Role of Structural Defects in the Water Adsorption Properties of MOF-801

Choi, Jongwon; Lin, Li-Chiang; Grossman, Jeffrey C.

doi:10.1021/acs.jpcc.8b00014

Title: Role of Structural Defects in the Water Adsorption Properties of MOF-801

Abstract

The nanoporous and tunable nature of metal–organic frameworks (MOFs) has made them promising adsorbents for water adsorption applications such as water harvesting and adsorptive heat pumps. In these applications, water adsorption properties in MOFs play a crucial role. However, understanding their structural defects and how defects influence adsorption thermodynamics remains limited to date. In this work, by employing Monte Carlo techniques and first-principle density functional theory calculations, we investigate the effect of defects on the water adsorption properties in MOF-801 structures at an atomic level. Our calculations show that the adsorption isotherm in perfect MOF-801 (without defects) greatly deviates from that measured experimentally. With the introduction of defects with a high density, a reasonably good agreement can be achieved, suggesting that a high defect density in MOF-801 may be responsible for its hydrophilic adsorptive behaviors. Further, water adsorption properties in MOF-801 structures are found to depend on the spatial configuration of defects, and water condensation in nanoporous MOF-801 is identified to occur preferentially along the $$\langle$$110$$\rangle$$ direction. Detailed structural characteristics (accessible volume, etc.) of MOF-801 structures and the adsorption energetics of water in the frameworks are also studied and correlated with the computed adsorption isotherms. Our findings reveal important insights into the role of defects, offering a microscopic picture to help facilitate the rational design of better MOFs for water adsorption applications.

Authors:

Choi, Jongwon ^[1];

^[2]; Grossman, Jeffrey C. ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
The Ohio State Univ., Columbus, OH (United States). William G. Lowrie Dept. of Chemical and Biomolecular Engineering

Publication Date:: 2018-02-21

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Org.:: USDOE Office of Science (SC); National Science Foundation (NSF)

OSTI Identifier:: 1483797

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 122; Journal Issue: 10; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Choi, Jongwon, Lin, Li-Chiang, and Grossman, Jeffrey C. Role of Structural Defects in the Water Adsorption Properties of MOF-801.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.jpcc.8b00014.

Copy to clipboard


                    Choi, Jongwon, Lin, Li-Chiang, & Grossman, Jeffrey C. Role of Structural Defects in the Water Adsorption Properties of MOF-801.  United States.  doi:https://doi.org/10.1021/acs.jpcc.8b00014

Copy to clipboard


                    Choi, Jongwon, Lin, Li-Chiang, and Grossman, Jeffrey C. Wed .  
        "Role of Structural Defects in the Water Adsorption Properties of MOF-801".  United States.  doi:https://doi.org/10.1021/acs.jpcc.8b00014.  https://www.osti.gov/servlets/purl/1483797.

Copy to clipboard


                    
@article{osti_1483797,

  title        = {Role of Structural Defects in the Water Adsorption Properties of MOF-801},

  author       = {Choi, Jongwon and Lin, Li-Chiang and Grossman, Jeffrey C.},

  abstractNote = {The nanoporous and tunable nature of metal–organic frameworks (MOFs) has made them promising adsorbents for water adsorption applications such as water harvesting and adsorptive heat pumps. In these applications, water adsorption properties in MOFs play a crucial role. However, understanding their structural defects and how defects influence adsorption thermodynamics remains limited to date. In this work, by employing Monte Carlo techniques and first-principle density functional theory calculations, we investigate the effect of defects on the water adsorption properties in MOF-801 structures at an atomic level. Our calculations show that the adsorption isotherm in perfect MOF-801 (without defects) greatly deviates from that measured experimentally. With the introduction of defects with a high density, a reasonably good agreement can be achieved, suggesting that a high defect density in MOF-801 may be responsible for its hydrophilic adsorptive behaviors. Further, water adsorption properties in MOF-801 structures are found to depend on the spatial configuration of defects, and water condensation in nanoporous MOF-801 is identified to occur preferentially along the $\langle$110$\rangle$ direction. Detailed structural characteristics (accessible volume, etc.) of MOF-801 structures and the adsorption energetics of water in the frameworks are also studied and correlated with the computed adsorption isotherms. Our findings reveal important insights into the role of defects, offering a microscopic picture to help facilitate the rational design of better MOFs for water adsorption applications.},

  doi          = {10.1021/acs.jpcc.8b00014},

  journal      = {Journal of Physical Chemistry. C},

  number       = 10,

  volume       = 122,

  place        = {United States},

  year         = {2018},

  month        = {2}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: https://doi.org/10.1021/acs.jpcc.8b00014

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 16 works

Citation information provided by
Web of Science

Figures / Tables:

Figure 1: Five MOF-801 defect structures with different defect densities and/or spatial configurations considered in this work. Green polyhedra represent the metal clusters, while missing linkers are highlighted in red. The relative position of the missing linkers is schematically illustrated in cubic boxes. The first number in the structure namemore »

All figures and tables (6 total)

Save / Share:

Export Metadata

Save to My Library

Works referencing / citing this record:

Dipeptide-functionalized MIL-101(Fe) as efficient material for ibuprofen delivery: Dipeptide functionalized MIL-101(Fe) for Ibuprofen delivery
journal, September 2018

