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Metal organic frameworks and organic cages for highly selective gas separation membranes and heavy metal capture devices

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Newsletter - Cariplo MOCA grant n. 2019-2090
Newsletter 3 July 2022
Metal organic frameworks and organic cages for highly
selective gas separation membranes and heavy metal
capture devices
Fondazione Cariplo
Grant 2019-2090
Coordinator: Valeria Amendola
Università di Pavia
Dipartimento di Chimica
E-mail: amendola@unipv.it
https://www.mocaproject.com
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2022
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Great news from the MOCA team!
Marcello Monteleone has recently obtained a permanent position as Ricercatore at CNR-
ITM. He will continue to work on the MOCA project, also supporting the activity of the
new post-doc, Mariagiulia.
Dear Marcello, congrats and thanks for your contribution!
The MOCA project WORKSHOP will be held in Pavia in June (7th -9th ) 2023, details will be
available soon on our website
During the last year (1st July 2021-30th June 2022) the MOCA team and
collaboration between groups have increased a lot In particular, the research period
spent by Sonia at the Unical and ITM laboratories was an opportunity for the team
members to exchange scientific ideas, consolidate old collaborations, and forge new
ones. The obtained results have been published in high impact scientific journals,
other works are in progress: this Newsletter reports a summary of the recent
published works we are most proud of.
Valeria Amendola
A new post-doc joined our team @ ITM: Mariagiulia Longo
On the May 1st, 2022, Mariagiulia Longo was recruited as Post-doc researcher in the frame
of the MOCA project, where she follows in the footsteps of Dr. Marcello Monteleone, who
moved to a new position at ITM. She graduated in Material Science in 2017 at the University
of Calabria and got the PhD degree in Physical, chemical and material sciences and
technologies in February 2022. Her research activities were focused on the study of different
types of polymeric membranes for gas separation processes in order to understand their
structure-properties relationships, with emphasis on the correlation between the mechanical
and transport properties. She spent the seven months of the international training period at
University of Edinburgh under the supervision of prof Neil McKeown, where she developed
novel PIM-based polymeric blend membranes.
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Organic cages: recognition, sensing, and separation processes
by Valeria Amendola
Organic cages are fascinating systems that can be efficiently applied in recognition, sensing, and
separation processes. The recognition and trapping of noxious pollutants, including heavy metals,
in aqueous solution is of great interest for the scientific community, and it is also one of the major
goals of the MOCA project. Within this context, a chiroptical response has the advantage of being
very sensitive and selective, allowing the detection of the target species in the presence of
interfering analytes. Our group in Pavia recently developed new chiral organic cages, that were
successfully applied in the recognition and sensing of heavy metals in beverages or artificial urine
medium. Details on our studies and results can be found in our recent publication Chem. Commun.
2022,58, 3897-3900
We also developed novel imide/imine-based organic cages, that were investigated as materials for
gas separation processes as both pure solids and loaded in polymeric membranes. SCXRD analyses
showed that the cages crystallize forming a thick network of intermolecular H-bonds. Gas
adsorption studies were conducted on the solids precipitated from the reaction mixtures, and then
ball-milled to achieve materials that could be homogenously dispersed into polymer matrices for
the preparation of MMMs. Both the materials and corresponding MMMs a good selectivity for CO2
vs. N2 and CH4. This study is object of a just accepted publication: Chem Eur J. 2022
10.1002/chem.202201631
A series of imine cages have been synthesized and studied with gases. One of the goals of
the MOCA project is the development of organic cages, to be applied alone and as fillers in mixed-
matrix membranes) for gas separation applications. Within this context, four different organic cages
have been prepared and dispersed in the poly(ether ether ketone) with cardo group (PEEK-WC). The
obtained mixed-matrix membranes, developed at ITM-CNR, were studied with various gases. Two
of the employed fillers yielded mechanically robust and selective films after silicone coating, while
the other cages did not allow the formation of selective films. Pure gas permeability tests were
performed with H2, He, O2, N2, CH4 and CO2 on both the neat polymer and the MMMs. The fillers
