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Title: Pore-Engineered Metal–Organic Frameworks with Excellent Adsorption of Water and Fluorocarbon Refrigerant for Cooling Applications

Abstract

Metal–organic frameworks (MOFs) are found to be promising sorbents for adsorption cooling applications. Using organic ligands with 1, 2, and 3 phenylene rings, we construct moisture-stable Ni-MOF-74 members with adjustable pore apertures. These pore-engineered materials exhibit excellent sorption capabilities towards water and fluorocarbons. The adsorption patterns for these materials differ significantly and are attributed to variances in the hydrophobic/hydrophilic pore character, associated with differences in pore size. Complementary ex situ characterizations and in situ FTIR spectra are deployed to understand the correlations between the mechanisms of gas loadings and the pore environment of the MOFs.

Authors:
ORCiD logo [1];  [2];  [2];  [2]; ORCiD logo [3];  [1];  [1];  [2]; ORCiD logo [2]
  1. Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
  2. Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
  3. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Geothermal Technologies Office (EE-4G)
OSTI Identifier:
1378045
Report Number(s):
PNNL-SA-124980
Journal ID: ISSN 0002-7863; GT0200000
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 139; Journal Issue: 31
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; metal-organic frameworks; pore-engineering; adsorption cooling; adsorption isotherm; insitu FTIR; fluorocarbon

Citation Formats

Zheng, Jian, Vemuri, Rama S., Estevez, Luis, Koech, Phillip K., Varga, Tamas, Camaioni, Donald M., Blake, Thomas A., McGrail, B. Peter, and Motkuri, Radha Kishan. Pore-Engineered Metal–Organic Frameworks with Excellent Adsorption of Water and Fluorocarbon Refrigerant for Cooling Applications. United States: N. p., 2017. Web. doi:10.1021/jacs.7b04872.
Zheng, Jian, Vemuri, Rama S., Estevez, Luis, Koech, Phillip K., Varga, Tamas, Camaioni, Donald M., Blake, Thomas A., McGrail, B. Peter, & Motkuri, Radha Kishan. Pore-Engineered Metal–Organic Frameworks with Excellent Adsorption of Water and Fluorocarbon Refrigerant for Cooling Applications. United States. doi:10.1021/jacs.7b04872.
Zheng, Jian, Vemuri, Rama S., Estevez, Luis, Koech, Phillip K., Varga, Tamas, Camaioni, Donald M., Blake, Thomas A., McGrail, B. Peter, and Motkuri, Radha Kishan. 2017. "Pore-Engineered Metal–Organic Frameworks with Excellent Adsorption of Water and Fluorocarbon Refrigerant for Cooling Applications". United States. doi:10.1021/jacs.7b04872.
@article{osti_1378045,
title = {Pore-Engineered Metal–Organic Frameworks with Excellent Adsorption of Water and Fluorocarbon Refrigerant for Cooling Applications},
author = {Zheng, Jian and Vemuri, Rama S. and Estevez, Luis and Koech, Phillip K. and Varga, Tamas and Camaioni, Donald M. and Blake, Thomas A. and McGrail, B. Peter and Motkuri, Radha Kishan},
abstractNote = {Metal–organic frameworks (MOFs) are found to be promising sorbents for adsorption cooling applications. Using organic ligands with 1, 2, and 3 phenylene rings, we construct moisture-stable Ni-MOF-74 members with adjustable pore apertures. These pore-engineered materials exhibit excellent sorption capabilities towards water and fluorocarbons. The adsorption patterns for these materials differ significantly and are attributed to variances in the hydrophobic/hydrophilic pore character, associated with differences in pore size. Complementary ex situ characterizations and in situ FTIR spectra are deployed to understand the correlations between the mechanisms of gas loadings and the pore environment of the MOFs.},
doi = {10.1021/jacs.7b04872},
journal = {Journal of the American Chemical Society},
number = 31,
volume = 139,
place = {United States},
year = 2017,
month = 7
}
  • Metal-organic frameworks (MOFs) have recently attracted enormous interest over the past few years in energy storage and gas separation, yet there have been few reports for adsorption cooling applications. Adsorption cooling technology is an established alternative to mechanical vapor compression refrigeration systems and is an excellent alternative in industrial environments where waste heat is available. We explored the use of MOFs that have very high mass loading and relatively low heats of adsorption, with certain combinations of refrigerants to demonstrate a new type of highly efficient adsorption chiller. Computational fluid dynamics combined with a system level lumped-parameter model have beenmore » used to project size and performance for chillers with a cooling capacity ranging from a few kW to several thousand kW. These systems rely on stacked micro/mini-scale architectures to enhance heat and mass transfer. Recent computational studies of an adsorption chiller based on MOFs suggests that a thermally-driven coefficient of performance greater than one may be possible, which would represent a fundamental breakthrough in performance of adsorption chiller technology. Presented herein are computational and experimental results for hydrophyilic and fluorophilic MOFs.« less
  • Water adsorption in porous materials is important for many applications such as dehumidification, thermal batteries, and delivery of drinking water in remote areas. In this study, we have identified three criteria for achieving high performing porous materials for water adsorption. These criteria deal with condensation pressure of water in the pores, uptake capacity, and recyclability and water stability of the material. In search of an excellently performing porous material, we have studied and compared the water adsorption properties of 23 materials, 20 of which are metal organic frameworks (MOFs). Among the MOFs are 10 zirconium(IV) MOFs with a subset ofmore » these, MOF-801-SC (single crystal form), -802, -805, -806, -808, -812, and -841 reported for the first time. MOF-801-P (microcrystalline powder form) was reported earlier and studied here for its water adsorption properties. MOF-812 was only made and structurally characterized but not examined for water adsorption because it is a byproduct of MOF-841 synthesis. All the new zirconium MOFs are made from the Zr6O4(OH)(4)(-CO2)(n) secondary building units (n = 6, 8, 10, or 12) and variously shaped carboxyl organic linkers to make extended porous frameworks. The permanent porosity of all 23 materials was confirmed and their water adsorption measured to reveal that MOF-801-P and MOF-841 are the highest performers based on the three criteria stated above; they are water stable, do not lose capacity after five adsorption/desorption cycles, and are easily regenerated at room temperature. An X-ray single-crystal study and a powder neutron diffraction study reveal the position of the water adsorption sites in MOF-801 and highlight the importance of the intermolecular interaction between adsorbed water molecules within the pores.« less