separation, sensing, and catalysis. However, it is still challenging to synthesize 2D MOFs with controllable size and functionalities using direct and scalable approaches at mild conditions (e.g., room temperature). Herein, we demonstrated onestep, room-temperature synthesis of a series of 2D MOFs based on Cu(II) paddle-wheel units, where the intrinsically anisotropic building blocks led to the anisotropic growth of 2D MOF nanoparticles, and the pillared structure led to high surface areas. The size of 2D MOFs can be adjusted by using a DMF/H2O mixed solvent. The thinnest particles were around 3 nm, and the highest aspect ratio was up to 200. The functionalization of 2D MOFs was also achieved by selecting ligands with desired functional groups. The gas sorption results revealed that amino and nitro-functionalized 2D MOFs showed higher CO2 sorption selectivity over CH4 and N2, suggesting these materials can be further applied in natural gas sweetening (CO2/CH4 separation) and carbon capture from flue gas (CO2/N2 separation).},
doi = {10.1021/acs.cgd.8b00349},
journal = {Crystal Growth and Design},
number = 5,
volume = 18,
place = {United States},
year = {2018},
month = {4}
}

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Works referenced in this record:

Reticular synthesis and the design of new materials
journal, June 2003

  • Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W.
  • Nature, Vol. 423, Issue 6941, p. 705-714
  • DOI: 10.1038/nature01650

Introduction to Metal–Organic Frameworks
journal, September 2011

  • Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 673-674
  • DOI: 10.1021/cr300014x

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Beyond post-synthesis modification: evolution of metal–organic frameworks via building block replacement
journal, January 2014

  • Deria, Pravas; Mondloch, Joseph E.; Karagiaridi, Olga
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00067F

Selective gas adsorption and separation in metal–organic frameworks
journal, January 2009

  • Li, Jian-Rong; Kuppler, Ryan J.; Zhou, Hong-Cai
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1477-1504
  • DOI: 10.1039/b802426j

Metal–organic framework materials as catalysts
journal, January 2009

  • Lee, JeongYong; Farha, Omar K.; Roberts, John
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459
  • DOI: 10.1039/b807080f

Metal–Organic Frameworks for Separations
journal, September 2011

  • Li, Jian-Rong; Sculley, Julian; Zhou, Hong-Cai
  • Chemical Reviews, Vol. 112, Issue 2, p. 869-932
  • DOI: 10.1021/cr200190s

Emerging Multifunctional Metal-Organic Framework Materials
journal, July 2016


CO 2 Capture and Separations Using MOFs: Computational and Experimental Studies
journal, April 2017


Metal-organic framework nanosheets as building blocks for molecular sieving membranes
journal, December 2014


Metal–organic framework nanosheets in polymer composite materials for gas separation
journal, November 2014

  • Rodenas, Tania; Luz, Ignacio; Prieto, Gonzalo
  • Nature Materials, Vol. 14, Issue 1
  • DOI: 10.1038/nmat4113

Two-Dimensional Metal–Organic Surfaces for Efficient Hydrogen Evolution from Water
journal, December 2014

  • Clough, Andrew J.; Yoo, Joseph W.; Mecklenburg, Matthew H.
  • Journal of the American Chemical Society, Vol. 137, Issue 1
  • DOI: 10.1021/ja5116937

Self-Supporting Metal-Organic Layers as Single-Site Solid Catalysts
journal, March 2016

  • Cao, Lingyun; Lin, Zekai; Peng, Fei
  • Angewandte Chemie International Edition, Vol. 55, Issue 16
  • DOI: 10.1002/anie.201512054

Fragmentation and exfoliation of 2-dimensional materials: a statistical approach
journal, January 2014

  • Kouroupis-Agalou, Konstantinos; Liscio, Andrea; Treossi, Emanuele
  • Nanoscale, Vol. 6, Issue 11
  • DOI: 10.1039/C3NR06919B

Combining Coordination Modulation with Acid–Base Adjustment for the Control over Size of Metal–Organic Frameworks
journal, December 2011

  • Guo, Hailing; Zhu, Yongzhong; Wang, Song
  • Chemistry of Materials, Vol. 24, Issue 3
  • DOI: 10.1021/cm202593h

Impact of ligands on CO2 adsorption in metal-organic frameworks: First principles study of the interaction of CO2 with functionalized benzenes. II. Effect of polar and acidic substituents
journal, January 2010

  • Torrisi, Antonio; Mellot-Draznieks, Caroline; Bell, Robert G.
  • The Journal of Chemical Physics, Vol. 132, Issue 4
  • DOI: 10.1063/1.3276105

Large-scale screening of hypothetical metal–organic frameworks
journal, November 2011

  • Wilmer, Christopher E.; Leaf, Michael; Lee, Chang Yeon
  • Nature Chemistry, Vol. 4, Issue 2, p. 83-89
  • DOI: 10.1038/nchem.1192

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    2D Metal–Organic Frameworks as Multifunctional Materials in Heterogeneous Catalysis and Electro/Photocatalysis
    journal, August 2019

    • Dhakshinamoorthy, Amarajothi; Asiri, Abdullah M.; Garcia, Hermenegildo
    • Advanced Materials, Vol. 31, Issue 41
    • DOI: 10.1002/adma.201900617

    Crystallization of high aspect ratio HKUST-1 thin films in nanoconfined channels for selective small molecule uptake
    journal, January 2019

    • Guthrie, Stephanie; Huelsenbeck, Luke; Salahi, Armita
    • Nanoscale Advances, Vol. 1, Issue 8
    • DOI: 10.1039/c9na00254e

    Rational Construction of a 2D PbII Coordination Polymer as a Sensitive Turn-Off Fluorescent Switch for Fe3+, Cr2O72−, and NFT
    journal, January 2020

    • Yi, Li; Guo, Feng
    • Australian Journal of Chemistry, Vol. 73, Issue 1
    • DOI: 10.1071/ch19416

    Two-dimensional metal–organic frameworks and their derivatives for electrochemical energy storage and electrocatalysis
    journal, January 2020

    • Zhao, Kuangmin; Zhu, Weiwei; Liu, Suqin
    • Nanoscale Advances, Vol. 2, Issue 2
    • DOI: 10.1039/c9na00719a