skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Hierarchical Metal–Organic Framework Hybrids: Perturbation-Assisted Nanofusion Synthesis

Abstract

Metal–organic frameworks (MOFs) represent a new family of microporous materials; however, microporous–mesoporous hierarchical MOF materials have been less investigated because of the lack of simple, reliable methods to introduce mesopores to the crystalline microporous particles. State-of-the-art MOF hierarchical materials have been prepared by ligand extension methods or by using a template, resulting in intrinsic mesopores of longer ligands or replicated pores from template agents, respectively. However, mesoporous MOF materials obtained through ligand extension often collapse in the absence of guest molecules, which dramatically reduces the size of the pore aperture. Although the template-directed strategy allows for the preparation of hierarchical materials with larger mesopores, the latter requires a template removal step, which may result in the collapse of the implemented mesopores. Recently, a general template-free synthesis of hierarchical microporous crystalline frameworks, such as MOFs and Prussian blue analogues (PBAs), has been reported. Our new method is based on the kinetically controlled precipitation (perturbation), with simultaneous condensation and redissolution of polymorphic nanocrystallites in the mother liquor. This method further eliminates the use of extended organic ligands and the micropores do not collapse upon removal of trapped guest solvent molecules, thus yielding hierarchical MOF materials with intriguing porosity in the gram scale.more » The hierarchical MOF materials prepared in this way exhibited exceptional properties when tested for the adsorption of large organic dyes over their corresponding microporous frameworks, due to the enhanced pore accessibility and electrolyte diffusion within the mesopores. As for PBAs, the pore size distribution of these materials can be tailored by changing the metals substituting Fe cations in the PB lattice. For these, the textural mesopores increased from approximately 10 nm for Cu analogue (mesoCuHCF), to 16 nm in Co substituted compound (mesoCoHCF), and to as large as 30 nm for the Ni derivative (mesoNiHCF). And while bulk PB and analogues have a higher capacitance than hierarchical analogues for Na-batteries, the increased accessibility to the microporous channels of PBAs allow for faster intercalated ion exchange and diffusion than in bulk PBA crystals. Therefore, hierarchical PBAs are promising candidates for electrodes in future electrochemical energy storage devices with faster charge–discharge rates than batteries, namely pseudocapacitors. Finally, this new synthetic method opens the possibility to prepare hierarchical materials having bimodal distribution of mesopores, and to tailor the structural properties of MOFs for different applications, including contrasting agents for MRI, and drug delivery.« less

Authors:
 [1];  [2];  [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Sul Ross State Univ., Alpine, TX (United States)
  2. Univ. of Puerto Rico, San Juan, PR (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
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:
1286961
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Accounts of Chemical Research
Additional Journal Information:
Journal Volume: 48; Journal Issue: 12; Journal ID: ISSN 0001-4842
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yue, Yanfeng, Fulvio, Pasquale F., and Dai, Sheng. Hierarchical Metal–Organic Framework Hybrids: Perturbation-Assisted Nanofusion Synthesis. United States: N. p., 2015. Web. doi:10.1021/acs.accounts.5b00349.
Yue, Yanfeng, Fulvio, Pasquale F., & Dai, Sheng. Hierarchical Metal–Organic Framework Hybrids: Perturbation-Assisted Nanofusion Synthesis. United States. doi:10.1021/acs.accounts.5b00349.
Yue, Yanfeng, Fulvio, Pasquale F., and Dai, Sheng. Fri . "Hierarchical Metal–Organic Framework Hybrids: Perturbation-Assisted Nanofusion Synthesis". United States. doi:10.1021/acs.accounts.5b00349. https://www.osti.gov/servlets/purl/1286961.
@article{osti_1286961,
title = {Hierarchical Metal–Organic Framework Hybrids: Perturbation-Assisted Nanofusion Synthesis},
author = {Yue, Yanfeng and Fulvio, Pasquale F. and Dai, Sheng},
abstractNote = {Metal–organic frameworks (MOFs) represent a new family of microporous materials; however, microporous–mesoporous hierarchical MOF materials have been less investigated because of the lack of simple, reliable methods to introduce mesopores to the crystalline microporous particles. State-of-the-art MOF hierarchical materials have been prepared by ligand extension methods or by using a template, resulting in intrinsic mesopores of longer ligands or replicated pores from template agents, respectively. However, mesoporous MOF materials obtained through ligand extension often collapse in the absence of guest molecules, which dramatically reduces the size of the pore aperture. Although the template-directed strategy allows for the preparation of hierarchical materials with larger mesopores, the latter requires a template removal step, which may result in the collapse of the implemented mesopores. Recently, a general template-free synthesis of hierarchical microporous crystalline frameworks, such as MOFs and Prussian blue analogues (PBAs), has been reported. Our new method is based on the kinetically controlled precipitation (perturbation), with simultaneous condensation and redissolution of polymorphic nanocrystallites in the mother liquor. This method further eliminates the use of extended organic ligands and the micropores do not collapse upon removal of trapped guest solvent molecules, thus yielding hierarchical MOF materials with intriguing porosity in the gram scale. The hierarchical MOF materials prepared in this way exhibited exceptional properties when tested for the adsorption of large organic dyes over their corresponding microporous frameworks, due to the enhanced pore accessibility and electrolyte diffusion within the mesopores. As for PBAs, the pore size distribution of these materials can be tailored by changing the metals substituting Fe cations in the PB lattice. For these, the textural mesopores increased from approximately 10 nm for Cu analogue (mesoCuHCF), to 16 nm in Co substituted compound (mesoCoHCF), and to as large as 30 nm for the Ni derivative (mesoNiHCF). And while bulk PB and analogues have a higher capacitance than hierarchical analogues for Na-batteries, the increased accessibility to the microporous channels of PBAs allow for faster intercalated ion exchange and diffusion than in bulk PBA crystals. Therefore, hierarchical PBAs are promising candidates for electrodes in future electrochemical energy storage devices with faster charge–discharge rates than batteries, namely pseudocapacitors. Finally, this new synthetic method opens the possibility to prepare hierarchical materials having bimodal distribution of mesopores, and to tailor the structural properties of MOFs for different applications, including contrasting agents for MRI, and drug delivery.},
doi = {10.1021/acs.accounts.5b00349},
journal = {Accounts of Chemical Research},
number = 12,
volume = 48,
place = {United States},
year = {2015},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Generation of Hierarchical Porosity in Metal-Organic Frameworks by the Modulation of Cation Valence
journal, June 2019

