Storage and separation of gases by porous solids (S2G)

Group leader: Philip Llewellyn

Our group focuses on the fundamental understanding of adsorption on nanostructured and/or nanoporous materials, principally in view of applications in gas storage and gas separation. This work includes several aspects ranging from materials synthesis, their characterization via thermal methods and gas adsorption, to  more complex thermodynamic and structural studies of the adsorbed phase using both experimental and computer simulation methods.

Adsorption is a universal phenomenon that can be found in a wide range of domains in science and technology where nanostructured and nanoporous solids play a central role in adsorption based processes (gas storage, separation, ...). It is essential to be able to both characterize the materials involved and understand the adsorption phenomena in play. The “Separation and Storage of Gases” (S2G) group works to fill gaps in our understanding in these two areas with a focus on societal relevant applications in order to strengthen the link between blue sky research and product development.

From a fundamental standpoint, our knowledge base consists of a three pronged approach :

  • an understanding of adsorption phenomena. Here, in particular, we have developed a hand-in-hand experiment/simulation approach, in which it has been possible to interpret macroscopic experimental data via the use of different theoretical approaches including Density Functional Theory (for local structure analysis), Grand Canonical Monte Carlo (to understand thermodynamics and energies) and Molecular Dynamics (to follow adsorption kinetics).    
  • the characterization of porous solids. This has been our traditional strong point with for example, yearly specialist courses aimed at industrial participation and writing of reference books. Here, recent effort has been made to renew, upgrade and enlarge the panel of apparatus devoted to this topic. 
  • the development of unique methods to address the above two axes. A strong point in our work has been the use of microcalorimetry to gain an energetic understanding of the adsorption phenomena and/or material under study. More recently we have coupled calorimetry with structure analysis at large scale facilities (EXAFS, SXRPD) as well as developed a unique calorimetry/poromechanical set-up. 

Our unique experimental approaches are the main reason for our attractiveness, which, coupled with our knowledge base has allowed us to develop a number of strategic collaborations both nationally and internationally. These collaborations have been successful in terms of project funding and valorization (high level publications, invited talks, …). Note that several of these projects (see below) have been coordinated by the group. The research topics that we have focused on in the last few years have essentially replied to Horizon 2020 targets of ‘climate change’ and ‘energy’.

Experimental Expertise

We are able to follow gas adsorption under a wide variety of conditions :

  • Porous solids characterization : we have 6 ‘BET’ manometric experiments which operate typically at 77K and up to 1 bar. One of these is able to measure isotherms in the temperature range: 20-300K. We equally have a mercury porosimeter to evaluate larger pores than possible via adsorption manometry at 77 K.

  • Vapour adsorption : we have 3 different gravimetric set-ups of which one is able to work above atmospheric pressure. We also have a manometric apparatus which can study two samples at a time.

  • High pressure adsorption : we have 2 automatic gravimetric systems from Rubotherm able to attain 135 bars. We also have a manometric system able to attain 200 bars.

  • Mixture coadsorption : we have developed a combined manometric / gravimetric / chromatographic method to measure gas mixture adsorption.

  • High throughput : we have recently developed a manometric systems to be able to simultaneously measure isotherms on six samples up to 30 bars. We can program cycling experiments and sequential adsorption of up to 4 gases in the temperature range -10 to 120°C.

  • Mechanical milling and sieving : we are equipped with various ball mills allowing the synthesis of nanopowders (planetary, vario-planetary and vibrational milling). We can work on various kinds of powder. We also equipped with vibrational sieving that permits powder separation down to 20 µm.

  • Calorimetry : a traditional specialty of the laboratory, we are able to directly measure the enthalpies of adsorption with 8 calorimeters :

    • 2 unique calorimeters able to work at 77K
    • 2 calorimeters dedicated to vapour phase adsorption at room temperature
    • 3 calorimeters for high pressure adsorption (up to 80 bars) of which one is set-up for carbon monoxide experiments
    • 1 calorimeter dedicated to flow experiments in which we can follow water vapour and/or carbon dioxide
    • 1 differential scanning calorimeter devoted to kinetic studies under gas flow. It has been specially adapted to perform simultaneous EXAFS and calorimetric measurements at the ESRF (Grenoble).
  • We have built a portable gas dosing system which is able to be coupled with other experiments such as at large scale synchrotron or neutron facilities.

  • We also have access on site to other characterization experiments including: TGA, DSC, IR, FTIR and XRD for the further characterization of our solids.

Permanent Staff

The group currently comprises of 7 permanent staff. Over our last assessment period an average of 22 articles were published per year with an average impact factor of >4. Most of our work is carried out in the framework of national or international programs of which several are coordinated by us. The group was classed A+ by the French AERES in 2011.