effect was compared with the maximum limits expected for infinitely permeable and impermeable
fillers, using the Maxwell model. These studies of transport properties showed that, the
permeability of all the tested gases increased in presence of the furanyl cage (Fura) as filler, while a
lowering was obtained with the m-xylyl cage (m-xy). In term of selectivity, an increase was observed
for the gas pairs CO2/CH4, CO2/N2, O2/N2 and He/CH4 in presence of m-xy. On the other hand, the
CO2/N2 selectivity did not significantly change with Fura, while a decrease was observed for the
other gas pairs. As remarked in our publication: “The use of these cages as fillers generally increased
the diffusivity for all the investigated gases. In particular, the slight increase of diffusivity promoted
by m-xy enhanced the size-selectivity of the membrane. On the other hand, the diffusivity of bulky
gases increased remarkably with the Fura cage, thus causing a loss in diffusion selectivity. The
mechanism of the gas transport follows the solution-diffusion model also after the loading of cages
in the membranes, because it does not change the linear correlation between the logarithm of the
The MOCA Project - Newsletter 3
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diffusion coefficient, (D), and the square of the effective gas diameter d2eff. The obtained results
are a good starting point for studying the effect of cages concentration on the gas transport
properties of MMMs, which will be evaluated in detail in further studies.” The results of this fruitful
collaboration between Pavia and ITM research units are reported in Molecules 2021, 26(18):5557
News from the Unical unit
by Rosaria Bruno & Donatella Armentano
Metal organic frameworks (MOFs), a class of crystalline highly porous materials, have
provided an excellent platform for the capture of several pollutants from water. Novel and versatile
Bio-inspired MOFs (Bio-MOFs), including multivariate metal-organic frameworks (MTV-MOFs), have
been prepared, characterized and tested for water remediation by the UNICAL team, in
collaboration with Emilio Pardo and co-workers from the University of Valencia. The rational
exploitation of the interactions between MOFs and the adsorbed species has been useful for the
efficient removal of harmful organic molecules or metal ions from water.
A MOF, prepared from the amino acid L-methionine and possessing channels decorated with
thioalkyl chains, was used to efficiently capture four different organic dyes, commonly used as
antiseptics in hospitals or in textile industries, at very low concentrations (10 ppm) from real water
samples from Turia river (Valencia, Spain). The compound was processed in the form of extruded
pellets, by mixing the polycrystalline powders with commercial Matrimid polymer. The adsorbent
material was able to remove dyes with a very fast kinetic, reaching within five minutes nearly the
maximum removal. Remarkably, the crystal structures of the different organic dyes adsorbed within
the MOFs channels, determined by SCXRD, enabled the direct visualization of the significant role
that sulfur σ-hole interactions play on the removal of organic dyes. The results of this study are
reported in Chem. Eur.J. 2022, 28, e202200034. The easiness to produce this BioMOF at multigram-
scale, the environmentally benign nature of its components, and its outstanding performances
make this material an attracting candidate to be tested in pilot plants or structured in mixed-matrix
membranes for decontamination.
An eco-friendly single-walled carbon nanotube
buckypaper (SWCNT-BP), enriched with a multivariate amino
acid-based metal−organic framework (MTV-MOF), have
been prepared, characterized and tested for the efficient and
selective removal of Pb2+, an environmentally harmful heavy
metal, in multicomponent water systems. ACS Appl. Nano
Mater. 2022, 5, 5223−5233. The pristine MTV-MOF was
easily immobilized within the porous network of entangled
SWCNTs, thus obtaining a stable self-standing adsorbing
membrane filter (MTV-MOF/SWCNT-BP). The MTV-
MOF/SWCNT-BP membrane filter exhibited enhanced
selectivity and adsorption capacity, allowing to reduce the lead concentration from the dangerous
1000 ppb level to acceptable limits for drinking water, i.e. below 10 ppb, in agreement with the
The MOCA Project - Newsletter 3
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current EPA and WHO established limits. Remarkably, we also performed an in-depth experimental
study through SCXRD of the MTV-MOF···Pb2+ interactions, which represent the first reported
example of such hostguest interaction. This eco-friendly composite MTV-MOF/SWCNT-BP shows
the potential to be effectively used as a reliable adsorbent for household drinking water production
or in industrial treatment plants for water and wastewater lead decontamination.
