Supercritical Fluids and Functional Materials

Led by Prof. Concepción Domingo

The SFFM group focuses its research in the use of Supercritical CO2 for the design and preparation of functional materials for a wide variety of applications ranging from energy and environment to biomedical applications

scCO2 and general applications
scCO2 is a non-toxic and environmentally benign green solvent that has been widely used in the food and pharmaceutical industries. However, scCO2 (which reaches its supercritical conditions at 31.1 °C and 7.4 MPa) also has many outstanding properties, which give it a great potential for advanced synthesis and materials processing. In particular, it is an attractive alternative to organic solvents that are widely recognized as pollutant or toxic. ScCO2 is a non-destructive fluid with null surface tension, thus adequate to create or manipulate complex primary nanoparticles, functional nanomaterials and nanostructures. Moreover, the low viscosity of the compressed fluid and its high diffusivity allow for exceptionally effective penetration in nanopores.

The overall objective of the SFFM group is to use this clean supercritical fluid technology, coupled with other chemical processing approaches, as a platform to develop flexible manufacturing routes for the cost-effective production of nanoporous materials as well as 3D nanostructures using sustainable processes. scCO2 technology is used for the production of high performance existing and new products with unique characteristics in regard to composition (purity), size (micro or nanoscale) and architecture (fibres, foams).

Contact

conchi@icmab.es
Prof. Concepción Domingo
amlopez@icmab.es
Dr. Ana Mª López-Periago
julio@icmab.es
Julio Fraile

Research Topics

Our current interest is largely focused on the preparation of porous polymers, coordination polymers and graphene-based aerogel composites. These research lines interlink to create further advanced and more sophisticated structures.

Polymeric porous materials

Godoy-Gallardo, Maria; Portolés-Gil, Núria; López-Periago, Ana M; Domingo, Concepción; Hosta-Rigau, Leticia, Materials Science and Engineering C, 2020, 117,11124

Materials employed for the fabrication of scaffolds have mainly relied on bioceramics and biodegradable polymer.

In our group, we propose the use of scCO2 for the preparation of composite scaffolds made from bioceramics and polymers such as hydroxyapatite (HA) and polycraprolactone (PCL) matrix.

The scaffolds are fabricated using scCO2 technology and controlled pressurization/depressurization regimens, which help to display a highly interconnected network of pores with a multimodal pore size distribution. This architecture can mimic the extracellular matrix of natural tissue, in which the macropores can promote cell growth, proliferation and migration, and the microporous network allows the diffusion of the necessary oxygen, nutrients and waste.

Coordination Polymers and Metal organic frameworks

The SFFM research group pioneered the synthesis of coordination polymers in scCO2, showing that this fluid can act simultaneously as solvent and activation agent.

MOFs are hybrid network structures formed by self-assembly of metal ions or clusters and organic linking groups. These structures have a great variety of applications in catalysis, drug delivery, or gas separation and storage.

In this research topic, we propose an attractive synthetic method for the preparation of MOFs and coordination polymers. These hybrid materials can be obtained by using bidentate and tridentate N donor ligands, such as bipyridyl and triazine derivative organic linkers, respectively. Among the coordination polymers based on M2+ transition metals, there is a large variety of structural motifs when reacted with the different linkers, including simple and sinusoidal 1D chains, 2D double helices with simple and interpenetrating layers and even 3D frameworks.

Since the first synthesis of a coordination polymer using scCO2, more than 25 structures have been synthesised, from rigid to flexible structures, as well as very well known MOFs using carboxylate linkers such as ZIF-8, H-Kust-1 or MIL-100 (Fe).

ZIF-8

HKUST-1

MIL-100 (Fe)

BIO-MOFs.    A promising field of application of MOFs is the biomedical one. In this case, it is a bioactive molecule, such a curcumine, the linker in the MOF network

  • Nuria Portoles-Gil, Arianna Lanza, Nuria Aliaga-Alcalde, José A Ayllón, Mauro Gemmi, Enrico Mugnaioli, Ana M López-Periago*, Concepción Domingo, “Crystalline curcumin bioMOF obtained by precipitation in supercritical CO2 and structural determination by electron diffraction tomography”. ACS Sustainable Chemistry & Engineering. 2018, 6, 12309-12319

Graphene oxide aerogels and composites

We own a patented technology for producing GO aerogels starting from an alcoholic dispersion of graphene oxide. The procedure is developed under isothermal and isobaric conditions, and it is readily reproducible, scalable and cost-effective, leading to a non-reduced end-product.