Currently hosted non-permanent staff

  • Virginie Benoit is a PhD fellow (Oct. 2014 - Sept.2017) working with Isabelle and Philip on an EU project (M4CO2). She is involved in the characterization and evaluation of MOF materials for CO2 separations.

  • Nicolas Chanut worked with Sandrine and Bogdan on the effect of external parameters (water, mechanical pressure) on the adsorption and separation of gases. This PhD work (Dec. 2016) was funded by the French Government (MENRT). Nicolas will be staying on for a few months to continue his work on understanding the use of mechanical pressure on adsorption properties in compliant systems.

  • Claire Dazon works at the INRS in Nancy on a PhD in collaboration with Philip and Emily. She is working on problems linked to the characterization of nanopowders typically used in industry, their dustiness and the role of humidity on thier physical properties.

  • Pierre-Henry Esposito worked with Vanessa on the ANR ANPA project dealing with the preparation of nanoparticular aluminium via ball milling and its characterization, mostly via TGA-DTA. This work is being continued in the form of a PhD funded by the DGA.

  • Christophe Giovannangeli is a computer engineer who is developing a database to archive our adsorption data, make published data available for download and program our research into structure-property relationships. This work falls into the framework of the ANR project 'CHESDENS'.

  • Rifan Hardian is a PhD student (Nov. 2015-Oct. 2018) funded by the EU in the Marie-Curie 'DEFNET' project. He will be working, with Vanessa, on the characterization of defect engineered MOFs using low temperature calorimetry and local structure methods such as EXAFS. 

  • Paul Iacomi is a PhD student (Nov. 2015-Oct. 2018) funded by the EU in the Marie-Curie 'DEFNET' project. He will be working, with Philip, on the evaluation of defect engineered MOFs for gas adsorption and separation, in collaboration with BAT in the UK and Rob Ameloot (KU Leuven).

  • Damien Presle is an engineer (Dec. 2015-Nov. 2016) working with Isabelle and funded by the ANR 'MODS' project looking into the mechanical properties of MOFs. Damien will be staying with us to work on the EU Gramofon project dealing with the evaluation of hybrid graphene oxide/MOF materials for carbon dioxide capture.

  • Kasia Walczak is a PhD student in the Hystor project. In this project Kasia spends one year in each of three laboratories. She is currently working with Bogdan on the characterization of carbon nanosheets and their evaluation fo hydrogen uptake. 

Previous collaborators

  • Ege Dundar (2014-2016) was a post-doc funded by the ANR project 'Hystor', working with Bogdan and Philip on developing simple modeling tools for experimentalists. Ege is now in Brussels.

  • Victor Bresson (April 2014- Sept 2015) was an Engineer working with Philip on the ANR CHESDENS project where he initiated a database for our adsorption experiments.

  • Deborah Fernand (PhD MENRT Dec. 2014, ATER 2015) worked with V. Hornebecq on the synthesis of functionalized mesoporous materials in view of the adsorption of hydrogen.

  • Eder Garcia was a Post-Doc (2013) working with Bogdan in the framework of the ANR MATEX project. He was involved in the simulation of fluid transport in porous media.

  • Estelle Lenoir worked with Christelle and Philip on the effect of water on CO2 adsorption in Metal Organic Frameworks. The PhD (Dec. 2012) was funded by the EU FP7 Large project ‘MACADEMIA’. Estele now works for the DGA in Paris.

  • Ali Mohammadhosseini worked with Bogdan on the molecular modeling of hydrogen adsorption in modified nanoporous carbons. This PhD (September 2013) was funded by the French Government (MENRT). Ali is now in Italy.

  • Julien Rodriguez (ATER 2013, Post-doc 2014) worked with Isabelle and Philip on the ANR MODS project which deals with the mechanical properties of MOFs .

  • Andrew Wiersum was interested in the evaluation of Metal Organic Frameworks for gas separations. This work (PhD, December 2013) was also funded by the EU FP7 Large project ‘MACADEMIA’. Andrew now works for Exxon Mobil in Brussels.

National and International projects

  • EU 'M4CO2' (Jan. 2014-Dec. 2017) is a large-scale collaborative research project within the 7th European Framework Program for Research and Technological Development (FP7/2014, Grant Agreement n° 608490). see here for more info.

  • EU 'DEFNET' is a Marie-Curie Network (Jan. 2015-Dec.2018) for Early Stage Researchers. Here we shall be working with materials with engineered defects. We shall work on the basic characterization of these materials as well as their evaluation in gas separations. Link to the H2020 Cordis project page here.

  • EU 'GRAMOFON' (Oct 2016-March 2020) is an EU project with collaboration with South Korea. Our role in this project will be to characterize and evaluate "Graphene Oxide / MOF" composites for carbon dioxide capture. Link to the H2020 Cordis project page here.

