Materials suitable for CO2 capture and sequestration, through chemical reaction, based on azomethine derivatives
- Project leaders
- Williamumberto Porzio, Luminita Marin
- ROMANIA - RA - The Romanian Academy
- CNR-RA 2017-2019
- Chemical sciences and materials technology
- Thematic area
- Chemical sciences and materials technology
- Status of the project
The project aims to bring together researchers with complementary expertize from "Petru Poni" Institute of Macromolecular Chemistry (PPIMC), Iasi, Romania and Istituto per lo Studio delle Macromolecole (ISMAC-CNR), Milan, Italy, to work together on a multidisciplinary theme around a very hot topic related to the preparation of materials suitable for carbon dioxide (CO2) capture and sequestration (CCS). The two partners already have a collaboration history which started in 2006, materialized in scientific articles published together [1-3].
As global warming threatens to dramatic change the human life on the Earth, the scientific community is searching for solutions to limit it [4-6]. Considering that fossil fuels continue to play a significant role as energy sources, the systems for CO2 capture and sequestration from point sources were found as viable solutions to reduce the greenhouse gas emission. Up to now reliable efforts to face the above problem were addressed towards two different synthetic approaches: (i) pi-conjugated molecules capable to organize into covalent organic frameworks (COF), properly complexed with non-precious metals and (ii) copolymers based on conjugated molecules; both of them displaying remarkable CCS capability [6-8]. The future perspective of this research stems on the significant increase of the CCS achieved through the catalytic reaction of CO2.
The long time experience of both groups on conjugated oligomeric and polymeric systems based on azomethine connections [3, 9-13] enabled the design of suitable polymers with such a chemical constitution, with the subsequent aim of complexation of transition metals, based on the azomethine/nitrogen ability to act as ligand. The main building blocks of the proposed design originates from reagents occurred in natural renewable feedstock, which are commercially available, cheap and environmentally friendly, increasing the potential of the targeted materials to replace the petro-chemically derived and potential hazardous products and to provide cost-effective and environmentally friendly technology for CO2 capture and sequestration. A list of the proposed reagents, as (i) amines are: melamine - a rich nitrogen tri-amine prepared from urea, which already proved its ability to generate resins with good film forming ability and flame retardancy - useful properties in preparation of membranes for flue gases; spermine - a polyamine found in a large variety of organisms and tissues; and chitosan - a polyamine originating from crustaceus exoskeletons; and as (ii) aldehydes: vanillin - extracted from vanilla beans; cynamaldehyde - extracted from cinnamon; and furfural - derived from a large variety of agriculture byproducts. The reagent choice has been made taking into consideration their ability to react toward targeted complex structures via dynamic imine chemistry  or to form aminals  to give nanoporous amorphous or crystalline materials.
In this respect we plan to synthesize molecules constituted by such moieties, subsequently suitable films made of nanoparticles or nanofibers will be prepared based on these compounds, and will be characterized in terms of both electrochemical (cyclic and linear sweep voltammetries) and isothermal gas absorption properties.
To this end, the conventional characterization (molecular, micro-structural, and surface analysis structural, microscopic etc.) are preparatory to the electrochemistry investigations and, mostly, the gas uptake and its cycling completing the overall project development. The subsequent chemical modification of molecules obtained and a possible complexation with non-precious metals to enhance the CCS ability constitutes the evolution of the present project.
The two teams aim to work together on this joint research project, combining their previous experience and research collaboration, as well as the complementary infrastructure.
The Romanian research team (R) includes researchers with expertise in synthesis of azomethine compounds and their study by structural,spectroscopical and morphological methods as well as obtaining of films [8-11]. The Italian research team (I) includes researchers with expertise in synthesis, structural, and electrochemical methods as well as obtaining of films and nanofibers. The project work plan has been thought in independent tasks for each team but also common tasks based on their complementary expertize, as follow.
1. Design, synthesis, and molecular characterization of proper molecules (NMR, FTIR, MALDI, SEC); R and I scientists
2. Electrochemistry of the produced materials (I) and their structural and morphological characterization (AFM, XRD (single crystal and wide angle), POM, DSC); R
3. Absorption isotherms and cycling, spectroscopical characterization (absorption and emission), CO2 uptake; I
4. Perspectives, modifications; R and I scientists
 Porzio W.; Destri S.; Pasini M.; Giovanella U.; Marin L.; Damaceanu, M.D.; Campione, M. Thin Solid Films 515, 7318-7323, 2007;  Destri S., Porzio W., Marin L., Damaceanu M.D., Bruma M. J. Optoelectr. Adv. Mat. 9, 1337-1341, 2007;  Marin L., Destri S., Porzio W., Bertini F., Liq. Cryst. 36, 21-32, 2009;  Chu S. Science 325, 1599, 2009;  Pera-Titus M., Chem. Rev. 114, 1413, 2014;  Kundu S.K., Bhaumik A. ACS Sust. Chem.Eng. 4, 3697, 2016;  Wang Z.L., Li C., Yamauchi Y. NanoToday 11, 373, 2016;  Aiyappa H.B., et. al. Chem Mater. 28, 4375, 2016;  Olinga T.E., Destri S., Botta C., Porzio W., Consonni R. Macromolecules 31, 1070-1078, 1998;  Marin L., Perju E., Damaceanu M.D, Eur. Polym. J. 47, 1284-1299, 2011;  Marin L. et al. New J. Chem. 39, 6404-6420, 2015;  Marin L., Ailincai D., et al. Carbohyd. Polym. 117, 762-770, 2015;  Marin L., Simionescu B.C., Barboiu M. Chem. Comm. 48, 8778-8780, 2012;  Liu Y. et al.Aust. J. Chem., 66, 9-22, 2013;  Li G., Zhang B. et al.Macromolecules 49 2575, 2016.
The main objective of the project is the realization of robust film materials by using novel covalent chemical frameworks for developing technology for CO2 capture. This main objective will be attained by reaching following sub-objectives:
o The design and synthesis of linear and cyclic conjugate oligomers constituted by condensation of benzene, triazine, furane moieties via azomethine linkage to realize microporous polymers or COF
o Preparation of films from the synthesized materials, suitable for electrochemical and gas-absorption analyses.
o Preparation of properly thick films to subject to CCS checking.
o Subsequent complexation of the prepared compounds with non-precious metals like Co, Ni, Re.
o Testing the materials obtained as absorbers and possibly reduction to fix and utilize CO2 gas.
o Chemical modification to improve CCS ability.
o Repeating the above tests
Last update: 02/12/2023