The aerogel obtained combines stability and robustness with a high functionalization capacity granted by the large number of functional groups maintained from the starting graphene oxide. Aerogels obtained have a high surface area, ca. 250 m2/g, and a high pore volume, between 0.9 and 1.5 mL/g.

The possibility of preparing multifunctional composites using graphene oxide as a basic unit for the controlled self-assembly of 3D carbon macrostructures by supercritical CO2 is enormous. Possible applications include adsorption material in membrane technologies, batteries, supercapacitors, metal catalyst supports, among others.

In particular, composites of metal nanoparticles and GO aerogels are promising for a myriad of applications. As an example, the development of an all-green synthesis approach allowed the preparation of hybrid materials shaped into aerogels with large mesoporosity, involving the loading of SPIONs onto a GO surface via a simple one-pot supercritical CO2 technique for MRI applications

Relevant Publications 2015-2020

  • Multi-layered polydopamine coatings for the immobilization of growth factors onto highly-interconnected and bimodal PCL/HA-based scaffolds
    Godoy-Gallardo, M., Portolés-Gil, N., López-Periago, A.M., Domingo, C., Hosta-Rigau, L.
    Materials Science and Engineering: C 117, 111245, 2020

  • Novel Zn (II) coordination polymers based on the natural molecule bisdemethoxycurcumin (BDMC)
    L Rodríguez-Cid, EC Sañudo, AM López-Periago, A González-Campo, N. Aliaga, C. Domingo
    Crystal Growth & Design, 2020, 20, 10, 6555–6564
  • Green and Solvent-Free Supercritical CO2-Assisted Production of Superparamagnetic Graphene Oxide Aerogels: Application as a Superior Contrast Agent in MRI
    A Borrás, J Fraile, A Rosado, G Marbán, G Tobias, AM López-Periago, C Domingo
    ACS Sustainable Chemistry & Engineering 8 (12), 4877-4888, 2020

  • Preparation and Characterization of Graphene Oxide Aerogels: Exploring the Limits of Supercritical CO2 Fabrication Methods
    A Borrás, G Gonçalves, G Marbán, S Sandoval, S Pinto, PAAP Marques, J Fraile, G Tobias, AM López-Periago, C. Domingo, Chemistry–A European Journal 24 (59), 15903-15911, 2018

  • Crystalline Curcumin bioMOF Obtained by Precipitation in Supercritical CO2 and Structural Determination by Electron Diffraction Tomography
    N Portolés-Gil, A Lanza, N Aliaga-Alcalde, JA Ayllón, M Gemmi, E Mugnaioli, AM López-Periago, C Domingo.  ACS Sustainable Chemistry & Engineering 6 (9), 12309-12319, 2018

  • An Unprecedented Stimuli‐Controlled Single‐Crystal Reversible Phase Transition of a Metal–Organic Framework and Its Application to a Novel Method of Guest Encapsulation
    F Tan, A López‐Periago, ME Light, J Cirera, E Ruiz, A Borrás, F Teixidor, C Viñas, C Domingo, J.G. Planas.  Advanced Materials 30 (29), 1800726, 2018

  • Features of supercritical CO2 in the delicate world of the nanopores
    AM López-Periago, C Domingo
    The Journal of Supercritical Fluids 134, 204-213, 2018

  • Supercritical CO2 utilization for the crystallization of 2D metal-organic frameworks using tert-butylpyridine additive
    N Portolés-Gil, S Gowing, O Vallcorba, C Domingo, AM López-Periago, …
    Journal of CO2 Utilization 24, 444-453, 2018

  • Metal–Organic Frameworks Precipitated by Reactive Crystallization in Supercritical CO2
    AM López-Periago, N Portoles-Gil, P López-Domínguez, J Fraile, …
    Crystal Growth & Design 17 (5), 2864-2872, 2017

  • Supercritical CO2 for the synthesis of nanometric ZIF-8 and loading with hyperbranched aminopolymers. Applications in CO2 capture
    P López-Domínguez, AM López-Periago, FJ Fernández-Porras, J Fraile, …
    Journal of CO2 Utilization 18, 147-155, 2017

