Solvent-free vacuum growth of oriented HKUST-1 thin films

Han, Sungmin; Ciufo, Ryan A.; Meyerson, Melissa L.; Keitz, Benjamin K.; Mullins, C. Buddie

doi:10.1039/c9ta05179a

Cited by 65 publications

(71 citation statements)

References 115 publications

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“…18 Unlike in the solvothermal conversion of metal oxide layers to MOFs, 19 metal ions cannot be removed from the surface during MOF-CVD, leading to pinhole-free and conformal films. Vapor-phase growth of MOFs is a rapidly expanding area, 20 as illustrated by reports on the deposition of ZIF-67, 21 CuBDC, 22 CuCDC, 22 HKUST-1, 23 and a Zn-carboxylate-pyrazolate MOF-5 isotype structure. 24 Furthermore, related approaches have been developed such as CVD of amorphous precursors followed by postdeposition crystallization to form MOF-5, 25 IRMOF-8, 26 UiO-66 27 and UiO-66-NH2 28 , and the deposition of crystalline coordination compounds (e.g., CaBDC 29 , different CuBDC polymorphs 22,30 ).…”

Section: Introductionmentioning

confidence: 99%

Solvent-Free Powder Synthesis and MOF-CVD Thin Films of the Mesoporous Metal-Organic Framework MAF-6

Stassin¹,

Stassen²,

Marreiros³

et al. 2019

Preprint

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A simple solvent- and catalyst-free method is presented for the synthesis of the mesoporous metal-organic framework (MOF) MAF-6 (RHO-Zn(eIm)2) based on the reaction of ZnO with 2-ethylimidazole vapor at temperatures ≤ 100 °C. By translating this method to a chemical vapor deposition (CVD) protocol, mesoporous crystalline films could be deposited for the first time entirely from the vapor phase. A combination of PALS and Kr physisorption measurements confirmed the porosity of these MOF-CVD films and the size of the MAF-6 supercages (diam. ~2 nm), in close agreement with powder data and calculations. MAF-6 powders and films were further characterized by XRD, TGA, SEM, FTIR, PDF and EXAFS. The exceptional uptake capacity of the mesoporous MAF-6 in comparison to the microporous ZIF-8 is demonstrated by vapor-phase loading of a molecule larger than the ZIF-8 windows.

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Section: Introductionmentioning

confidence: 99%

Solvent-Free Powder Synthesis and MOF-CVD Thin Films of the Mesoporous Metal-Organic Framework MAF-6

Stassin¹,

Stassen²,

Marreiros³

et al. 2019

Preprint

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“…[42][43][44][45][46] In this case, a precursor/seeds layer is firstly coated on the support, followed by steam/vapor-assisted conversion to form a continuous membrane layer. [42][43][44] Herein, as schematically shown in Figure S1 (Supporting Information), the a-Al 2 O 3 support is firstly coated with an oriented and thin ZIF-95 seeds layer by vacuum filtration of a suspension of ZIF-95 nanosheets. Then, in-plane epitaxial growth is done in mixed DMF/water vapor atmosphere to form an oriented and thin ZIF-95 membrane.…”

mentioning

confidence: 99%

Anisotropic Gas Separation in Oriented ZIF‐95 Membranes Prepared by Vapor‐Assisted In‐Plane Epitaxial Growth

Zheng

et al. 2020

Angew Chem Int Ed

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Control of the microstructure grain orientation, grain boundaries and thickness are crucial for MOF membranes. We report a novel synthesis strategy to prepare highly c‐oriented ZIF‐95 membranes through vapor‐assisted in‐plane epitaxial growth. In a mixed DMF/water vapor atmosphere, in‐plane epitaxial growth of a ZIF‐95 seeds layer was achieved to obtain an oriented and well‐intergrown ZIF‐95 membrane with a thickness of only 600 nm. Demonstrated by both experimental and simulation studies, the c‐oriented ZIF‐95 membrane displayed superior separation performance because a perfectly oriented structure resulted in a notable reduction of intercrystalline defects and transport pathways. For the separation of equimolar binary mixtures at 100 °C and 1 bar, the mixture separation factors of H2/CO2 and H2/CH4 were 32.2 and 53.7, respectively, with an H2 permeance of over 7.9×10−7 mol m−2 s−1 Pa−1, which was 4.6 times higher than that of a randomly oriented ZIF‐95 membrane.

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“…[20] Adopting a LBL deposition technique, this PVD and CVD combined method was first developed for HKUST-1 thin films in our recent work as a bottom-up approach by sequential deposition cycles of metal atoms and ligand molecules. [20] As schematically described in Figure 6a, H 3 BTC (Benzene-1,3,5-tricarboxylic acid) molecules are known to form hydrogen bonded (H-bonded) 2D networks (typically one layer thickness) on a Cu (100) surface and also on various metal surfaces, such as Ag and Au. [51][52][53] Moreover, it was found that low coverages (~0.06 ML) of Fe on a Cu(100) surface can be coordinated with adsorbed H 3 BTC molecules forming 2D metalorganic network.…”

Section: Pvd and Cvd Combined Gas-phase Mof Thin Film Growthmentioning

confidence: 99%

“…We have recently made additional progress regarding bottom-up gas-phase MOF growth strategies adopting physical vapor deposition (PVD) of Cu and CVD of H 3 BTC in order to grow a HKUST-1 thin film under vacuum. [20] Developing gas-phase MOF thin film growth methods is important since such procedures can broaden the use of MOFs for various electronic and chemical applications. Thus, in this paper, we primarily investigate the current progress of gas-phase MOF thin film growth methods and also discuss future directions.…”

Section: Introductionmentioning

confidence: 99%

Current Progress and Future Directions in Gas‐Phase Metal‐Organic Framework Thin‐Film Growth

Han

Mullins

2020

ChemSusChem

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Deposition of materials as a thin film is important for various applications, such as sensors, microelectronic devices, and membranes. There have been breakthroughs in gas-phase metal-organic framework (MOF) thin-film growth, which is more applicable to micro-and nanofabrication processes and also less harmful to the environment than solvent-based methods. Three different types of gas-phase MOF thin film deposition methods have been developed using chemical vapor deposition (CVD), atomic layer deposition (ALD), and physical vapor deposition (PVD)-CVD combined techniques. The CVD-based method basically converts metal oxide layers into MOF thin films by exposing the surface to ligand vapor. The ALD-based method allows growing MOF thin films following layer-by-layer (LBL) growth by sequentially exposing gas-phase metal and ligand precursors. The PVD-CVD method uses PVD for metal deposition and CVD for ligand deposition, which is similar to LBL growth. These gas-phase growth methods can broaden the use of MOFs in diverse areas. Herein, the current progress of gas-phase MOF thin film growth is discussed and future directions suggested.

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Solvent-free vacuum growth of oriented HKUST-1 thin films

Abstract: H3BTC and Cu are sequentially deposited to form highly oriented HKUST-1 thin films under vacuum without the use of solvents.

Cited by 65 publications

References 115 publications

Solvent-Free Powder Synthesis and MOF-CVD Thin Films of the Mesoporous Metal-Organic Framework MAF-6

Solvent-Free Powder Synthesis and MOF-CVD Thin Films of the Mesoporous Metal-Organic Framework MAF-6

Anisotropic Gas Separation in Oriented ZIF‐95 Membranes Prepared by Vapor‐Assisted In‐Plane Epitaxial Growth

Current Progress and Future Directions in Gas‐Phase Metal‐Organic Framework Thin‐Film Growth

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