Tailoring Metal–Organic Frameworks for Water Harvesting
Water sorbents enable technologies that have the potential to mediate water insecurity, meet an increasing energy demand, and push towards sustainability. Metal-organic frameworks (MOFs) are candidate sorbents for such technologies as a direct result of their inherent chemical modularity – facilitat...
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| Format: | Thesis |
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Massachusetts Institute of Technology
2024
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| Online Access: | https://hdl.handle.net/1721.1/157060 |
| _version_ | 1824458327053041664 |
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| author | Oppenheim, Julius Jacob |
| author2 | Dincă, Mircea |
| author_facet | Dincă, Mircea Oppenheim, Julius Jacob |
| author_sort | Oppenheim, Julius Jacob |
| collection | MIT |
| description | Water sorbents enable technologies that have the potential to mediate water insecurity, meet an increasing energy demand, and push towards sustainability. Metal-organic frameworks (MOFs) are candidate sorbents for such technologies as a direct result of their inherent chemical modularity – facilitating the use of MOF sorbents to adsorb over a large range of relative humidity (RH). However, the underlying structure–function relationships between MOF composition and structure with sorption properties have yet to be explicitly determined. In this thesis, the author explores and defines such structure–function relationships. Chapter 1 introduces the important sorption properties as well as the top performing MOFs and MOF families. In Chapter 2, the author presents a derivation for a relationship between pore composition and the observable sorption parameters (critical RH, maximum gravimetric capacity, and presence of hysteresis loops). Chapter 3 realizes the insights from the preceding chapter to design and synthesize an industrially viable sorbent with high capacity below 30% RH and excellent cycling stability. Chapter 4 further explores these insights, with a focus on the observation that ions contained within the framework pore can greatly increase the hydrophilicity of a framework. Within Chapter 5, the author investigates the relationship between pore hydrophilicity and kinetic hysteresis, finding that kinetic limitations arise in sufficiently hydrophilic frameworks. Chapter 6 explores the driving differences in interaction between a framework and π-backbonding sorbates, for a framework in which the water sorption properties have been previously reported. Within Chapter 7, the author explores an alternative method for post-synthetic modification, whereby chlorine radical abstraction is utilized to reduce a framework, which may be useful for the synthesis of new sorbents. |
| first_indexed | 2025-02-19T04:24:07Z |
| format | Thesis |
| id | mit-1721.1/157060 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2025-02-19T04:24:07Z |
| publishDate | 2024 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/1570602024-09-27T03:13:44Z Tailoring Metal–Organic Frameworks for Water Harvesting Oppenheim, Julius Jacob Dincă, Mircea Massachusetts Institute of Technology. Department of Chemistry Water sorbents enable technologies that have the potential to mediate water insecurity, meet an increasing energy demand, and push towards sustainability. Metal-organic frameworks (MOFs) are candidate sorbents for such technologies as a direct result of their inherent chemical modularity – facilitating the use of MOF sorbents to adsorb over a large range of relative humidity (RH). However, the underlying structure–function relationships between MOF composition and structure with sorption properties have yet to be explicitly determined. In this thesis, the author explores and defines such structure–function relationships. Chapter 1 introduces the important sorption properties as well as the top performing MOFs and MOF families. In Chapter 2, the author presents a derivation for a relationship between pore composition and the observable sorption parameters (critical RH, maximum gravimetric capacity, and presence of hysteresis loops). Chapter 3 realizes the insights from the preceding chapter to design and synthesize an industrially viable sorbent with high capacity below 30% RH and excellent cycling stability. Chapter 4 further explores these insights, with a focus on the observation that ions contained within the framework pore can greatly increase the hydrophilicity of a framework. Within Chapter 5, the author investigates the relationship between pore hydrophilicity and kinetic hysteresis, finding that kinetic limitations arise in sufficiently hydrophilic frameworks. Chapter 6 explores the driving differences in interaction between a framework and π-backbonding sorbates, for a framework in which the water sorption properties have been previously reported. Within Chapter 7, the author explores an alternative method for post-synthetic modification, whereby chlorine radical abstraction is utilized to reduce a framework, which may be useful for the synthesis of new sorbents. Ph.D. 2024-09-26T18:16:09Z 2024-09-26T18:16:09Z 2024-05 2024-09-23T17:38:35.715Z Thesis https://hdl.handle.net/1721.1/157060 0000-0002-5988-0677 Attribution-ShareAlike 4.0 International (CC BY-SA 4.0) Copyright retained by author(s) https://creativecommons.org/licenses/by-sa/4.0/ application/pdf Massachusetts Institute of Technology |
| spellingShingle | Oppenheim, Julius Jacob Tailoring Metal–Organic Frameworks for Water Harvesting |
| title | Tailoring Metal–Organic Frameworks for Water Harvesting |
| title_full | Tailoring Metal–Organic Frameworks for Water Harvesting |
| title_fullStr | Tailoring Metal–Organic Frameworks for Water Harvesting |
| title_full_unstemmed | Tailoring Metal–Organic Frameworks for Water Harvesting |
| title_short | Tailoring Metal–Organic Frameworks for Water Harvesting |
| title_sort | tailoring metal organic frameworks for water harvesting |
| url | https://hdl.handle.net/1721.1/157060 |
| work_keys_str_mv | AT oppenheimjuliusjacob tailoringmetalorganicframeworksforwaterharvesting |