Rajab Asadi, Fatemeh; Hamzavi, Seyedeh Fazileh; Shahverdizadeh, Gholam Hossein
Applied Organometallic Chemistry, Vol. 32, Issue 12
DOI: 10.1002/aoc.4552

The Origin of the Reproduction of Different Nitrogen Uptakes in Covalent Organic Frameworks (COFs)
journal, January 2019

Guan, Yiran; Li, Wenliang; Wang, Hailong
Chemistry - A European Journal, Vol. 25, Issue 9
DOI: 10.1002/chem.201805117

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar Records in DOE PAGES and OSTI.GOV collections:

Water Adsorption and Insertion in MOF-5

Journal Article Ming, Yang ; Kumar, Nitin ; Siegel, Donald J. - ACS Omega

The high surface areas and tunable properties of metal–organic frameworks (MOFs) make them attractive materials for applications in catalysis and the capture, storage, and separation of gases. Nevertheless, the limited stability of some MOFs under humid conditions remains a point of concern. Understanding the atomic-scale mechanisms associated with MOF hydrolysis will aid in the design of new compounds that are stable against water and other reactive species. Toward revealing these mechanisms, the present study employs van der Waals-augmented density functional theory, transition-state finding techniques, and thermodynamic integration to predict the thermodynamics and kinetics of water adsorption/insertion into the prototype compound,more »« less
Cited by 10
DOI: https://doi.org/10.1021/acsomega.7b01129
Creating a Discovery Platform for Confined-Space Chemistry and Materials: Metal-Organic Frameworks.

Technical Report Allendorf, Mark D. ; Greathouse, Jeffery A. ; Simmons, Blake

Metal organic frameworks (MOF) are a recently discovered class of nanoporous, defect-free crystalline materials that enable rational design and exploration of porous materials at the molecular level. MOFs have tunable monolithic pore sizes and cavity environments due to their crystalline nature, yielding properties exceeding those of most other porous materials. These include: the lowest known density (91% free space); highest surface area; tunable photoluminescence; selective molecular adsorption; and methane sorption rivaling gas cylinders. These properties are achieved by coupling inorganic metal complexes such as ZnO4 with tunable organic ligands that serve as struts, allowing facile manipulation of pore size andmore »« less
DOI: https://doi.org/10.2172/1130392

Full Text Available
Engineering Accessible Adsorption Sites in MOFs for CO2 Capture

Technical Report Ingram, Conrad ; Tandabany, Dinadayalane

The overall goal of this project was to synthesize metal-organic frameworks (MOFs) with improved CO2 adsorption and selectivity properties for potential application in removing this greenhouse gas from flue gas streams during fossil fuel processing. MOFs are an important class of 2-dimensional (2D) and 3D supramolecular coordination polymer networks that are comprised of organic linkers (ligands) and metal ion-units or clusters. They generally possess very high surface area, porosity, variable thermal stability and tunable chemistry, which make them potential candidates for CO2 adsorption. The three specific objectives of this project were as follows: 1) To synthesize MOFs with metal ionmore »« less
DOI: https://doi.org/10.2172/1582449

Full Text Available
Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

Journal Article Kim, Hyunho ; Cho, H. Jeremy ; Narayanan, Shankar ; ... - Scientific Reports

Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metalorganic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated asmore »« less
DOI: https://doi.org/10.1038/srep19097

Full Text Available
Ab Initio Derived Force Fields for Predicting CO₂ Adsorption and Accessibility of Metal Sites in the Metal–Organic Frameworks M-MOF-74 (M = Mn, Co, Ni, Cu)

Journal Article Haldoupis, Emmanuel ; Borycz, Joshua ; Shi, Huiliang ; ... - Journal of Physical Chemistry. C

Metal–organic frameworks (MOFs) are versatile nanoporous materials that have gained significant interest as low heat capacity, high selectivity sorbents for CO₂ capture applications. Large-scale atomistic simulations for identifying high-performance MOFs are possible, but are limited to systems for which existing molecular mechanics force fields describe the interactions between the guest and framework atoms with sufficient accuracy. However, standard force fields are not applicable to cases involving coordinatively unsaturated metal centers that can strongly bind specific sorbate molecules. It has been previously shown that improved force fields can be derived from quantum mechanical calculations. We derived force fields for an isostructuralmore »« less
Cited by 47
DOI: https://doi.org/10.1021/acs.jpcc.5b03700

Full Text Available

Similar Records

Title: Role of Structural Defects in the Water Adsorption Properties of MOF-801

Abstract

Citation Formats

Figures / Tables:

Dipeptide-functionalized MIL-101(Fe) as efficient material for ibuprofen delivery: Dipeptide functionalized MIL-101(Fe) for Ibuprofen delivery journal, September 2018

The Origin of the Reproduction of Different Nitrogen Uptakes in Covalent Organic Frameworks (COFs) journal, January 2019

Dipeptide-functionalized MIL-101(Fe) as efficient material for ibuprofen delivery: Dipeptide functionalized MIL-101(Fe) for Ibuprofen delivery
journal, September 2018

The Origin of the Reproduction of Different Nitrogen Uptakes in Covalent Organic Frameworks (COFs)
journal, January 2019