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).
- 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. doi: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}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 8 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
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
Functional Porous Coordination Polymers
journal, April 2004
- Kitagawa, Susumu; Kitaura, Ryo; Noro, Shin-ichiro
- Angewandte Chemie International Edition, Vol. 43, Issue 18, p. 2334-2375
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
Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks
journal, February 2010
- Deng, H.; Doonan, C. J.; Furukawa, H.
- Science, Vol. 327, Issue 5967, p. 846-850
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
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
Best Practices for the Synthesis, Activation, and Characterization of Metal–Organic Frameworks
journal, September 2016
- Howarth, Ashlee J.; Peters, Aaron W.; Vermeulen, Nicolaas A.
- Chemistry of Materials, Vol. 29, Issue 1
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
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
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
Metal–organic framework membranes: from synthesis to separation application
journal, January 2014
- Qiu, Shilun; Xue, Ming; Zhu, Guangshan
- Chem. Soc. Rev., Vol. 43, Issue 16
Metal–Organic Frameworks as Platforms for Functional Materials
journal, February 2016
- Cui, Yuanjing; Li, Bin; He, Huajun
- Accounts of Chemical Research, Vol. 49, Issue 3
Emerging Multifunctional Metal-Organic Framework Materials
journal, July 2016
- Li, Bin; Wen, Hui-Min; Cui, Yuanjing
- Advanced Materials, Vol. 28, Issue 40
Flexible–Robust Metal–Organic Framework for Efficient Removal of Propyne from Propylene
journal, June 2017
- Li, Libo; Lin, Rui-Biao; Krishna, Rajamani
- Journal of the American Chemical Society, Vol. 139, Issue 23
CO 2 Capture and Separations Using MOFs: Computational and Experimental Studies
journal, April 2017
- Yu, Jiamei; Xie, Lin-Hua; Li, Jian-Rong
- Chemical Reviews, Vol. 117, Issue 14
Metal-organic framework nanosheets as building blocks for molecular sieving membranes
journal, December 2014
- Peng, Y.; Li, Y.; Ban, Y.
- Science, Vol. 346, Issue 6215
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
Mixed matrix membranes composed of two-dimensional metal–organic framework nanosheets for pre-combustion CO 2 capture: a relationship study of filler morphology versus membrane performance
journal, January 2015
- Kang, Zixi; Peng, Yongwu; Hu, Zhigang
- Journal of Materials Chemistry A, Vol. 3, Issue 41
On the direct synthesis of Cu(BDC) MOF nanosheets and their performance in mixed matrix membranes
journal, March 2018
- Shete, Meera; Kumar, Prashant; Bachman, Jonathan E.
- Journal of Membrane Science, Vol. 549
Ultrathin 2D Metal-Organic Framework Nanosheets
journal, October 2015
- Zhao, Meiting; Wang, Yixian; Ma, Qinglang
- Advanced Materials, Vol. 27, Issue 45
Metal–organic framework nanosheets for fast-response and highly sensitive luminescent sensing of Fe 3+
journal, January 2016
- Xu, Hui; Gao, Junkuo; Qian, Xuefeng
- Journal of Materials Chemistry A, Vol. 4, Issue 28
Bioinspired Design of Ultrathin 2D Bimetallic Metal-Organic-Framework Nanosheets Used as Biomimetic Enzymes
journal, March 2016
- Wang, Yixian; Zhao, Meiting; Ping, Jianfeng
- Advanced Materials, Vol. 28, Issue 21
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
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
Competitive coordination strategy for the synthesis of hierarchical-pore metal–organic framework nanostructures
journal, January 2016
- He, Su; Chen, Yifeng; Zhang, Zhicheng
- Chemical Science, Vol. 7, Issue 12
Solvent-Induced Delamination of a Multifunctional Two Dimensional Coordination Polymer
journal, January 2013
- Gallego, Almudena; Hermosa, Cristina; Castillo, Oscar
- Advanced Materials, Vol. 25, Issue 15
Mechanical and optical properties of ultralarge flakes of a metal–organic framework with molecular thickness
journal, January 2015
- Hermosa, Cristina; Horrocks, Benjamin R.; Martínez, José I.
- Chemical Science, Vol. 6, Issue 4
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
Frameworks for Extended Solids: Geometrical Design Principles
journal, June 2000
- O'Keeffe, M.; Eddaoudi, M.; Li, Hailian
- Journal of Solid State Chemistry, Vol. 152, Issue 1, p. 3-20
Advances in the chemistry of metal–organic frameworks
journal, January 2002
- Rosi, Nathaniel L.; Eddaoudi, Mohamed; Kim, Jaheon
- CrystEngComm, Vol. 4, Issue 68, p. 401-404
Ultrathin 2D Coordination Polymer Nanosheets by Surfactant-Mediated Synthesis
journal, April 2013
- Junggeburth, Sebastian C.; Diehl, Leo; Werner, Stephan
- Journal of the American Chemical Society, Vol. 135, Issue 16
Rational Synthesis of Metal–Organic Framework Nanocubes and Nanosheets Using Selective Modulators and Their Morphology-Dependent Gas-Sorption Properties
journal, May 2012
- Pham, Minh-Hao; Vuong, Gia-Thanh; Fontaine, Frédéric-Georges
- Crystal Growth & Design, Vol. 12, Issue 6
Functionalized MOFs for Enhanced CO 2 Capture
journal, July 2010
- Torrisi, Antonio; Bell, Robert G.; Mellot-Draznieks, Caroline
- Crystal Growth & Design, Vol. 10, Issue 7
Enhancing Gas Adsorption and Separation Capacity through Ligand Functionalization of Microporous Metal-Organic Framework Structures
journal, March 2011
- Zhao, Yonggang; Wu, Haohan; Emge, Thomas J.
