In situ growing of ZIF-8 crystals into TiO2 micro columnar films
This study proposes a fast and simple method for the in situ growth of metal-organic frameworks (MOFs) on metal oxide substrates as an alternative to the traditional approaches of using gold substrates and self-assembled monolayers (SAMs). As a case study, zeolitic imidazolate framework 8 (ZIF-8) cr...
Saved in:
| Main Authors: | , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Elsevier
2025-01-01
|
| Series: | Next Materials |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S2949822824003034 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1849773197911654400 |
|---|---|
| author | Juan J. Romero-Guerrero Francisco G. Moscoso Said Hamad Gloria P. Moreno Víctor Rico Ángel Barranco Quero Tânia Lopes-Costa José M. Pedrosa |
| author_facet | Juan J. Romero-Guerrero Francisco G. Moscoso Said Hamad Gloria P. Moreno Víctor Rico Ángel Barranco Quero Tânia Lopes-Costa José M. Pedrosa |
| author_sort | Juan J. Romero-Guerrero |
| collection | DOAJ |
| description | This study proposes a fast and simple method for the in situ growth of metal-organic frameworks (MOFs) on metal oxide substrates as an alternative to the traditional approaches of using gold substrates and self-assembled monolayers (SAMs). As a case study, zeolitic imidazolate framework 8 (ZIF-8) crystals were grown in micro columnar TiO2 films through simple alternate and successive immersions of the TiO2 films into solutions containing the MOFs precursors. The growth process of the MOF crystals in the interstitial spaces between the TiO2 columns was investigated by varying the metal-to-ligand ratio (1:2, 1:4, and 1:8) and by employing modulating agents such as triethylamine. It was found that the optimal deposition of ZIF-8 occurred when using a higher excess of ligand and the addition of triethylamine after a controlled number of immersion cycles. These results were obtained by using glancing angle X-ray diffraction (GAXRD) and scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS) as characterization techniques. Additionally, a density functional theory (DFT) study as well as Fourier-transform infrared spectroscopy (FTIR) and GAXRD experiments were conducted to elucidate the nucleation process. It was concluded that the starting point is the formation of a covalent bond between the Zn cations and the TiO2 on the metal oxide surface after immersion of the film into a Zinc (II) nitrate solution, allowing for the formation of MOF nuclei once the film is subsequently immersed in the 2-methylimidazole solution. The results demonstrate the feasibility of in situ growth of MOF crystals onto metal oxide structures by a layer-by-layer strategy, offering a promising alternative to conventional methods. |
| format | Article |
| id | doaj-art-375cd2f508264917bf253d799b5834c7 |
| institution | DOAJ |
| issn | 2949-8228 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Next Materials |
| spelling | doaj-art-375cd2f508264917bf253d799b5834c72025-08-20T03:02:07ZengElsevierNext Materials2949-82282025-01-01610040610.1016/j.nxmate.2024.100406In situ growing of ZIF-8 crystals into TiO2 micro columnar filmsJuan J. Romero-Guerrero0Francisco G. Moscoso1Said Hamad2Gloria P. Moreno3Víctor Rico4Ángel Barranco Quero5Tânia Lopes-Costa6José M. Pedrosa7Center for Nanoscience and Sustainable Technologies (CNATS), Departamento de Sistemas Físicos, Químicos y Naturales, Universidad Pablo de Olavide, Ctra. Utrera km. 1, Seville 41013, SpainCenter for Nanoscience and Sustainable Technologies (CNATS), Departamento de Sistemas Físicos, Químicos y Naturales, Universidad Pablo de Olavide, Ctra. Utrera km. 1, Seville 41013, Spain; Corresponding authors.Center for Nanoscience and Sustainable Technologies (CNATS), Departamento de Sistemas Físicos, Químicos y Naturales, Universidad Pablo de Olavide, Ctra. Utrera km. 1, Seville 41013, SpainNanotechnology on Surfaces and Plasma Laboratory. Instituto de Ciencias de Materiales de Sevilla (ICMSE-CSIC), Americo Vespucio 49, Sevilla 41092, SpainNanotechnology on Surfaces and Plasma Laboratory. Instituto de Ciencias de Materiales