News from the CNR-ITM Unit
by Marcello Monteleone & John Jansen
In the first half of 2022, the activities of the MOCA project continued to be focused on the two main
lines of research: 1) development of mixed matrix membranes for gas separation and 2) water
decontamination to remove heavy metals. In the first topic, a set of polyimine cages, synthesised by
the group of Prof. Valeria Amendola from the University of Pavia, were dispersed in the amorphous
glassy poly(ether-ether ketone) PEEK-WC, and in Matrimid®9725. The gas transport properties of
the membranes were determined under single and mixed gas conditions. An improvement of the
membrane performance in terms of selectivity and/or permeability compared to that of the neat
polymer for the gas pairs CO2/CH4, CO2/N2 was achieved. These results are reported in the accepted
manuscript: S. La Cognata et al. in Chem. Eur. J. The second research topic of CNR-ITM in the MOCA
project is focused on the development of mixed matrix membranes containing multivariate Metal
Organic Frameworks (MOFs), synthesized by the group of Prof. Donatella Armentano, from the
university of Calabria (UNICAL), for the capture of heavy metals from waste waters. A systematic
study for the optimization of porous Polyacrylonitrile (PAN) and cellulose acetate membranes was
carried out in order to yield the desired membrane morphology. Commercial MOFs (as a reference)
and the novel multivariate MOFs, were dispersed in the polymer matrix at different concentrations.
The characterization of the prepared membranes in terms of water purification and heavy metals
retentions are currently in progress.
A
B
Cross section SEM images of cellulose acetate (A) and PAN
membranes (B), both loaded with 50% of ZIF-94
The MOCA Project - Newsletter 3
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Dissemination activities
Scientific education and seminars
1) Valeria Amendola in Gabbie molecolari e altri materiali per la separazione dell’anidride
carbonica (lesson/seminar), Pavia, Almo Collegio Borromeo, 4th May 2022 (6.30 pm)
2) Valeria Amendola in Organic cages in sensing and separation processes (seminar),
Dipartimento di Chimica, Università di Padova, Padova, 15th June 2022 (3.00 pm)
1) Rosaria Bruno, Sonia La Cognata, Marcello Monteleone and Valeria Amendola in Materiali
innovativi per purificare l'aria e l'acqua: ecco il progetto MOCA (webinar), FESTIVAL DELLO
SVILUPPO SOSTENIBILE, 29th September 2021
Presentations to national and international conferences:
1) Valeria Amendola, Sonia La Cognata, Riccardo Mobili, Azacryptands: versatile molecular cages
for recognition and separation processes (OC), 1st WISC Workshop, 6th-8th September 2021
2) Sonia La Cognata, Riccardo Mobili, Chiara Milanese, Marcello Monteleone, Johannes C. Jansen,
Valeria Amendola, Azacryptands as fillers in Mixed Matrix Membranes for Gas Separation (OC),
1st WISC Workshop, Cagliari, 6th-8th September 2021
3) Riccardo Mobili, Sonia La Cognata, Ariana R. Antonangelo, Mariolino Carta, Marcello Monteleone,
Johannes C. Jansen, Valeria Amendola, Molecular organic cages for gas separation (poster),
1st International Supramolecular Chemistry Summer School, Santa Margherita di Pula, 29th May -
2nd June 2022
4) Donatella Armentano, Atomically Precise Chemistry in Confined Spaces of Metal-Organic
Frameworks, (Plenary Lecture) GDCh Science Forum Chemistry WIFO2021- Monaco, 29th August
1st September 2021
5) Rosaria Bruno, Cristina Negro, Héctor Martínez Pérez-Cejuela, Ernesto F. Simó-Alfonso,
José Manuel Herrero-Martínez, Donatella Armentano, Jess Ferrando-Soria, Emilio Pardo, Highly
Efficient Removal of Neonicotinoid Insecticides by Thioether-Based (Multivariate)
Metal−Organic Frameworks (Poster) XLIX Meeting of the Italian Crystallographic Association (AIC)
Parma, 6th-8th September 2021, online event.
