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Gram-scale synthesis of MIL-125 nanoparticles and their solution processability
Although metal–organic framework (MOF) photocatalysts have become ubiquitous, basic aspects of their photoredox mechanisms remain elusive. Nanosizing MOFs enables solution-state techniques to probe size-dependent properties and molecular reactivity, but few MOFs have been prepared as nanoparticles (...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10445466/ https://www.ncbi.nlm.nih.gov/pubmed/37621428 http://dx.doi.org/10.1039/d3sc02257a |
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author | Fabrizio, Kevin Gormley, Eoghan L. Davenport, Audrey M. Hendon, Christopher H. Brozek, Carl K. |
author_facet | Fabrizio, Kevin Gormley, Eoghan L. Davenport, Audrey M. Hendon, Christopher H. Brozek, Carl K. |
author_sort | Fabrizio, Kevin |
collection | PubMed |
description | Although metal–organic framework (MOF) photocatalysts have become ubiquitous, basic aspects of their photoredox mechanisms remain elusive. Nanosizing MOFs enables solution-state techniques to probe size-dependent properties and molecular reactivity, but few MOFs have been prepared as nanoparticles (nanoMOFs) with sufficiently small sizes. Here, we report a rapid reflux-based synthesis of the photoredox-active MOF Ti(8)O(8)(OH)(4)(terephthalate)(6) (MIL-125) to achieve diameters below 30 nm in less than 2 hours. Whereas MOFs generally require ex situ analysis by solid-state techniques, sub-30 nm diameters ensure colloidal stability for weeks and minimal light scattering, permitting in situ analysis by solution-state methods. Optical absorption and photoluminescence spectra of free-standing colloids provide direct evidence that the photoredox chemistry of MIL-125 involves Ti(3+) trapping and charge accumulation onto the Ti-oxo clusters. Solution-state potentiometry collected during the photochemical process also allows simultaneous measurement of MOF Fermi-level energies in situ. Finally, by leveraging the solution-processability of these nanoparticles, we demonstrate facile preparation of mixed-matrix membranes with high MOF loadings that retain the reversible photochromism. Taken together, these results demonstrate the feasibility of a rapid nanoMOF synthesis and fabrication of a photoactive membrane, and the fundamental insights they offer into heterogeneous photoredox chemistry. |
format | Online Article Text |
id | pubmed-10445466 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-104454662023-08-24 Gram-scale synthesis of MIL-125 nanoparticles and their solution processability Fabrizio, Kevin Gormley, Eoghan L. Davenport, Audrey M. Hendon, Christopher H. Brozek, Carl K. Chem Sci Chemistry Although metal–organic framework (MOF) photocatalysts have become ubiquitous, basic aspects of their photoredox mechanisms remain elusive. Nanosizing MOFs enables solution-state techniques to probe size-dependent properties and molecular reactivity, but few MOFs have been prepared as nanoparticles (nanoMOFs) with sufficiently small sizes. Here, we report a rapid reflux-based synthesis of the photoredox-active MOF Ti(8)O(8)(OH)(4)(terephthalate)(6) (MIL-125) to achieve diameters below 30 nm in less than 2 hours. Whereas MOFs generally require ex situ analysis by solid-state techniques, sub-30 nm diameters ensure colloidal stability for weeks and minimal light scattering, permitting in situ analysis by solution-state methods. Optical absorption and photoluminescence spectra of free-standing colloids provide direct evidence that the photoredox chemistry of MIL-125 involves Ti(3+) trapping and charge accumulation onto the Ti-oxo clusters. Solution-state potentiometry collected during the photochemical process also allows simultaneous measurement of MOF Fermi-level energies in situ. Finally, by leveraging the solution-processability of these nanoparticles, we demonstrate facile preparation of mixed-matrix membranes with high MOF loadings that retain the reversible photochromism. Taken together, these results demonstrate the feasibility of a rapid nanoMOF synthesis and fabrication of a photoactive membrane, and the fundamental insights they offer into heterogeneous photoredox chemistry. The Royal Society of Chemistry 2023-08-07 /pmc/articles/PMC10445466/ /pubmed/37621428 http://dx.doi.org/10.1039/d3sc02257a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Fabrizio, Kevin Gormley, Eoghan L. Davenport, Audrey M. Hendon, Christopher H. Brozek, Carl K. Gram-scale synthesis of MIL-125 nanoparticles and their solution processability |
title | Gram-scale synthesis of MIL-125 nanoparticles and their solution processability |
title_full | Gram-scale synthesis of MIL-125 nanoparticles and their solution processability |
title_fullStr | Gram-scale synthesis of MIL-125 nanoparticles and their solution processability |
title_full_unstemmed | Gram-scale synthesis of MIL-125 nanoparticles and their solution processability |
title_short | Gram-scale synthesis of MIL-125 nanoparticles and their solution processability |
title_sort | gram-scale synthesis of mil-125 nanoparticles and their solution processability |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10445466/ https://www.ncbi.nlm.nih.gov/pubmed/37621428 http://dx.doi.org/10.1039/d3sc02257a |
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