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Title: Versatile Surface Functionalization of Metal-Organic Frameworks through Direct Metal Coordination with a Phenolic Lipid Enables Diverse Applications

A novel strategy for the versatile functionalization of the external surface of metal-organic frameworks (MOFs) has been developed based on the direct coordination of a phenolic-inspired lipid molecule DPGG (1,2-dipalmitoyl-sn-glycero-3-galloyl) with metal nodes/sites surrounding MOF surface. X-ray diffraction and Argon sorption analysis prove that the modified MOF particles retain their structural integrity and porosity after surface modification. Density functional theory calculations reveal that strong chelation strength between the metal sites and the galloyl head group of DPGG is the basic prerequisite for successful coating. Due to the pH-responsive nature of metal-phenol complexation, the modification process is reversible by simple washing in weak acidic water, showing an excellent regeneration ability for water-stable MOFs. Moreover, the colloidal stability of the modified MOFs in the nonpolar solvent allows them to be further organized into 2 dimensional MOF or MOF/polymer monolayers by evaporation-induced interfacial assembly conducted on an air/water interface. Lastly, the easy fusion of a second functional layer onto DPGG-modified MOF cores, enabled a series of MOF-based functional nanoarchitectures, such as MOFs encapsulated within hybrid supported lipid bilayers (so-called protocells), polyhedral core-shell structures, hybrid lipid-modified-plasmonic vesicles and multicomponent supraparticles with target functionalities, to be generated. for a wide range of applications.
Authors:
 [1] ;  [2] ;  [3] ;  [1] ;  [4] ;  [1] ;  [1] ;  [5] ; ORCiD logo [6]
  1. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemical and Biological Engineering
  2. Univ. of Cambridge (United Kingdom). Melville Lab. for Polymer Synthesis, Dept. of Chemistry
  3. City Univ. of Hong Kong, Hong Kong (China). Joint Lab. for Energy and Environmental Catalysis School of Energy and Environment
  4. Monash Univ., Melbourne, VIC (Australia). Dept. of Mechanical and Aerospace Engineering
  5. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Advanced Materials Lab.
  6. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemical and Biological Engineering; Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Advanced Materials Lab.
Publication Date:
Report Number(s):
SAND-2017-12256J
Journal ID: ISSN 1616-301X; 658659
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 16; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; metal-organic framework; surface functionalization; metal-phenolic coordination; interfacial assembly; bioapplication
OSTI Identifier:
1464182
Alternate Identifier(s):
OSTI ID: 1422236

Zhu, Wei, Xiang, Guolei, Shang, Jin, Guo, Jimin, Motevalli, Benyamin, Durfee, Paul, Agola, Jacob Ongudi, Coker, Eric N., and Brinker, C. Jeffrey. Versatile Surface Functionalization of Metal-Organic Frameworks through Direct Metal Coordination with a Phenolic Lipid Enables Diverse Applications. United States: N. p., Web. doi:10.1002/adfm.201705274.
Zhu, Wei, Xiang, Guolei, Shang, Jin, Guo, Jimin, Motevalli, Benyamin, Durfee, Paul, Agola, Jacob Ongudi, Coker, Eric N., & Brinker, C. Jeffrey. Versatile Surface Functionalization of Metal-Organic Frameworks through Direct Metal Coordination with a Phenolic Lipid Enables Diverse Applications. United States. doi:10.1002/adfm.201705274.
Zhu, Wei, Xiang, Guolei, Shang, Jin, Guo, Jimin, Motevalli, Benyamin, Durfee, Paul, Agola, Jacob Ongudi, Coker, Eric N., and Brinker, C. Jeffrey. 2018. "Versatile Surface Functionalization of Metal-Organic Frameworks through Direct Metal Coordination with a Phenolic Lipid Enables Diverse Applications". United States. doi:10.1002/adfm.201705274.
@article{osti_1464182,
title = {Versatile Surface Functionalization of Metal-Organic Frameworks through Direct Metal Coordination with a Phenolic Lipid Enables Diverse Applications},
author = {Zhu, Wei and Xiang, Guolei and Shang, Jin and Guo, Jimin and Motevalli, Benyamin and Durfee, Paul and Agola, Jacob Ongudi and Coker, Eric N. and Brinker, C. Jeffrey},
abstractNote = {A novel strategy for the versatile functionalization of the external surface of metal-organic frameworks (MOFs) has been developed based on the direct coordination of a phenolic-inspired lipid molecule DPGG (1,2-dipalmitoyl-sn-glycero-3-galloyl) with metal nodes/sites surrounding MOF surface. X-ray diffraction and Argon sorption analysis prove that the modified MOF particles retain their structural integrity and porosity after surface modification. Density functional theory calculations reveal that strong chelation strength between the metal sites and the galloyl head group of DPGG is the basic prerequisite for successful coating. Due to the pH-responsive nature of metal-phenol complexation, the modification process is reversible by simple washing in weak acidic water, showing an excellent regeneration ability for water-stable MOFs. Moreover, the colloidal stability of the modified MOFs in the nonpolar solvent allows them to be further organized into 2 dimensional MOF or MOF/polymer monolayers by evaporation-induced interfacial assembly conducted on an air/water interface. Lastly, the easy fusion of a second functional layer onto DPGG-modified MOF cores, enabled a series of MOF-based functional nanoarchitectures, such as MOFs encapsulated within hybrid supported lipid bilayers (so-called protocells), polyhedral core-shell structures, hybrid lipid-modified-plasmonic vesicles and multicomponent supraparticles with target functionalities, to be generated. for a wide range of applications.},
doi = {10.1002/adfm.201705274},
journal = {Advanced Functional Materials},
number = 16,
volume = 28,
place = {United States},
year = {2018},
month = {2}
}

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