  • Qi, Shi-Chao; Qian, Xin-Yu; He, Qiu-Xia
  • Angewandte Chemie International Edition, Vol. 58, Issue 30
  • DOI: 10.1002/anie.201903323

Recent Advances of MOFs and MOF-Derived Materials in Thermally Driven Organic Transformations
journal, November 2018

  • Yang, Shuliang; Peng, Li; Bulut, Safak
  • Chemistry - A European Journal, Vol. 25, Issue 9
  • DOI: 10.1002/chem.201803157

Construction of hierarchically porous metal–organic frameworks through linker labilization
journal, May 2017

  • Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15356

A highly stable and hierarchical tetrathiafulvalene-based metal–organic framework with improved performance as a solid catalyst
journal, January 2018

  • Souto, Manuel; Santiago-Portillo, Andrea; Palomino, Miguel
  • Chemical Science, Vol. 9, Issue 9
  • DOI: 10.1039/c7sc04829g

Formation of trigons in a metal–organic framework: The role of metal–organic polyhedron subunits as meta-atoms
journal, January 2019

  • Lee, Jiyoung; Choi, Jae Sun; Jeong, Nak Cheon
  • Chemical Science, Vol. 10, Issue 24
  • DOI: 10.1039/c9sc00513g

Generation of Hierarchical Porosity in Metal-Organic Frameworks by the Modulation of Cation Valence
journal, June 2019

  • Qi, Shi-Chao; Qian, Xin-Yu; He, Qiu-Xia
  • Angewandte Chemie International Edition, Vol. 58, Issue 30
  • DOI: 10.1002/anie.201903323

Recent Advances of MOFs and MOF-Derived Materials in Thermally Driven Organic Transformations
journal, November 2018

  • Yang, Shuliang; Peng, Li; Bulut, Safak
  • Chemistry - A European Journal, Vol. 25, Issue 9
  • DOI: 10.1002/chem.201803157

Construction of hierarchically porous metal–organic frameworks through linker labilization
journal, May 2017

  • Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15356

A highly stable and hierarchical tetrathiafulvalene-based metal–organic framework with improved performance as a solid catalyst
journal, January 2018

  • Souto, Manuel; Santiago-Portillo, Andrea; Palomino, Miguel
  • Chemical Science, Vol. 9, Issue 9
  • DOI: 10.1039/c7sc04829g

Formation of trigons in a metal–organic framework: The role of metal–organic polyhedron subunits as meta-atoms
journal, January 2019

  • Lee, Jiyoung; Choi, Jae Sun; Jeong, Nak Cheon
  • Chemical Science, Vol. 10, Issue 24
  • DOI: 10.1039/c9sc00513g

Hollow Co3O4@MnO2 Cubic Derived From ZIF-67@Mn-ZIF as Electrode Materials for Supercapacitors
journal, December 2019