On-Surface Synthesis of Highly Oriented Thin Metal–Organic Framework Films through Vapor-Assisted Conversion
Controlled on-surface film growth of porous and crystalline frameworks is a central prerequisite for incorporating these materials into functional platforms and operational devices. Here, we present the synthesis of thin zirconium-based metal–organic framework (MOF) films by vapor-assisted conversio...
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| Published in | Journal of the American Chemical Society Vol. 140; no. 14; pp. 4812 - 4819 |
|---|---|
| Main Authors | , , , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
United States
American Chemical Society
11.04.2018
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| Subjects | |
| Online Access | Get full text |
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| Abstract | Controlled on-surface film growth of porous and crystalline frameworks is a central prerequisite for incorporating these materials into functional platforms and operational devices. Here, we present the synthesis of thin zirconium-based metal–organic framework (MOF) films by vapor-assisted conversion (VAC). We established protocols adequate for the growth of UiO-66, UiO-66(NH2), UiO-67, and UiO-68(NH2) as well as the porous interpenetrated Zr–organic framework, PPPP–PIZOF-1, as highly oriented thin films. Through the VAC approach, precursors in a cast solution layer on a bare gold surface are reacting to form a porous continuous MOF film, oriented along the [111] crystal axis, by exposure to a solvent vapor at elevated temperature of 100 °C and 3 h reaction time. It was found that the concentration of dicarboxylic acid, the modulator, the droplet volume, and the reaction time are vital parameters to be controlled for obtaining oriented MOF films. Using VAC for the MOF film growth on gold surfaces modified with thiol SAMs and on a bare silicon surface yielded oriented MOF films, rendering the VAC process robust toward chemical surface variations. Ethanol sorption experiments show that a substantial part of the material pores is accessible. Thereby, the practical VAC method is an important addition to the toolbox of synthesis methods for thin MOF films. We expect that the VAC approach will open new horizons in the formation of highly defined functional thin MOF films for numerous applications. |
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| AbstractList | Controlled on-surface film growth of porous and crystalline frameworks is a central prerequisite for incorporating these materials into functional platforms and operational devices. Here, we present the synthesis of thin zirconium-based metal–organic framework (MOF) films by vapor-assisted conversion (VAC). We established protocols adequate for the growth of UiO-66, UiO-66(NH₂), UiO-67, and UiO-68(NH₂) as well as the porous interpenetrated Zr–organic framework, PPPP–PIZOF-1, as highly oriented thin films. Through the VAC approach, precursors in a cast solution layer on a bare gold surface are reacting to form a porous continuous MOF film, oriented along the [111] crystal axis, by exposure to a solvent vapor at elevated temperature of 100 °C and 3 h reaction time. It was found that the concentration of dicarboxylic acid, the modulator, the droplet volume, and the reaction time are vital parameters to be controlled for obtaining oriented MOF films. Using VAC for the MOF film growth on gold surfaces modified with thiol SAMs and on a bare silicon surface yielded oriented MOF films, rendering the VAC process robust toward chemical surface variations. Ethanol sorption experiments show that a substantial part of the material pores is accessible. Thereby, the practical VAC method is an important addition to the toolbox of synthesis methods for thin MOF films. We expect that the VAC approach will open new horizons in the formation of highly defined functional thin MOF films for numerous applications. Controlled on-surface film growth of porous and crystalline frameworks is a central prerequisite for incorporating these materials into functional platforms and operational devices. Here, we present the synthesis of thin zirconium-based metal-organic framework (MOF) films by vapor-assisted conversion (VAC). We established protocols adequate for the growth of UiO-66, UiO-66(NH ), UiO-67, and UiO-68(NH ) as well as the porous interpenetrated Zr-organic framework, PPPP-PIZOF-1, as highly oriented thin films. Through the VAC approach, precursors in a cast solution layer on a bare gold surface are reacting to form a porous continuous MOF film, oriented along the [111] crystal axis, by exposure to a solvent vapor at elevated temperature of 100 °C and 3 h reaction time. It was found that the concentration of dicarboxylic acid, the modulator, the droplet volume, and the reaction time are vital parameters to be controlled for obtaining oriented MOF films. Using VAC for the MOF film growth on gold surfaces modified with thiol SAMs and on a bare silicon surface yielded oriented MOF films, rendering the VAC process robust toward chemical surface variations. Ethanol sorption experiments show that a substantial part of the material pores is accessible. Thereby, the practical VAC method is an important addition to the toolbox of synthesis methods for thin MOF films. We expect that the VAC approach will open new horizons in the formation of highly defined functional thin MOF films for numerous applications. Controlled on-surface film growth of porous and crystalline frameworks is a central prerequisite for incorporating these materials into functional platforms and operational devices. Here, we present the synthesis of thin zirconium-based metal–organic framework (MOF) films by vapor-assisted conversion (VAC). We established protocols adequate for the growth of UiO-66, UiO-66(NH2), UiO-67, and UiO-68(NH2) as well as the porous interpenetrated Zr–organic framework, PPPP–PIZOF-1, as highly oriented thin films. Through the VAC approach, precursors in a cast solution layer on a bare gold surface are reacting to form a porous continuous MOF film, oriented along the [111] crystal axis, by exposure to a solvent vapor at