Metal-organic framework thin films: from fundamentals to applications.

Metal organic frameworks (MOFs) offer the highest surface areas per gram of any known material. As such, they epitomise resource productivity in uses where specific surface area is critical, such as adsorption, storage, filtration and catalysis. However, the ability to control the position of MOFs is also crucial for their use in devices for applications such as sensing, delivery, sequestration, molecular transport, electronics, energy production, optics, bioreactors and catalysis. In this review we present the current technologies that enable the precise positioning of MOFs onto different platforms. Methods for permanent localisation, dynamic localisation, and spatial control of functional materials within MOF crystals are described. Finally, examples of devices in which the control of MOF position and functionalisation will play a major technological role are presented.

/pdf/mof-positioning-technology-and-device-fabrication-4u1gfhfdpr.pdf

MOF positioning technology and device fabrication

Electroreduction of oxoanions affords hydroxide equivalents that induce selective deposition of crystalline metal-organic frameworks (MOFs) on conductive surfaces. The method is illustrated by cathodic electrodeposition of Zn(4)O(BDC)(3) (MOF-5; BDC = 1,4-benzenedicarboxylate), which is deposited at room temperature in only 15 min under cathodic potential. Although many crystalline phases are known in the Zn(2+)/BDC(2-) system, MOF-5 is the only observed crystalline MOF phase under these conditions. This fast and mild method of synthesizing MOFs is amenable to direct surface functionalization and could impact applications requiring conformal coatings of microporous MOFs, such as gas separation membranes and electrochemical sensors.

/pdf/reductive-electrosynthesis-of-crystalline-metal-organic-1fs2nrl1cd.pdf

Reductive electrosynthesis of crystalline metal-organic frameworks

Formation of oriented and patterned films of metal–organic frameworks by liquid phase epitaxy: A review

A highly luminescent LnMOF {[Eu2(bqdc)3(H2O)(DMF)3]·0.5DMF·H2O}n (1, bqdc = 2,2′-biquinoline-4,4′-dicarboxylate) was designed and synthesized. It was characterized by single crystal X-ray diffraction, PXRD, TGA, EA and FT-IR. A new strategy for preparing mechanically robust MOF thin films was developed by electrodeposition in combination with subsequent solvothermal synthesis. A portable sensor device prototype consisting of a film of 1 was conveniently fabricated by using this new strategy and this sensor device exhibits a highly selective response to Hg2+. Its luminescence quenching can be distinguished clearly with the naked eye when illuminated by a handy UV banknote detector. The diffusion kinetics of Hg2+ into the LnMOF film is first proposed.

A novel highly luminescent LnMOF film: a convenient sensor for Hg2+ detecting

The controlled growth of metal-organic frameworks (MOFs) over surfaces has been investigated using a variety of surface analytical techniques. The use of microcontact printing to prepare surfaces, patterned with regions capable of nucleating the growth of MOFs, has been explored by employing copper-catalyzed alkyne-azide cycloaddition (CuAAC) to pattern silicon wafers with carboxylic acids, a functional group that has been shown to nucleate the growth of MOFs on surfaces. Upon subjecting the patterned silicon surfaces to solvothermal conditions, MOF thin films were obtained and characterized subsequently by AFM, SEM, and grazing-incidence XRD (GIXRD). Large crystals (∼0.5 mm) have also been nucleated, as indicated by the presence of a bas-relief of the original pattern on one surface of the crystal, suggesting that it is possible to transfer the template surface pattern onto a single crystal of a MOF.

Microcontact click printing for templating ultrathin films of metal - Organic frameworks

The self-assembly of CdSe quantum dots (QDs) onto a patterned silica surface generated from surface microcontact click printing is presented. The mechanically robust self-assembly process produces patterns of QDs which remain steadfast, even as subsequent reactions are performed on the substrate, demonstrating the utility and ease of this self-assembly process.

Petra M. Erne

Papers

Microcontact click printing for templating ultrathin films of metal - Organic frameworks

Patterned assembly of quantum dots onto surfaces modified with click microcontact printing.