Adsorption‐based cooling systems, which can be driven by waste heat and solar energy, are promising alternatives to conventional, compression‐based cooling systems, as they demand less energy and ...emit less CO2. The performance of adsorption‐based cooling systems relates directly to the performance of the working pairs (sorbent–water). Accordingly, improvement of these systems relies on the continual discovery of new sorbents that enable greater mass exchange while requiring less energy for regeneration. Here, it is proposed that covalent‐organic frameworks (COFs) can replace traditional sorbents for adsorption‐based cooling. In tests mimicking standard operating conditions for industry, the imine‐based COF TpPa‐1 exhibits a regeneration temperature below 65 °C and a cooling coefficient of performance of 0.77 – values which are comparable to those reported for the best metal–organic framework sorbents described to date. Moreover, TpPa‐1 exhibits a photothermal effect and can be regenerated by visible light, thereby opening the possibility for its use in solar‐driven cooling.
The imine‐based covalent‐organic framework TpPa‐1 is proposed as an adsorbent for cooling systems. TpPa‐1 can be regenerated upon heating at temperatures present in cogeneration plants (<65 °C) or when exposed to visible light and shows a high value for cooling coefficient of performance of 0.77.
Adsorptive heat transformation systems such as adsorption thermal batteries and chillers can provide space heating and cooling in a more environmental friendly way. However, their use is still ...hindered by their relatively poor performances and large sizes due to the limited properties of solid adsorbents. Here, the spray‐drying continuous‐flow synthesis of a new type of solid adsorbents that results from combining metal‐organic frameworks (MOFs), such as UiO‐66, and hygroscopic salts, such as CaCl2 has been reported. These adsorbents, commonly named as composite salt in porous matrix (CSPM) materials, allow improving the water uptake capabilities of MOFs while preventing their dissolution in the water adsorbed; a common characteristic of these salts due to the deliquescence effect. It is anticipated that MOF‐based CSPMs, in which the percentage of salt can be tuned, are promising candidates for thermal batteries and chillers. In these applications, it is showed that a CSPM made of UiO‐66 and CaCl2 (38% w/w) exhibits a heat storage capacity of 367 kJ kg−1 , whereas a second CSPM made of UiO‐66 and CaCl2 (53% w/w) shows a specific cooling power of 631 W kg−1 and a coefficient of performance of 0.83, comparable to the best solid adsorbents reported so far.
A new type of composite salt in porous matrix adsorbents that results from combining metal‐organic frameworks (MOFs) and hygroscopic salts (CaCl2, LiCl) has been synthesized by spray‐drying continuous‐flow method. The applicability of these MOF‐based CSPMs has been demonstrated for potential applications in thermal batteries and refrigerator systems, demonstrating high capacity and energetic efficiency.
The use of covalent organic frameworks (COFs) in practical applications demands shaping them into macroscopic objects, which remains challenging. Herein, we report a simple three‐step method to ...produce COF aerogels, based on sol‐gel transition, solvent‐exchange, and supercritical CO2 drying, in which 2D imine‐based COF sheets link together to form hierarchical porous structures. The resultant COF aerogel monoliths have extremely low densities (ca. 0.02 g cm−3), high porosity (total porosity values of ca. 99 %), and mechanically behave as elastic materials under a moderate strain (<25–35 %) but become plastic under greater strain. Moreover, these COF aerogels maintain the micro‐ and meso‐porosity of their constituent COFs, and show excellent absorption capacity (e.g. toluene uptake: 32 g g−1), with high removal efficiency (ca. 99 %). The same three‐step method can be used to create functional composites of these COF aerogels with nanomaterials.
A three‐step method produces COF aerogel monoliths, based on sol–gel transition, solvent‐exchange, and supercritical CO2 drying. 2D imine‐based COF sheets link together to form hierarchical porous structures. The aerogels have extremely low densities, high porosity, and mechanically behave as elastic or plastic materials under different strain. They show excellent absorption capacity with high removal efficiency.
Herein, we describe a new class of porous composites comprising metal–organic framework (MOF) crystals confined in single spherical matrices made of packed covalent‐organic framework (COF) ...nanocrystals. These MOF@COF composites are synthesized through a two‐step method of spray‐drying and subsequent amorphous (imine‐based polymer)‐to‐crystalline (imine‐based COF) transformation. This transformation around the MOF crystals generates micro‐ and mesopores at the MOF/COF interface that provide far superior porosity compared to that of the constituent MOF and COF components added together. We report that water sorption in these new pores occurs within the same pressure window as in the COF pores. Our new MOF@COF composites, with their additional pores at the MOF/COF interface, should have implications for the development of new composites.
Open pore remedy: A new class of porous composites comprising metal–organic framework (MOF) crystals confined in single spherical matrices made of packed covalent‐organic framework (COF) nanocrystals is described. These MOF@COF composites show the formation of micro‐ and mesopores at the MOF/COF interface that provide superior porosity compared to that of the constituent MOF and COF components added together.
Herein, we exploit the well‐known swelling behaviour of metal–organic frameworks (MOFs) to create a self‐folding polymer film. Namely, we show that incorporating crystals of the flexible MOF MIL‐88A ...into a polyvinylidene difluoride (PVDF) matrix affords a polymer composite film that undergoes reversible shape transformations upon exposure to polar solvents and vapours. Since the self‐folding properties of this film correlate directly with the swelling properties of the MIL‐88A crystals, it selectively bends to certain solvents and its degree of folding can be controlled by controlling the relative humidity. Moreover, it shows a shape‐memory effect at relative humidity values from 60 % to 90 %. As proof of concept, we demonstrate that these composite films can lift cargo and can be used to assemble 3D structures from 2D patterns. Our strategy is a straightforward method for designing autonomous soft materials with folding properties that can be tuned by judicious choice of the constituent flexible MOF.
MOF‐n‐Fold: The swelling behaviour of the metal–organic framework MIL‐88A is used to impart self‐folding properties to a polymer film upon exposure to polar solvents and vapours. The degree of folding of the resulting film can be controlled by changing the relative humidity, showing a shape memory effect.
Here, we report the design, synthesis, and functional testing of enzyme-powered porous micromotors built from a metal-organic framework (MOF). We began by subjecting a presynthesized microporous ...UiO-type MOF to ozonolysis, to confer it with mesopores sufficiently large to adsorb and host the enzyme catalase (size: 6-10 nm). We then encapsulated catalase inside the mesopores, observing that they are hosted in those mesopores located at the subsurface of the MOF crystals. In the presence of H
O
fuel, MOF motors (or MOFtors) exhibit jet-like propulsion enabled by enzymatic generation of oxygen bubbles. Moreover, thanks to their hierarchical pore system, the MOFtors retain sufficient free space for adsorption of additional targeted species, which we validated by testing a MOFtor for removal of rhodamine B during self-propulsion.
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