Defect‐Controlled Preparation of UiO‐66 Metal–Organic Framework Thin Films with Molecular Sieving Capability

Zhang, Caiqin; Zhao, Yajing; Li, Yali; Zhang, Xuetong; Chi, Lifeng; Lü, Guang

doi:10.1002/asia.201501079

Cited by 20 publications

(13 citation statements)

References 43 publications

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“…Control over the MOF crystallite orientation in films is crucial for expanding the scope of their applications. Previous reports emphasized the beneficial role of a modulator for obtaining highly crystalline MOF materials , and preferential crystallite orientation in films. , To this end, we focused on the synthesis of UiO-66(NH 2 ) and PPPP–PIZOF-1 films as model systems for the different structures.…”

Section: Results and Disscusionmentioning

confidence: 99%

On-Surface Synthesis of Highly Oriented Thin Metal–Organic Framework Films through Vapor-Assisted Conversion

et al. 2018

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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.

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Section: Results and Disscusionmentioning

confidence: 99%

On-Surface Synthesis of Highly Oriented Thin Metal–Organic Framework Films through Vapor-Assisted Conversion

et al. 2018

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“…Continuous growth of UiO-66 results in either a polycrystalline or an epitaxial film. As free-standing films were not mechanically robust, porous and nonporous substrates were employed to support UiO-66 membranes [28,59,[86][87][88][89][90][91][92][93][94][95][96] and films [96,[99][100][101][102][103][104][105][106][107][108][109][110][111][112], respectively. Porous metal and ceramic substrates with minimal permeation resistance in the configuration of flat sheets and tubes were adopted for supporting UiO-66 membranes.…”

Section: Approaches For Fabricating Uio-66 Membranesmentioning

confidence: 99%

“…Apart from fabrication on bare substrates, modified substrates were adopted to facilitate membrane growth, such as ZrO 2 [90] and 3-aminopropy-ltriethoxysilane (APTES) modified α-alumina tubes [89]. In addition, attempts were made to obtain UiO-66 films by in situ synthesis using bare ZrO 2 fibrous mats [101], and modified substrates including fluorine-doped tin oxide (FTO) glasses [99], polyurethane (PU) foams [100], polyacrylonitrile (PAN) fibers [102], silanized α-alumina and ob-SiC foams [103].…”

Section: In Situ Synthesismentioning

confidence: 99%

Metal-organic framework UiO-66 membranes

Liu

2019

Front. Chem. Sci. Eng.

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Metal-organic frameworks (MOFs) have emerged as a class of promising membrane materials. UiO-66 is a prototypical and stable MOF material with a number of analogues. In this article, we review five approaches for fabricating UiO-66 polycrystalline membranes including in situ synthesis, secondary synthesis, biphase synthesis, gas-phase deposition and electrochemical deposition, as well as their applications in gas separation, pervaporation, nanofiltration and ion separation. On this basis, we propose possible methods for scalable synthesis of UiO-66 membranes and their potential separation applications in the future.

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“…To evaluate the effects of the mesoporous structures in MOF films on the sensing performances, a sensor (DS) configured with a dense UiO-66 film, which was fabricated by the solvothermal growth method, 62 was used for comparison. As shown in Figure 6a, the deposited MOF film in DS possesses an intergrown surface morphology and a uniform thickness of ∼462 nm that is close to the size of building crystals in CS 468/0.26 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Metal–Organic Framework Crystal-Assembled Optical Sensors for Chemical Vapors: Effects of Crystal Sizes and Missing-Linker Defects on Sensing Performances

Zhang

Yao

et al. 2019

ACS Appl. Mater. Interfaces

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Microporous metal–organic frameworks (MOFs) are promising candidate materials for chemical sensing, but the reproducible fabrication of MOF-based sensors with optimized and stable performances remains a significant challenge. Here, we report the fabrication of MOF optical sensors with steady but tunable optical properties via assembling UiO-66 crystals with controllable sizes and missing-linker defects. The well-defined but tunable microscopic and mesoscopic structural features of MOF sensing components greatly facilitate the optimization of device performance. The UiO-66 crystal-assembled sensors display fast response (2.00 s) and short recovery (3.00 s) to ethanol vapor (one of the analytes we tested). Our systematical investigation indicates that the mesoporous features of sensing components contribute greatly to the enhanced sensitivity (by ∼24.6% to the saturated ethanol vapor), response speed (by ∼42.9%), and recovery speed (by ∼59.7%) of the crystal-assembled sensors in comparison to their dense counterpart. The building crystal sizes show a slight influence on the response speed but profound effects on the sensitivity and recovery performances of sensors. The missing-linker defects have obvious beneficial effects on the desorption kinetics of analyte and can cause a faster recovery of sensors.

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Defect‐Controlled Preparation of UiO‐66 Metal–Organic Framework Thin Films with Molecular Sieving Capability

Cited by 20 publications

References 43 publications

On-Surface Synthesis of Highly Oriented Thin Metal–Organic Framework Films through Vapor-Assisted Conversion

On-Surface Synthesis of Highly Oriented Thin Metal–Organic Framework Films through Vapor-Assisted Conversion

Metal-organic framework UiO-66 membranes

Metal–Organic Framework Crystal-Assembled Optical Sensors for Chemical Vapors: Effects of Crystal Sizes and Missing-Linker Defects on Sensing Performances

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