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Title: Continuous, One-pot Synthesis and Post-Synthetic Modification of NanoMOFs Using Droplet Nanoreactors

Here, metal-organic frameworks (MOFs); also known as porous coordination polymers (PCP) are a class of porous crystalline materials constructed by connecting metal clusters via organic linkers. The possibility of functionalization leads to virtually infinite MOF designs using generic modular methods. Functionalized MOFs can exhibit interesting physical and chemical properties including accelerated adsorption kinetics and catalysis. Although there are discrete methods to synthesize well-defined nanoscale MOFs, rapid and flexible methods are not available for continuous, one-pot synthesis and post synthesis modification (functionalization) of MOFs. Here, we show a continuous, scalable nanodroplet-based microfluidic route that not only facilitates the synthesis of MOFs at nanoscale, but also offers flexibility for direct functionalization with desired functional groups (e.g., -NH 2, -COCH 3, fluorescein isothiocyanate; FITC). In addition, the presented route of continuous manufacturing of functionalized MOFs takes significantly less time compared to state-of-the-art batch methods currently available (1 hr vs. several days). We envisage our approach to be a breakthrough method for synthesizing complex functionalized nanomaterials (metal, metal oxides, quantum dots and MOFs) that are not accessible by direct batch processing, and expand the range of a new class of functionalized MOF-based functional nanomaterials.
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Report Number(s):
PNNL-SA-119000
Journal ID: ISSN 2045-2322; 48731; GT0200000
Grant/Contract Number:
AC05-76RL01830
Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Research Org:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; nanomaterials; synthesis; functionalization; metal organic frameworks; microfluidics; nanofluids; Environmental Molecular Sciences Laboratory
OSTI Identifier:
1344650

Jambovane, Sachin R., Nune, Satish K., Kelly, Ryan T., McGrail, B. Peter, Wang, Zheming, Nandasiri, Manjula I., Katipamula, Shanta, Trader, Cameron, and Schaef, Herbert T.. Continuous, One-pot Synthesis and Post-Synthetic Modification of NanoMOFs Using Droplet Nanoreactors. United States: N. p., Web. doi:10.1038/srep36657.
Jambovane, Sachin R., Nune, Satish K., Kelly, Ryan T., McGrail, B. Peter, Wang, Zheming, Nandasiri, Manjula I., Katipamula, Shanta, Trader, Cameron, & Schaef, Herbert T.. Continuous, One-pot Synthesis and Post-Synthetic Modification of NanoMOFs Using Droplet Nanoreactors. United States. doi:10.1038/srep36657.
Jambovane, Sachin R., Nune, Satish K., Kelly, Ryan T., McGrail, B. Peter, Wang, Zheming, Nandasiri, Manjula I., Katipamula, Shanta, Trader, Cameron, and Schaef, Herbert T.. 2016. "Continuous, One-pot Synthesis and Post-Synthetic Modification of NanoMOFs Using Droplet Nanoreactors". United States. doi:10.1038/srep36657. https://www.osti.gov/servlets/purl/1344650.
@article{osti_1344650,
title = {Continuous, One-pot Synthesis and Post-Synthetic Modification of NanoMOFs Using Droplet Nanoreactors},
author = {Jambovane, Sachin R. and Nune, Satish K. and Kelly, Ryan T. and McGrail, B. Peter and Wang, Zheming and Nandasiri, Manjula I. and Katipamula, Shanta and Trader, Cameron and Schaef, Herbert T.},
abstractNote = {Here, metal-organic frameworks (MOFs); also known as porous coordination polymers (PCP) are a class of porous crystalline materials constructed by connecting metal clusters via organic linkers. The possibility of functionalization leads to virtually infinite MOF designs using generic modular methods. Functionalized MOFs can exhibit interesting physical and chemical properties including accelerated adsorption kinetics and catalysis. Although there are discrete methods to synthesize well-defined nanoscale MOFs, rapid and flexible methods are not available for continuous, one-pot synthesis and post synthesis modification (functionalization) of MOFs. Here, we show a continuous, scalable nanodroplet-based microfluidic route that not only facilitates the synthesis of MOFs at nanoscale, but also offers flexibility for direct functionalization with desired functional groups (e.g., -NH2, -COCH3, fluorescein isothiocyanate; FITC). In addition, the presented route of continuous manufacturing of functionalized MOFs takes significantly less time compared to state-of-the-art batch methods currently available (1 hr vs. several days). We envisage our approach to be a breakthrough method for synthesizing complex functionalized nanomaterials (metal, metal oxides, quantum dots and MOFs) that are not accessible by direct batch processing, and expand the range of a new class of functionalized MOF-based functional nanomaterials.},
doi = {10.1038/srep36657},
journal = {Scientific Reports},
number = ,
volume = 6,
place = {United States},
year = {2016},
month = {11}
}

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