  • Bottom-up approach for the preparation of hybrid nanosheets based on coordination polymers made of metal–diethyloxaloacetate complexes linked by 4, 4′-bipyridine
    N Portoles-Gil, R Parra-Aliana, Á Álvarez-Larena, C Domingo, JA Ayllón, …
    CrystEngComm 19 (34), 4972-4982, 2017

  • Binary supercritical CO2 solvent mixtures for the synthesis of 3D metal-organic frameworks
    A López-Periago, P López-Domínguez, JP Barrio, G Tobias, C Domingo
    Microporous and Mesoporous Materials 234, 155-161, 2016

  • Hollow Microcrystals of Copper Hexafluoroacetylacetonate-Pyridine Derivative Adducts via Supercritical CO2 Recrystallization
    A López-Periago, O Vallcorba, C Domingo, JA Ayllón
    Crystal Growth & Design 16 (3), 1725-1736, 2016

  • Hybrid aerogel preparations as drug delivery matrices for low water-solubility drugs
    P Veres, AM López-Periago, I Lázár, J Saurina, C Domingo
    International journal of pharmaceutics 496 (2), 360-370, 2015

  • Hybrid aminopolymer–silica materials for efficient CO 2 adsorption
    P López-Aranguren, S Builes, J Fraile, A López-Periago, LF Vega, …
    RSC advances 5 (127), 104943-104953, 2015

  • Exploring a novel preparation method of 1D metal organic frameworks based on supercritical CO 2
    A López-Periago, O Vallcorba, C Frontera, C Domingo, JA Ayllón
    Dalton Transactions 44 (16), 7548-7553, 2015

Collaborations

uab

iit

Projects 2015-2020

  • Severo Ochoa: SEV-2015-0496 – SO18. Preparation of bifunctional nanodevices for photodynamic therapy obtained from surface anchored Metal Organic Frameworks using sustainable CO2 technology (15.07.18-31.12.19). A. López- Periago, A. Gonzalez-Campo. Budget: 60000€
  • Plan Nacional: CTQ2017-83632-C2-2-P. Materiales Nanoporosos Y Tecnología De Fluidos Supercríticos (NAMASTE) (2018-2020). IP.- López- Periago, IP: C. Domingo. Budget: 101.640 €.
  • AGAUR- 2017-SGR-171. Nanostructures per vies sostenibles (NASSOS). Grups de Recerca Consolidats (Generalitat de Catalunya)- IP: C. Domingo. 2017-2020.
  • Severo Ochoa SEV- 2015-0496. Curcuminoid-MOF-based systems to control the electronic response by reliable microscaled hybrid transistors obtained using sustainable CO2 methods MOFTrans. IP. N. Aliaga. C. Domingo.
  • Plan Nacional: CTQ2014-56324-C2-1-P. Tecnología de fluidos sostenible para la ingeniería de materiales porosos multicomponentes nanoestructurados (subp1: tecnología limpia para la nanoestructuración de productos (SUPERFACTORY) (2015-2017).
  • AGAUR- 2014-SGR-33. Nanostructures per vies sostenibles (NASSOS). Grups de Recerca Consolidats (Generalitat de Catalunya)- IP: C. Domingo. 2014-2017. Budget: 40.000 €-

European

  • EULANET- PIRSES-GA-2011-295197. Materials with environmental and industrial applications CERMAT – From: 2012- 2016. PI: JL. Brianso (UAB)

  • COST action. MPNS (OC-2011-2-10820). Rational design of hybrid organic-inorganic interfaces: the next step towards advanced functional materials- (HINT) – From: 2012- 2016. PI: Marie Helene Delville

  • NMP2-CT-2005-013524 STRP 013524. “Sustainable Surface technology for multifunctional materials (SURFACET)”. IP: C. Domingo. Dates 2005- Budget: 2M €.

Patents

  • Patent Nº: ES1641.1351_12022018.: “Procedimiento de obtención de un aerogel de óxido de grafeno”. Authors: Domingo, C.; López Periago, Ana María; Borrás Caballero, A.; Tobías Rossell, G.; Gonçalves, G.; Sandoval Rojano, S.; Fraile Sainz, J.

Books

  • Supercritical Fluid Nanotechnology: Advances and Applications in Composites and Hybrid Nanomaterials
    2015 Pan Stanford Publishing Pte. Ltd.
    ISBN 978-981-4613-40-8 (Hardcover), 978-981-4613-41-5 (eBook)

 

Outreach activities

Contact

Address

  • ICMAB-CSIC
    Campus de la UAB
    08193 Bellaterra