de Sevilla (ICMSE-CSIC), Americo Vespucio 49, Sevilla 41092, SpainNanotechnology on Surfaces and Plasma Laboratory. Instituto de Ciencias de Materiales de Sevilla (ICMSE-CSIC), Americo Vespucio 49, Sevilla 41092, SpainCenter for Nanoscience and Sustainable Technologies (CNATS), Departamento de Sistemas Físicos, Químicos y Naturales, Universidad Pablo de Olavide, Ctra. Utrera km. 1, Seville 41013, SpainCenter for Nanoscience and Sustainable Technologies (CNATS), Departamento de Sistemas Físicos, Químicos y Naturales, Universidad Pablo de Olavide, Ctra. Utrera km. 1, Seville 41013, Spain; Corresponding authors.This study proposes a fast and simple method for the in situ growth of metal-organic frameworks (MOFs) on metal oxide substrates as an alternative to the traditional approaches of using gold substrates and self-assembled monolayers (SAMs). As a case study, zeolitic imidazolate framework 8 (ZIF-8) crystals were grown in micro columnar TiO2 films through simple alternate and successive immersions of the TiO2 films into solutions containing the MOFs precursors. The growth process of the MOF crystals in the interstitial spaces between the TiO2 columns was investigated by varying the metal-to-ligand ratio (1:2, 1:4, and 1:8) and by employing modulating agents such as triethylamine. It was found that the optimal deposition of ZIF-8 occurred when using a higher excess of ligand and the addition of triethylamine after a controlled number of immersion cycles. These results were obtained by using glancing angle X-ray diffraction (GAXRD) and scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS) as characterization techniques. Additionally, a density functional theory (DFT) study as well as Fourier-transform infrared spectroscopy (FTIR) and GAXRD experiments were conducted to elucidate the nucleation process. It was concluded that the starting point is the formation of a covalent bond between the Zn cations and the TiO2 on the metal oxide surface after immersion of the film into a Zinc (II) nitrate solution, allowing for the formation of MOF nuclei once the film is subsequently immersed in the 2-methylimidazole solution. The results demonstrate the feasibility of in situ growth of MOF crystals onto metal oxide structures by a layer-by-layer strategy, offering a promising alternative to conventional methods.http://www.sciencedirect.com/science/article/pii/S2949822824003034Metal-organic frameworksStructured metal oxide filmsSeed surface CrystallizationComposite films |
| spellingShingle | Juan J. Romero-Guerrero Francisco G. Moscoso Said Hamad Gloria P. Moreno Víctor Rico Ángel Barranco Quero Tânia Lopes-Costa José M. Pedrosa In situ growing of ZIF-8 crystals into TiO2 micro columnar films Next Materials Metal-organic frameworks Structured metal oxide films Seed surface Crystallization Composite films |
| title | In situ growing of ZIF-8 crystals into TiO2 micro columnar films |
| title_full | In situ growing of ZIF-8 crystals into TiO2 micro columnar films |
| title_fullStr | In situ growing of ZIF-8 crystals into TiO2 micro columnar films |
| title_full_unstemmed | In situ growing of ZIF-8 crystals into TiO2 micro columnar films |
| title_short | In situ growing of ZIF-8 crystals into TiO2 micro columnar films |
| title_sort | in situ growing of zif 8 crystals into tio2 micro columnar films |
| topic | Metal-organic frameworks Structured metal oxide films Seed surface Crystallization Composite films |
| url | http://www.sciencedirect.com/science/article/pii/S2949822824003034 |
| work_keys_str_mv | AT juanjromeroguerrero insitugrowingofzif8crystalsintotio2microcolumnarfilms AT franciscogmoscoso insitugrowingofzif8crystalsintotio2microcolumnarfilms AT saidhamad insitugrowingofzif8crystalsintotio2microcolumnarfilms AT gloriapmoreno insitugrowingofzif8crystalsintotio2microcolumnarfilms AT victorrico insitugrowingofzif8crystalsintotio2microcolumnarfilms AT angelbarrancoquero insitugrowingofzif8crystalsintotio2microcolumnarfilms AT tanialopescosta insitugrowingofzif8crystalsintotio2microcolumnarfilms AT josempedrosa insitugrowingofzif8crystalsintotio2microcolumnarfilms |