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Social Media #Mocaproject
All the news on the project can be found on the website: https://www.mocaproject.com, and the
project results and activities can be followed on the dedicated profiles on social networks: Twitter
(@moca_project), Linkedin (@moca-project), Facebook (@moca.project2020) and on
Researchgate. The dedicated tag #Mocaproject will help in following us.
https://twitter.com/moca_project
https://www.linkedin.com/in/moca-project/
https://www.facebook.com/moca.project2020
https://www.researchgate.net/project/Moca-Metal-Organic-frameworks-and-organic-CAges-
for-highly-selective-gas-separation-membranes-and-heavy-metal-capture-devices
Stay tuned to discover more on the MOCA Project!
The MOCA team
Università di Pavia
Valeria Amendola
Sonia La Cognata
Riccardo Mobili
Antonio Poggi
Lucio Toma
Università della Calabria
Donatella Armentano
Rosaria Bruno
Teresa Mastropietro
CNR-ITM
John Jansen
Elisa Esposito
Alessio Fuoco
Adolfo Iulianelli
Marcello Monteleone
Mariagiulia Longo
Elena Tocci
ResearchGate has not been able to resolve any citations for this publication.
Gabbie molecolari e altri materiali per la separazione dell'anidride carbonica" (lesson/seminar)
  • Valeria Amendola
Valeria Amendola in "Gabbie molecolari e altri materiali per la separazione dell'anidride carbonica" (lesson/seminar), Pavia, Almo Collegio Borromeo, 4th May 2022 (6.30 pm)
Organic cages in sensing and separation processes" (seminar), Dipartimento di Chimica
  • Valeria Amendola In
Valeria Amendola in "Organic cages in sensing and separation processes" (seminar), Dipartimento di Chimica, Università di Padova, Padova, 15th June 2022 (3.00 pm)
Materiali innovativi per purificare l'aria e l'acqua: ecco il progetto MOCA" (webinar), FESTIVAL DELLO SVILUPPO SOSTENIBILE
  • Rosaria Bruno
  • Sonia La Cognata
  • Marcello Monteleone
  • Valeria Amendola
Rosaria Bruno, Sonia La Cognata, Marcello Monteleone and Valeria Amendola in "Materiali innovativi per purificare l'aria e l'acqua: ecco il progetto MOCA" (webinar), FESTIVAL DELLO SVILUPPO SOSTENIBILE, 29th September 2021 Presentations to national and international conferences:
Azacryptands: versatile molecular cages for recognition and separation processes (OC), 1st WISC Workshop
  • Valeria Amendola
  • Sonia La Cognata
  • Riccardo Mobili
Valeria Amendola, Sonia La Cognata, Riccardo Mobili, Azacryptands: versatile molecular cages for recognition and separation processes (OC), 1st WISC Workshop, 6th-8th September 2021
Molecular organic cages for gas separation
  • Riccardo Mobili
  • Sonia La Cognata
  • Ariana R Antonangelo
  • Mariolino Carta
  • Marcello Monteleone
  • Johannes C Jansen
  • Valeria Amendola
Riccardo Mobili, Sonia La Cognata, Ariana R. Antonangelo, Mariolino Carta, Marcello Monteleone, Johannes C. Jansen, Valeria Amendola, Molecular organic cages for gas separation (poster),
Atomically Precise Chemistry in Confined Spaces of Metal-Organic Frameworks, (Plenary Lecture) GDCh Science Forum Chemistry -WIFO2021-Monaco
  • Donatella Armentano
Donatella Armentano, Atomically Precise Chemistry in Confined Spaces of Metal-Organic Frameworks, (Plenary Lecture) GDCh Science Forum Chemistry -WIFO2021-Monaco, 29 th August -1 st September 2021