Award Abstract # 1836735
Collaborative Research: Enabling rational design of MOF-polymer mixed matrix membranes for liquid separations through understanding of microscale and macroscale properties

NSF Org: CBET
Division of Chemical, Bioengineering, Environmental, and Transport Systems
Recipient: UNIVERSITY OF FLORIDA
Initial Amendment Date: August 29, 2018
Latest Amendment Date: August 29, 2018
Award Number: 1836735
Award Instrument: Standard Grant
Program Manager: Christina Payne
cpayne@nsf.gov
 (703)292-2895
CBET
 Division of Chemical, Bioengineering, Environmental, and Transport Systems
ENG
 Directorate for Engineering
Start Date: October 1, 2018
End Date: September 30, 2022 (Estimated)
Total Intended Award Amount: $185,000.00
Total Awarded Amount to Date: $185,000.00
Funds Obligated to Date: FY 2018 = $185,000.00
History of Investigator:
  • Sergey Vasenkov (Principal Investigator)
    svasenkov@che.ufl.edu
Recipient Sponsored Research Office: University of Florida
1523 UNION RD RM 207
GAINESVILLE
FL  US  32611-1941
(352)392-3516
Sponsor Congressional District: 03
Primary Place of Performance: University of Florida
Gainesville
FL  US  32611-2002
Primary Place of Performance
Congressional District:
03
Unique Entity Identifier (UEI): NNFQH1JAPEP3
Parent UEI:
NSF Program(s): Interfacial Engineering Progra
Primary Program Source: 01001819DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s):
Program Element Code(s): 141700
Award Agency Code: 4900
Fund Agency Code: 4900
Assistance Listing Number(s): 47.041

ABSTRACT

Gasoline, plastics, laundry detergent, many pharmaceuticals, and cosmetics are all derived from organic liquids. Organic liquids are essentially the liquid fraction of crude oil. The molecules in crude oil are a complex mixture, that must first be separated before they can be converted to useful consumer products. Today, separation of the mixture requires the organic liquids be boiled and distilled. Boiling the liquid requires a large energy input, the cost of which is ultimately passed on to the consumer. Given the vast consumption of consumer products derived from organic liquids, this separation utilizes a sizable fraction (about 10%) of the nation's total energy consumption. The development of alternative, low-cost and low-energy separations of organic liquids will allow the nation to continue, or improve upon, its standard of living while reducing energy consumption. To achieve this goal, there is growing interest in using solid mass separating agents to separate organic liquids, rather than distilling the mixture. One such example of a mass separating agent is a membrane, which acts as a sieve to separate the components of the mixture. Unlike a macroscopic sieve, a membrane contains nanometer-sized pores with specific chemical functionalities. Molecules pass through the pores and interact with the chemical functionalities in different manners, leading to a separation of different types of molecules. To separate organic liquids, which can dissolve many materials, the membrane must be chemically robust. This research project will couple traditional and advanced characterization techniques to track the movement of the organic molecules through membranes, in order to advance the rational design of mass separating agents that separate organic liquids.

This research project will seek to understand changes of the transport, structural, and sorption properties of organic liquids in polymers, metal-organic frameworks (MOFs), and mixed-matrix membranes consisting of both of these components. Diffusion will be determined using both traditional transport measurements of molecular flux, as well as pulsed field gradient nuclear magnetic resonance spectroscopy. To evaluate diffusion with sub-micrometer spatial resolution, high magnetic field gradients and a high static magnetic field will be used. An analytical model will be developed to link microscopic and macroscopic diffusivities, transport properties, sorption, and structural properties. The goal of this model will be to develop design principles for MOF-based mixed-matrix membranes for organic liquid separations. Educational and outreach aspects of the work will leverage existing programs, introduce animations and educational demonstrations, and offer students participation in well-defined engineering projects related to membrane separations.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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Baniani, Amineh and Berens, Samuel J. and Rivera, Matthew P. and Lively, Ryan P. and Vasenkov, Sergey "Potentials and challenges of high-field PFG NMR diffusion studies with sorbates in nanoporous media" Adsorption , 2020 https://doi.org/10.1007/s10450-020-00255-y Citation Details
Baniani, Amineh and Rivera, Matthew P. and Lively, Ryan P. and Vasenkov, Sergey "Quantifying diffusion of organic liquids in a MOF component of MOF/Polymer mixed-matrix membranes by high field NMR" Journal of Membrane Science , v.640 , 2021 https://doi.org/10.1016/j.memsci.2021.119786 Citation Details
Baniani, Amineh and Rivera, Matthew P. and Lively, Ryan P. and Vasenkov, Sergey "Self-diffusion of mixed xylene isomers in ZIF-71 crystals dispersed in a polymer to form a hybrid membrane" Microporous and Mesoporous Materials , v.338 , 2022 https://doi.org/10.1016/j.micromeso.2022.111960 Citation Details
Baniani, Amineh and Rivera, Matthew P. and Marreiros, João and Lively, Ryan P. and Vasenkov, Sergey "Influence of polymer modification on intra-MOF self-diffusion in MOF-based mixed matrix membranes" Microporous and Mesoporous Materials , v.359 , 2023 https://doi.org/10.1016/j.micromeso.2023.112648 Citation Details

PROJECT OUTCOMES REPORT

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

Advanced hybrid membranes formed by mixing of innovative fillers known as metal–organic frameworks (MOFs) and processable polymers represent a promising class of membranes for separations of liquids required in industry. The liquid transport in such hybrid membranes is rather complex because transport rates are usually different in the two membrane components (i.e. MOF particles and the surrounding polymer). As a result, microscopic transport measurements performed selectively for a particular membrane component are needed in addition to conventional macroscopic transport measurements through the entire membrane for a detailed quantification and understanding of the intra-membrane transport process. Quantifying transport inside a MOF component of the membranes is important as transport properties of this component can change due to confinement in a polymer or required polymer modifications, which make the polymer more durable and suitable for separations. In this project, we used an advanced nuclear magnetic resonance technique for measurements of intra-MOF transport of pure and mixed liquids inside the membranes on microscopic (micrometer and sub-micrometer) length scales. The obtained results drastically broadened the existing knowledge on liquid transport in these membranes obtained by macroscopic techniques. In particular, it was observed that the conventional process of polymer modification can cause specific, well-defined changes in intra-MOF transport of liquids. The influence of the MOF crystal boundaries in the liquid transport process inside the membranes was quantified as well. This type of knowledge is required for knowledge-based design of the hybrid membranes for any specific separation of liquid mixtures.

Until now, the project results were disseminated in 3 full papers published in peer reviewed professional journals, 7 conference presentations and invited seminars, and 1 PhD dissertation. One additional full paper is currently in preparation. The PI Vasenkov has introduced and taught 3 mini-courses on NMR, diffusion NMR, and molecular diffusion in membranes for graduate and undergraduate students at the University of Florida (UF). Selected project results were integrated in the graduate elective course taught by the PI in the Spring 2022 semester. The in-person and online meetings between the UF and Georgia Tech groups participated in the project contributed to the development of interdisciplinary knowledge and skills by the participating students.   


Last Modified: 11/30/2022
Modified by: Sergey Vasenkov

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