Defect-induced confinement in zirconium metal-organic frameworks for enhanced hydrogen adsorption
Hydrogen is an essential gas to multiple industrial processes, and due to its high gravimetric density, it promises a large potential as a clean energy source. The risks of hydrogen at low pressures, however, have deterred substantial progress in improving hydrogen storage technology. Metal-organic...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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Elsevier
2023-09-01
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| Series: | Sustainable Chemistry for the Environment |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2949839223000329 |
| _version_ | 1797235369829203968 |
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| author | Joshua Duncan Debabrata Sengupta Saptasree Bose Kent O. Kirlikovali Omar K. Farha |
| author_facet | Joshua Duncan Debabrata Sengupta Saptasree Bose Kent O. Kirlikovali Omar K. Farha |
| author_sort | Joshua Duncan |
| collection | DOAJ |
| description | Hydrogen is an essential gas to multiple industrial processes, and due to its high gravimetric density, it promises a large potential as a clean energy source. The risks of hydrogen at low pressures, however, have deterred substantial progress in improving hydrogen storage technology. Metal-organic frameworks (MOFs) are crystalline porous materials that have emerged as excellent gas adsorbents, and their gas storage properties can be tuned using a variety of synthetic methods. Herein, we leveraged the tunability and porosity of MOFs to introduce defect engineering as a method to improve hydrogen storage technology at low pressure regimes in two zirconium-based MOFs (Zr-MOFs), UiO-66 and NU-403, which feature ideal pore apertures (7 Å) for studying the confinement effect and ease of defect engineering. By reducing the number of defects in these Zr-MOFs, and thereby decreasing the quantity of larger pores, we can induce a structural confinement effect that increases the selectivity of hydrogen adsorption. A combination of thermogravimetric analysis (TGA) and nuclear magnetic resonance (NMR) spectroscopic analysis enabled quantification of the defect levels, confirming that each sample exhibits a distinct level of defectiveness. Gas adsorption measurements revealed that the adsorption of hydrogen is greatly enhanced in samples with fewer defects, while the calculated isosteric heats of enthalpy (Qst) indicate that there are no open metal sites in these MOFs that could be the cause. Overall, we can conclude that defect engineering for pore tailoring is a viable strategy to enhance hydrogen adsorption at low-pressure regimes. |
| first_indexed | 2024-04-24T16:46:52Z |
| format | Article |
| id | doaj.art-04f766d822b04efea6e39c90d21a3a27 |
| institution | Directory Open Access Journal |
| issn | 2949-8392 |
| language | English |
| last_indexed | 2024-04-24T16:46:52Z |
| publishDate | 2023-09-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Sustainable Chemistry for the Environment |
| spelling | doaj.art-04f766d822b04efea6e39c90d21a3a272024-03-29T05:52:28ZengElsevierSustainable Chemistry for the Environment2949-83922023-09-013100032Defect-induced confinement in zirconium metal-organic frameworks for enhanced hydrogen adsorptionJoshua Duncan0Debabrata Sengupta1Saptasree Bose2Kent O. Kirlikovali3Omar K. Farha4Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, United StatesDepartment of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, United StatesDepartment of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, United StatesDepartment of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, United StatesDepartment of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, United States; International Institute of Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, United States; Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, United States; Corresponding author at: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, United States.Hydrogen is an essential gas to multiple industrial processes, and due to its high gravimetric density, it promises a large potential as a clean energy source. The risks of hydrogen at low pressures, however, have deterred substantial progress in improving hydrogen storage technology. Metal-organic frameworks (MOFs) are crystalline porous materials that have emerged as excellent gas adsorbents, and their gas storage properties can be tuned using a variety of synthetic methods. Herein, we leveraged the tunability and porosity of MOFs to introduce defect engineering as a method to improve hydrogen storage technology at low pressure regimes in two zirconium-based MOFs (Zr-MOFs), UiO-66 and NU-403, which feature ideal pore apertures (7 Å) for studying the confinement effect and ease of defect engineering. By reducing the number of defects in these Zr-MOFs, and thereby decreasing the quantity of larger pores, we can induce a structural confinement effect that increases the selectivity of hydrogen adsorption. A combination of thermogravimetric analysis (TGA) and nuclear magnetic resonance (NMR) spectroscopic analysis enabled quantification of the defect levels, confirming that each sample exhibits a distinct level of defectiveness. Gas adsorption measurements revealed that the adsorption of hydrogen is greatly enhanced in samples with fewer defects, while the calculated isosteric heats of enthalpy (Qst) indicate that there are no open metal sites in these MOFs that could be the cause. Overall, we can conclude that defect engineering for pore tailoring is a viable strategy to enhance hydrogen adsorption at low-pressure regimes.http://www.sciencedirect.com/science/article/pii/S2949839223000329Confinement effectHydrogen storageMetal-organic frameworksDefect engineeringGas adsorptionRenewable energy |
| spellingShingle | Joshua Duncan Debabrata Sengupta Saptasree Bose Kent O. Kirlikovali Omar K. Farha Defect-induced confinement in zirconium metal-organic frameworks for enhanced hydrogen adsorption Sustainable Chemistry for the Environment Confinement effect Hydrogen storage Metal-organic frameworks Defect engineering Gas adsorption Renewable energy |
| title | Defect-induced confinement in zirconium metal-organic frameworks for enhanced hydrogen adsorption |
| title_full | Defect-induced confinement in zirconium metal-organic frameworks for enhanced hydrogen adsorption |
| title_fullStr | Defect-induced confinement in zirconium metal-organic frameworks for enhanced hydrogen adsorption |
| title_full_unstemmed | Defect-induced confinement in zirconium metal-organic frameworks for enhanced hydrogen adsorption |
| title_short | Defect-induced confinement in zirconium metal-organic frameworks for enhanced hydrogen adsorption |
| title_sort | defect induced confinement in zirconium metal organic frameworks for enhanced hydrogen adsorption |
| topic | Confinement effect Hydrogen storage Metal-organic frameworks Defect engineering Gas adsorption Renewable energy |
| url | http://www.sciencedirect.com/science/article/pii/S2949839223000329 |
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