Metal-organic frameworks (MOFs) are typically highlighted for their potential application in gas storage, separations and catalysis. In contrast, the unique prospects these porous and crystalline materials offer for application in electronic devices, although actively developed, are often underexposed. This review highlights the research aimed at the implementation of MOFs as an integral part of solid-state microelectronics. Manufacturing these devices will critically depend on the compatibility of MOFs with existing fabrication protocols and predominant standards. Therefore, it is important to focus in parallel on a fundamental understanding of the distinguishing properties of MOFs and eliminating fabrication-related obstacles for integration. The latter implies a shift from the microcrystalline powder synthesis in chemistry labs, towards film deposition and processing in a cleanroom environment. Both the fundamental and applied aspects of this two-pronged approach are discussed. Critical directions for future research are proposed in an updated high-level roadmap to stimulate the next steps towards MOF-based microelectronics within the community.

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An updated roadmap for the integration of metal–organic frameworks with electronic devices and chemical sensors

Metal-organic frameworks (MOFs) represent the largest known class of porous crystalline materials ever synthesized Their narrow pore windows and nearly unlimited structural and chemical features have made these materials of significant interest for membrane-based gas separations In this comprehensive review, we discuss opportunities and challenges related to the formation of pure MOF films and mixed-matrix membranes (MMMs) Common and emerging separation applications are identified, and membrane transport theory for MOFs is described and contextualized relative to the governing principles that describe transport in polymers Additionally, cross-cutting research opportunities using advanced metrologies and computational techniques are reviewed To quantify membrane performance, we introduce a simple membrane performance score that has been tabulated for all of the literature data compiled in this review These data are reported on upper bound plots, revealing classes of MOF materials that consistently demonstrate promising separation performance Recommendations are provided with the intent of identifying the most promising materials and directions for the field in terms of fundamental science and eventual deployment of MOF materials for commercial membrane-based gas separations

MOF-Based Membranes for Gas Separations.

The potential commercial applications for metal organic frameworks (MOFs) are tantalizing. To address the opportunity, many novel approaches for their synthesis have been developed recently. These strategies present a critical step towards harnessing the myriad of potential applications of MOFs by enabling larger scale production and hence real-world applications. This review provides an up-to-date survey ( references) of the most promising novel synthetic routes, i.e., electrochemical, microwave, mechanochemical, spray drying and flow chemistry synthesis. Additionally, the essential topic of downstream processes, especially for large scale synthesis, is critically reviewed. Lastly we present the current state of MOF commercialization with direct feedback from commercial players.

/pdf/new-synthetic-routes-towards-mof-production-at-scale-33dzwiytlv.pdf

New synthetic routes towards MOF production at scale

Realization of heterogeneous electrochemical CO2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal–organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (∼1015 sites/cm2). The chemical products of the reduction, obtained with ∼100% Faradaic efficiency, are mixtures of CO and H2. These results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.

Fe-Porphyrin-Based Metal–Organic Framework Films as High-Surface Concentration, Heterogeneous Catalysts for Electrochemical Reduction of CO2

As research into metal–organic frameworks (MOFs) enters its third decade, efforts are naturally shifting from fundamental studies to applications, utilizing the unique features of these materials. Engineered forms of MOFs, such as membranes and films, are being investigated to transform laboratory-synthesized MOF powders to industrially viable products for separations, chemical sensors and catalysts. Following encouraging demonstrations of gas separations using MOF-based membranes, liquid-phase separations are now being explored in an effort to build effective membranes for these settings. In this Review, we highlight MOF applications that are in their nascent stages, specifically liquid-phase separations using MOF-based mixed-matrix membranes. We also highlight the analytical techniques that provide important insights into these materials, particularly at surfaces and interfaces, to better understand MOFs and their interactions with other materials, which will ultimately lead to their use in advanced technologies. The pores of metal–organic frameworks (MOFs) make them attractive materials for gas- and liquid-phase separations. In this Review, the fabrication of MOF-based membranes and analytical techniques used to characterize them are outlined with a focus on the surfaces and interfaces in these composite materials.

Metal–organic frameworks for membrane-based separations

Electrophoretic deposition (EPD) is used to assemble metal-organic framework (MOF) materials in nano- and micro-particulate, thin-film form. The flexibility of the method is demonstrated by the successful deposition of 4 types of MOFs: NU-1000, UiO-66, HKUST-1, and Al-MIL-53. Additionally, EPD is used to pattern the growth of NU-1000 thin films that exhibit full electrochemical activity.

Directed Growth of Electroactive Metal-Organic Framework Thin Films Using Electrophoretic Deposition

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Directed Growth of Electroactive Metal-Organic Framework Thin Films Using Electrophoretic Deposition