elevated temperature of 100 °C and 3 h reaction time. It was found that the concentration of dicarboxylic acid, the modulator, the droplet volume, and the reaction time are vital parameters to be controlled for obtaining oriented MOF films. Using VAC for the MOF film growth on gold surfaces modified with thiol SAMs and on a bare silicon surface yielded oriented MOF films, rendering the VAC process robust toward chemical surface variations. Ethanol sorption experiments show that a substantial part of the material pores is accessible. Thereby, the practical VAC method is an important addition to the toolbox of synthesis methods for thin MOF films. We expect that the VAC approach will open new horizons in the formation of highly defined functional thin MOF films for numerous applications. Controlled on-surface film growth of porous and crystalline frameworks is a central prerequisite for incorporating these materials into functional platforms and operational devices. Here, we present the synthesis of thin zirconium-based metal-organic framework (MOF) films by vapor-assisted conversion (VAC). We established protocols adequate for the growth of UiO-66, UiO-66(NH2), UiO-67, and UiO-68(NH2) as well as the porous interpenetrated Zr-organic framework, PPPP-PIZOF-1, as highly oriented thin films. Through the VAC approach, precursors in a cast solution layer on a bare gold surface are reacting to form a porous continuous MOF film, oriented along the [111] crystal axis, by exposure to a solvent vapor at elevated temperature of 100 °C and 3 h reaction time. It was found that the concentration of dicarboxylic acid, the modulator, the droplet volume, and the reaction time are vital parameters to be controlled for obtaining oriented MOF films. Using VAC for the MOF film growth on gold surfaces modified with thiol SAMs and on a bare silicon surface yielded oriented MOF films, rendering the VAC process robust toward chemical surface variations. Ethanol sorption experiments show that a substantial part of the material pores is accessible. Thereby, the practical VAC method is an important addition to the toolbox of synthesis methods for thin MOF films. We expect that the VAC approach will open new horizons in the formation of highly defined functional thin MOF films for numerous applications.Controlled on-surface film growth of porous and crystalline frameworks is a central prerequisite for incorporating these materials into functional platforms and operational devices. Here, we present the synthesis of thin zirconium-based metal-organic framework (MOF) films by vapor-assisted conversion (VAC). We established protocols adequate for the growth of UiO-66, UiO-66(NH2), UiO-67, and UiO-68(NH2) as well as the porous interpenetrated Zr-organic framework, PPPP-PIZOF-1, as highly oriented thin films. Through the VAC approach, precursors in a cast solution layer on a bare gold surface are reacting to form a porous continuous MOF film, oriented along the [111] crystal axis, by exposure to a solvent vapor at elevated temperature of 100 °C and 3 h reaction time. It was found that the concentration of dicarboxylic acid, the modulator, the droplet volume, and the reaction time are vital parameters to be controlled for obtaining oriented MOF films. Using VAC for the MOF film growth on gold surfaces modified with thiol SAMs and on a bare silicon surface yielded oriented MOF films, rendering the VAC process robust toward chemical surface variations. Ethanol sorption experiments show that a substantial part of the material pores is accessible. Thereby, the practical VAC method is an important addition to the toolbox of synthesis methods for thin MOF films. We expect that the VAC approach will open new horizons in the formation of highly defined functional thin MOF films for numerous applications. |
| Author | Virmani, Erika Godt, Adelheid Rotter, Julian M Mähringer, Andre Wuttke, Stefan Medina, Dana D von Zons, Tobias Bein, Thomas |
| AuthorAffiliation | Faculty of Chemistry and Center for Molecular Materials (CM University of Munich (LMU) ) Bielefeld University Department of Chemistry and Center for NanoScience (CeNS) |
| AuthorAffiliation_xml | – name: ) – name: Bielefeld University – name: Department of Chemistry and Center for NanoScience (CeNS) – name: Faculty of Chemistry and Center for Molecular Materials (CM – name: University of Munich (LMU) |
| Author_xml | – sequence: 1 givenname: Erika surname: Virmani fullname: Virmani, Erika organization: University of Munich (LMU) – sequence: 2 givenname: Julian M surname: Rotter fullname: Rotter, Julian M organization: University of Munich (LMU) – sequence: 3 givenname: Andre surname: Mähringer fullname: Mähringer, Andre organization: University of Munich (LMU) – sequence: 4 givenname: Tobias surname: von Zons fullname: von Zons, Tobias organization: Bielefeld University – sequence: 5 givenname: Adelheid orcidid: 0000-0001-8453-1439 surname: Godt fullname: Godt, Adelheid organization: Bielefeld University – sequence: 6 givenname: Thomas orcidid: 0000-0001-7248-5906 surname: Bein fullname: Bein, Thomas organization: University of Munich (LMU) – sequence: 7 givenname: Stefan orcidid: 0000-0002-6344-5782 surname: Wuttke fullname: Wuttke, Stefan email: stefan.wuttke@cup.uni-muenchen.de organization: University of Munich (LMU) – sequence: 8 givenname: Dana D orcidid: 0000-0003-4759-8612 surname: Medina fullname: Medina, Dana D email: dana.medina@cup.uni-muenchen.de organization: University of Munich (LMU) |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/29542320$$D View this record in MEDLINE/PubMed |
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| Snippet | Controlled on-surface film growth of porous and crystalline frameworks is a central prerequisite for incorporating these materials into functional platforms... |
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| SubjectTerms | coordination polymers dicarboxylic acids droplets ethanol gold silicon solvents sorption temperature thiols vapors |
| Title | On-Surface Synthesis of Highly Oriented Thin Metal–Organic Framework Films through Vapor-Assisted Conversion |
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