Energy and Adsorption of Powders and Porous Solids (EnAp)

Group leader: Sandrine Bourrelly

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 “Energy and Adsorption” (EnAP) 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 4 different gravimetric set-ups of which one is able to work above atmospheric pressure and another able to study mixtures. 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.

Currently hosted non-permanent staff

  • Luis TAPIA CASTRO is an engineer who is working with Isabelle dealing with flexible MOF materials in view of gas separations and energy storage applications. He is funded by the ANR 'Fun' project.
  • Mohammed el Amine BENCHAABANE​​​ is a PhD student working with Sandrine and Philip opn the evaluation of materials for propane/propene separations. He is funded through a bursary from Algeria.

  • Layla el HANACHE is a post-doc  working with Isabelle and Sandrine on the use of mechanical pressure to influence the adsorption properties of compliant porous materials. She is funded by the 'MEACOPA' project.

  • Sadain ZAFAR is a masters student (M2 Erasmus Mundus, Chemical Nano-Engineering) who studies the intrusion of non-wetting fluids into hierarchical porous materials with a view to energy storage.

Previous collaborators

  • Claire Dazon worked 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. P-H is now at the Institut Saint Louis, Mulhouse.

  • Rifan Hardian is a PhD student (Nov. 2015-Nov. 2018) funded by the EU in the Marie-Curie 'DEFNET' project. He worked with Vanessa, on the characterization of defect engineered MOFs using low temperature calorimetry and local structure methods such as EXAFS. Rifan has now a post-doc at KAUST, Saudia Arabia. Rifan was awarded the Prix Mahar Schützenberger in 2018. This prize given by the association of Franco-Indonesian for the development of Science (AFIDES) to some Indonesian PhD students in France. The event took place at the Indonesian Embassy for France in Paris on the 3rd May 2018.

  • Paul Iacomi is a PhD student (Nov. 2015-Nov. 2018) funded by the EU in the Marie-Curie 'DEFNET' project. He worked with Philip, on the evaluation of defect engineered MOFs for gas adsorption and separation. Paul is now a post-doc in the DAMP group at the ICG Montpellier.

  • Damien Presle was an engineer (Dec. 2015-Mar. 2019) working with Isabelle and funded by the ANR 'MODS' project looking into the mechanical properties of MOFs. Damien stayed on with us to work on the EU Gramofon project dealing with the evaluation of hybrid graphene oxide/MOF materials for carbon dioxide capture. Damien is now working at the French Defense Agency.

  • 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. Kasia is now in Pau.

  • Virginie Benoit is a PhD fellow (Oct. 2014 - Dec. 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.

  • 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.

  • 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 is now at the MultiScale Material Science for Energy and Environment lab at MIT.

  • 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.

  • 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.

  • Christophe Giovannangeli is a computer engineer developped 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'.

  • 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’. Estelle 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 Baton Rouge (USA).

National and International projects

  • 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. Sandrine, Emily and Philip are involved in this project. Video link 
  • ANR 'CHARMING' (Oct 2018-  )This project is in collaboration with the group of S. Gastaldi. Our role in this project is to characterize the behaviour and stability of materials towards water. Emily is the PI of this project at MADIREL.

  • ANR 'FUN' (May 2018- ) This project aims to gain information concerning the fundamental understanding of negative gas adsorption in DUT-49 and related materials. The project is coordinated by Sabine Devautour-Vinot (Uni. Montpellier) and is in collaboration with S. Kaskel (TU Dresden). Philip, Isabelle, Vanessa and Sandrine are involved in this project.

  • ANR 'MEACOPA' (Oct. 2018-Sept. 2021) This project explores the mechanical control of porosity to modulate the separation and storage properties of target molecules. This project is coordinated by G. Maurin (Uni. Montpellier) and is in collaboration with C. Serre (ENS/ESPCI, Paris). Philip, Isabelle, Vanessa and Sandrine are involved in this project.

  • DGA 'Characterization of filter materials' (June 2018-  ) This project is a direct collaboration with the French Army and deals with the characterization of current and potentially new filter materials. Emily and Philip are involved in this project.


Local and Regional Projects

  • PACA Region 'AENA' project centred on the Energetic applications of aluminium nano-petals
  • 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

  • Adsorption Contraction Mechanics: Understanding Breathing Energetics in Isoreticular Metal-Organic Frameworks, S. Krause, J.D. Evans, V. Bon, I. Senkovska, S. Ehrling, U. Stoeck, P. Yot, P. Iacomi, P. Llewellyn, G. Maurin, F.-X. Coudert, S. Kaskel, J. Phys. Chem. C, 2018, 122(33), 19171-19179 (DOI. 10.1021/acs.jpcc.8b04549)
  • A promising metal-organic framework (MOF), MIL-96(Al) for CO2 separation under humid conditions, V. Benoit, N. Chanut, R. S. Pillai, M. Benzaqui, I. Beurroies, S. Devautour-Vinot, C. Serre, N. Steunou, G. Maurin, P. L. Llewellyn, J. Mater. Chem. A, 2018, 6, 2081-2090 (DOI. 10.1039/c7ta09696h)
  • Revisiting the Aluminum Trimesate-based MOF (MIL-96): from Structure Determination to the Processing of Mixed Matrix Membranes for CO2 Capture, M. Benzaqui, R.S. Pillai, A. Sabetghadam, V. Benoit, P. Normand, J. Marrot, N. Menguy, D. Montero, W. Shepard, A. Tissot, C. Martineau-Corcos, C. Sicard, M. Mihaylov, F. Carn, I. Beurroeis, P.L. Llewellyn, G. De Weireld, K. Hadjiivanov, J.Gascon, F. Kapteijn, G. Maurin, N. Steunou,  C. Serre, Chem. Mater., 2017, 29 (24), 10326–10338 (DOI. 10.1021/acs.chemmater.7b03203)

    Adsorption induced structural phase transformation in nanopores, B. Kuchta, E. Dundar, F. Firmalik, P. L. Llewellyn & L. Firlej, Angewandte Chemie Int. Ed., 2017, 56(51), 16243–16246 (DOI. 10.1002/ange.201708993)

  • Investigating Unusual Organic Functional Groups to Engineer the Surface Chemistry of Mesoporous Silica to Tune CO2–Surface Interactions, E. Bloch, E. Besson, S. Queyroy, R. Llewellyn, S. Gastaldi, P.L. Llewellyn, ACS Appl. Mater. Interfaces, 2017, 9(16), 14490–14496 (DOI. 10.1021/acsami.7b0090)

  • 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]

  • 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]