Single layer growth of sub-micron metal–organic framework crystals observed by in situ atomic force microscopy

John, Neena S.; Scherb, Camilla; Shöâeè, Maryiam; Anderson, Michael W.; Attfield, Martin P.; Bein, Thomas

doi:10.1039/b908299a

Cited by 58 publications

(61 citation statements)

References 22 publications

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“…Careful cross-sectional analysis of single images of developing growth steps with 1.5 nm height suggests that the actual growth mechanism does not exclusively involve pre-formed paddle-wheel SBUs but is more likely to involve the simpler units such as individually solvated Cu 2+ and BTC 3-ions (BTC = benzene-1,3,5-tricarboxylate) ( Figure 3). It was established that the formation of the 1.5 nm high extended growth step occurs by a layer-by-layer mechanism [79]. According to this mechanism, each layer grows by initial attachment of BTC and copper species onto a stably terminated crystal surface A (Figure 3) to form a small volume of a d´2 22 step with metastable termination B.…”

Section: Crystal Surface Structurementioning

confidence: 99%

Multi-scale crystal engineering of metal organic frameworks

Seoane

Castellanos

Dikhtiarenko

et al. 2016

Coordination Chemistry Reviews

258

163

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Section: Crystal Surface Structurementioning

confidence: 99%

Multi-scale crystal engineering of metal organic frameworks

Seoane

Castellanos

Dikhtiarenko

et al. 2016

Coordination Chemistry Reviews

258

163

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“…[11][12][13][14] In situ AFM studies of differing resolution have been reported for a number of MOFs, [15][16][17][18][19] revealing valuable information concerning their crystal growth and the growth of nanoporous materials.…”

Section: Introductionmentioning

confidence: 99%

Crystal growth of MOF-5 using secondary building units studied by in situ atomic force microscopy

et al. 2014

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(2014) 'Crystal growth of MOF-5 using secondary building units studied by in situ atomic force microscopy. ', CrystEngComm., 16 (42). pp. 9834-9841. Further information on publisher's website:https://doi.org/10.1039/C4CE01710BPublisher's copyright statement:Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Crystal growth of the metal-organic framework, MOF-5, using basic zinc benzoate, [Zn 4 O(O 2 CC 6 H 5 ) 6 ], was studied in real time using atomic force microscopy. The twodimensional nuclei involved in layer growth were found to form by a two-step process whereby 1,4-benzenedicarboxylate units first attach to the MOF-5 surface followed by addition of a layer of Zn species and connecting 1,4-benzenedicarboxylate units. 6 ]-containing growth solutions were found to influence the relative growth rates along different crystallographic directions and to lead to a faster nucleation rate under certain conditions when compared to growth solutions containing simpler zinc salts. This suggests a degree of remnant association of the zinc species derived from the [Zn 4 O(O 2 CC 6 H 5 ) 6 ] cluster during crystal growth under these conditions. IntroductionPorous metal-organic frameworks (MOFs) are formed from the connection of metal ions and organic linkers to provide an enormous number of different structures of varying pore dimension, geometry and functionality that are finding potential use in a diverse array of new and traditional applications. [1][2][3][4] Considerable effort has been expended to optimise the synthesis of these materials with regards to numerous factors including: yield, crystal size, morphological control, the rate of product formation and the synthesis temperature. One such approach to the synthesis of MOFs is the so called "controlled secondary building unit (SBU) approach" (CSA) introduced by Serre et al. 5 The rationale behind the development of this approach was that MOF syntheses could be speeded up if the metal components added to the reaction solution were already preassembled to resemble the SBUs of the final crystalline MOF. This method has succeeded in decreasing reaction times and temperatures for several MOFs,[5][6][7] in addition to proving to be very useful in the synthesis of nanoparticles, 8 thin films, 9 and producing MOF homologues with new metal content. 6One of the questions arising from the CSA methodology is whether the SBU remains intact during synthesis. If it does then this would suggest that formation of the MOF can occur via a simple ligand substitution ...

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“…The periodicity along the [100] direction (the growth direction perpendicular to the surface) of HKUST-1 is measured at 2.634 nm; each deposition cycle (one layer) with a thickness of half this value, 1.317 nm, corresponds to a half of the calculated periodicity along the [100] direction and thus verifies the half unit-cell growth. In situ AFM studies on HUKST-1 growth from solvothermal reaction also suggest an LBL mechanism [49]. It is noteworthy that the linear growth mode is established after 20 cycles.…”

Section: Thickness Roughness and Homogeneitymentioning

confidence: 96%

“…A wide range of technologies have been involved in this study such as extended X-ray absorption fine structure (EXAFS) spectroscopy, electrospray ionization mass spectroscopic (ESI-MS) [50], time-resolved in situ XRD study, atomic force microscopy (AFM) [51,52] and in situ time-resolved light scattering (TLS) [53]. Possibly, the most direct evidence for important growth species comes from in situ AFM studies [48,49] in which the LBL-based growth processes of oriented HKUST-1 crystals on SAM-modified gold substrates were investigated. These studies indicated a layer-by-layer mechanism of a constituent 1.5 nm d 111 crystal-spacing step of HKUST-1 and the influence of the step vertex on the rate of growth.…”

Section: Growth Mechanismsmentioning

confidence: 99%

Liquid-phase epitaxy of metal organic framework thin films

Liu

Fischer

2011

Sci. China Chem.

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Metal-organic framework (MOF) thin films are multilayer materials ranging from nanometers to micrometers in thickness, physically or chemically adhesive to a (functionalized) substrate and, in an ideal case, exhibiting low roughness and high homogeneity. Various innovative approaches have been developed for MOF thin film fabrication. Among these advanced materials, surface-attached metal-organic frameworks (SURMOFs) are an important class of MOF films. SURMOFs, fabricated in a step-by-step liquid phase epitaxial (LPE) fashion by alternating deposition of metal and organic linker precursors on a functionalized substrate, for example, thiolate-based self-assembled monolayers (SAMs), have already exhibited their utility in both research and potential applications. SURMOFs combine surface science and the chemistry of MOFs, possessing the following unique advantages that cannot be accessed through other methods: (i) precisely controlling thickness, roughness and homogeneity as well as growth orientation, (ii) studying of MOF growth mechanism, (iii) modifying/tailoring MOFs' structures during the SURMOF growth and thus creating customizable properties, and (iv) existing in the form of thin film/membrane for direct applications, for example, as sensors. This review discusses the oriented and crystalline SURMOFs fabricated by LPE approach, covering their preparation, growth mechanism, and characterization methodology as well as applications based upon the most newly updated knowledge. coordination chemistry, metal-organic frameworks (MOFs), liquid phase epitaxy, step-by-step approach, surface science, thin film

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Single layer growth of sub-micron metal–organic framework crystals observed by in situ atomic force microscopy

Abstract: In situ atomic force microscopy was used to directly investigate the growth processes of the oriented metal-organic framework HKUST-1 grown on self-assembled monolayers on gold.

Cited by 58 publications

References 22 publications

Multi-scale crystal engineering of metal organic frameworks

Multi-scale crystal engineering of metal organic frameworks

Crystal growth of MOF-5 using secondary building units studied by in situ atomic force microscopy

Liquid-phase epitaxy of metal organic framework thin films

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