  • ANR CHESDENS This ANR SEED project (Jan. 2014-Jun. 2017) investigates the possibility to take a QPSR type approach to the choice of the most appropriate adsorbent for various applications involving CO2 capture. The project is coordinated by Philip with partners from Montpellier (Guillaume Maurin) and Rueil-Malmaison (IFPEN, Carlos Nieto).

  • ANR 'Hystor' This project (Dec. 2014-Nov. 2017) deals with the evaluation of hybrid nanographene sheets for hydrogen storage. Experimental and modeling aspects are under consideration. This project involved Vanessa, Bogdan and Philip from the group and is coordinated by Lucyna Firlej from the Charles Coulomb Laboratory in Montpellier.

Local and Regional Projects

  • PACA Region 'EMNAVE' project provides funding for equipment to evaluate the vapour sorption properties of materials, notably for their potential use in heat pump type applications.

Recent Publication Highlights

  • MIL-91(Ti), a small pore Metal-Organic Framework which fulfills several criteria: an upscaled green synthesis, excellent water stability, high CO2 selectivity and fast CO2 transport, V. Benoit, R. S. Pillai, A. Orsi, P. Normand, H. Jobic, F. Nouar, P. Billemont, E. Bloch, S. Bourrelly, T. Devic, P. A. Wright, G. de Weireld, C. Serre, G. Maurin & P. L. Llewellyn, J. Mater. Chem. A., 2016, 4, 1383-1389. (DOI: 10.1039/c5ta09349j) [web]
  • Silica materials with wall-embedded nitroxides provide efficient polarization matrices for dynamic nuclear polarization NMR, E. Besson, F. Ziarelli, E. Bloch, G. Gerbaud, S. Queyroy, S. Viel, S. Gastaldi, Chem. Commun., 2016, 52, 5531-5533 (DOI : 10.1039/C6CC01809B) [web]

  • Mechanical energy storage performances of an Aluminum Fumarate Metal–Organic Framework, P. G. Yot,   L. Vanduyfhuys,   E. Alvarez,   J. Rodriguez,   J.-P. Itié,   P. Fabry,   N. Guillou,   T. Devic,   I. Beurroies,   P. L. Llewellyn,   V. Van Speybroeck,   C. Serre, G. Maurin, Chemical Science, 2016, 7, 446-450 (DOI: 10.1039/C5SC02794B) [web]
  • Methane storage in flexible metal-organic frameworks with intrinsic thermal management, J. A. Mason, J. Oktawiec, M. K. Taylor, M. R. Hudson, J. Rodriguez, J. E. Bachman, M. Gonzalez, A. Guagliardi, C. M. Brown, P. L. Llewellyn, N. Masciocchi, J. R. Long, Nature, 2015, 527, 357–361.
    (DOI : 10.1038/nature15732) [web]

  • Oxidation Mechanism of Aluminum Nanopowders, M.-V. Coulet, B. Rufino, P.-H. Esposito, T. Neisius, O. Isnard, R. Denoyel, J. Phys. Chem. C, 2015, 119(44), 25063-25070. (DOI: 10.1021/acs.jpcc.5b07321) [web]

  • A robust infinite Zr-phenolate building unit to enhance the chemical stability of Zr MOFs, G. Mouchaham, L. Cooper, N. Guillou, C. Martineau, E. Elkaïm, S. Bourrelly, P. L. Llewellyn, C. Allain, G. Clavier, C. Serre, T. Devic, Angewandte Chemie Int. Ed., 2015, 54(45), 13297–13301 (DOI : 10.1002/anie.201507058) [web]

  • The direct heat measurement of mechanical energy storage metal-organic frameworks., Rodriguez, J., Beurroies, I., Loiseau, T., Denoyel, R., Llewellyn P.L., Angewandte Chemie Int. Ed., 2015, 54(15), 4626-30 (10.1002/anie.201411202) [web]
  • A robust infinite Zr-phenolate building unit to enhance the chemical stability of Zr MOFs, G. Mouchaham, L. Cooper, N. Guillou, C. Martineau, E. Elkaïm, S. Bourrelly, P. L. Llewellyn, C. Allain, G. Clavier, C. Serre, T. Devic, Angewandte Chemie Int. Ed., 2015, 54(45), 13297–13301. (DOI: 10.1002/anie.201507058) [web]
  • Design of Wall-Functionalized Hybrid Silicas Containing Diazene Radical Precursors. EPR Investigation of Their Photolysis and Thermolysis, F. Vibert, S.R.A. Marque, E. Bloch, S. Queyroy, M.P. Bertrand, S. Gastaldi, E. Besson, J. Phys. Chem. C, 2015, 119(10), 5434-5439. (DOI: 10.1021/jp5117382) [web]