- Chemistry - A European Journal, Vol. 17, Issue 18
Geometric requirements and examples of important structures in the assembly of square building blocks
journal, April 2002
- Eddaoudi, M.; Kim, J.; Vodak, D.
- Proceedings of the National Academy of Sciences, Vol. 99, Issue 8, p. 4900-4904
Microporous Pillared Paddle-Wheel Frameworks Based on Mixed-Ligand Coordination of Zinc Ions
journal, July 2005
- Ma, Bao-Qing; Mulfort, Karen L.; Hupp, Joseph T.
- Inorganic Chemistry, Vol. 44, Issue 14
Heterogeneously Hybridized Porous Coordination Polymer Crystals: Fabrication of Heterometallic Core-Shell Single Crystals with an In-Plane Rotational Epitaxial Relationship
journal, February 2009
- Furukawa, Shuhei; Hirai, Kenji; Nakagawa, Keiji
- Angewandte Chemie International Edition, Vol. 48, Issue 10, p. 1766-1770
Modular Chemistry: Secondary Building Units as a Basis for the Design of Highly Porous and Robust Metal−Organic Carboxylate Frameworks
journal, April 2001
- Eddaoudi, Mohamed; Moler, David B.; Li, Hailian
- Accounts of Chemical Research, Vol. 34, Issue 4, p. 319-330
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
Multi-scale crystal engineering of metal organic frameworks
journal, January 2016
- Seoane, Beatriz; Castellanos, Sonia; Dikhtiarenko, Alla
- Coordination Chemistry Reviews, Vol. 307
Rigid and Flexible: A Highly Porous Metal–Organic Framework with Unusual Guest-Dependent Dynamic Behavior
journal, September 2004
- Dybtsev, Danil N.; Chun, Hyungphil; Kim, Kimoon
- Angewandte Chemie, Vol. 116, Issue 38
Synthesis, X-ray Crystal Structures, and Gas Sorption Properties of Pillared Square Grid Nets Based on Paddle-Wheel Motifs: Implications for Hydrogen Storage in Porous Materials
journal, June 2005
- Chun, Hyungphil; Dybtsev, Danil N.; Kim, Hyunuk
- Chemistry - A European Journal, Vol. 11, Issue 12
Radical Polymerization of Vinyl Monomers in Porous Coordination Polymers: Nanochannel Size Effects on Reactivity, Molecular Weight, and Stereostructure
journal, December 2007
- Uemura, Takashi; Ono, Yukari; Kitagawa, Kana
- Macromolecules, Vol. 41, Issue 1
The Potential Theory of Adsorption of Gases and Vapors for Adsorbents with Energetically Nonuniform Surfaces.
journal, April 1960
- Dubinin, M. M.
- Chemical Reviews, Vol. 60, Issue 2
Application of Consistency Criteria To Calculate BET Areas of Micro- And Mesoporous Metal–Organic Frameworks
journal, December 2015
- Gómez-Gualdrón, Diego A.; Moghadam, Peyman Z.; Hupp, Joseph T.
- Journal of the American Chemical Society, Vol. 138, Issue 1
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
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
Separation of CO 2 from Flue Gas: A Review
journal, January 2005
- Aaron, Douglas; Tsouris, Costas
- Separation Science and Technology, Vol. 40, Issue 1-3
Works referencing / citing this record:
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
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
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
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
2D Free‐Standing Nitrogen‐Doped Ni‐Ni 3 S 2 @Carbon Nanoplates Derived from Metal–Organic Frameworks for Enhanced Oxygen Evolution Reaction
journal, March 2019
- Lin, Yifan; Chen, Gen; Wan, Hao
- Small, Vol. 15, Issue 18
Synthesis, Crystal Structure, and Properties of a Zn(II) Coordination Polymer Based on a Difunctional Ligand Containing Triazolyl and Carboxyl Groups
journal, November 2018
- Li, Jia-Le; Li, Wei-Dong; He, Zi-Wei
- Crystals, Vol. 8, Issue 11
Ultrathin 2D metal–organic framework nanosheets prepared via sonication exfoliation of membranes from interfacial growth and exhibition of enhanced catalytic activity by their gold nanocomposites
journal, January 2019
- Wu, Songting; Qin, Lu; Zhang, Ke
- RSC Advances, Vol. 9, Issue 17