Project

Moca - Metal Organic frameworks and organic CAges for highly selective gas separation membranes and heavy metal capture devices

Goal: Our goals:
1) capture of pollutants (e.g. heavy metals, anions, dyes) from liquid wastes,
2) capture of e.g. CO2 from gaseous streams,
3) the upgrading of methane from natural gas or biogas.

The MOCA project will make these separations possible by using selective extractants (Cages and MOFs) embedded in Mixed-Matrix Membranes. A further goal of MOCA is the valorisation of the recovered materials (e.g. decontaminated water, captured CO2, purified CH4) as valuable starting products for new processes, according to the principles of Circular Economy.
It is sponsored by Fondazione Cariplo.

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Project log

Valeria Amendola
added a research item
Two novel imide/imine‐based organic cages were prepared and studied as materials for the selective separation of CO 2 from N 2 and CH 4 in Vacuum Swing Adsorption conditions. Gas adsorption on the new compounds showed selectivity for CO 2 over N 2 and CH 4 . The cages were also tested as fillers in mixed‐matrix membranes for gas separation. Dense and robust membranes were obtained by loading the cages in either Matrimid ® or PEEK‐WC polymers. Improved gas transport properties and selectivity for CO 2 were achieved compared to the neat polymer membranes.
Teresa F. Mastropietro
added a research item
A self-assembled layered compound of formula {[Cu5(OH)8Cyt2]·2ClO4}n (1) was obtained from the direct reaction between copper perchlorate and cytosine. Thanks to its peculiar structural features, this coordination compound can be classified as an intermediate nonconventional analog of Layered Simple Hydroxides (LSHs) and Layered Double Hydroxides (LDHs), two fascinating classes of inorganic materials with variable chemical composition and structures. Like LDHs, 1 consists of positively charged layers of metal hydroxides and non-framework charge-balancing anions located between the layers. However, the hydroxide layers, similar to LSHs, contain only divalent copper(II) metal ions, supported by cytosine molecules with long contacts. Cytosine coordinates to the metal centers adopting an unusual µ3 coordination mode, the exocyclic oxygen atom simultaneously binding to three adjacent copper(II) centers. This coordination mode has not been observed with transition metal ions. This work further demonstrates that nucleobases and their derivatives, despite presenting a limited pool of molecules, can potentially afford a significantly expanded set of compounds with diverse nanostructures, owing to their multiple metal binding sites of different coordination properties and their ability to direct assembly of highly ordered structures. Their potential as building blocks should be further explored for the preparation of new bio-inorganic hybrid materials.
Valeria Amendola
added a research item
A chiral cage is proposed as an effective chiroptical sensor for perrhenate (surrogate for 99TcO4-) in water, fruit juice and artificial urine medium. The key mechanism for the chiroptical sensing...
Johannes Carolus (John) Jansen
added a research item
Membrane-based processes are taking a more and more prominent position in the search for sustainable and energy-efficient gas separation applications. It is known that the separation performance of pure polymers may significantly be improved by the dispersion of suitable filler materials in the polymer matrix, to produce so-called mixed matrix membranes. In the present work, four different organic cages were dispersed in the poly(ether ether ketone) with cardo group, PEEKWC. The m-xylyl imine and furanyl imine-based fillers yielded mechanically robust and selective films after silicone coating. Instead, poor dispersion of p-xylyl imine and diphenyl imine cages did not allow the formation of selective films. The H2, He, O2, N2, CH4, and CO2 pure gas permeability of the neat polymer and the MMMs were measured, and the effect of filler was compared with the maximum limits expected for infinitely permeable and impermeable fillers, according to the Maxwell model. Time lag measurements allowed the calculation of the diffusion coefficient and demonstrated that 20 wt % of furanyl imine cage strongly increased the diffusion coefficient of the bulkier gases and decreased the diffusion selectivity, whereas the m-xylyl imine cage slightly increased the diffusion coefficient and improved the size-selectivity. The performance and properties of the membranes were discussed in relation to their composition and morphology.
Teresa F. Mastropietro
added a research item
Today, it is extremely urgent to face the increasing shortage of clean and safe water resources, determined by the exponential growth of both world population and its consumerism, climate change...
Alessio Fuoco
added a project goal
Our goals:
1) capture of pollutants (e.g. heavy metals, anions, dyes) from liquid wastes,
2) capture of e.g. CO2 from gaseous streams,
3) the upgrading of methane from natural gas or biogas.
The MOCA project will make these separations possible by using selective extractants (Cages and MOFs) embedded in Mixed-Matrix Membranes. A further goal of MOCA is the valorisation of the recovered materials (e.g. decontaminated water, captured CO2, purified CH4) as valuable starting products for new processes, according to the principles of Circular Economy.
It is sponsored by Fondazione Cariplo.