DS0205 - Stockage, gestion et intégration dans les réseaux des énergies

Metal doped Metal-Organic-Frameworks for Energy Storage – MEMOS

Metal doped Metal-Organic-Frameworks for Energy Storage

Synthesis and characterisation of novel composites based on nanoparticles of transition metals confined into the pores of different solid porous hybrids

Synthesis and characterisation of novel composites based on metal doped Metal-Organic-Frameworks for energy storage

MEMOS project (Metal doped Metal-Organic-Frameworks for Energy Storage) proposes to prepare and analyze hybrid materials formed by bimetallic nanoparticles encapsulated into the pores of Metal-Organic-Frameworks (MOFs) for energy storage applications. These multi-component hybrid materials are very innovative and they never been studied for hydrogen storage application before. The aim of the insertion of mono- and bimetallic nanoparticles into the pores of MOFs is to increase the enthalpy of adsorption of H2 by physisorption and to boost the storage capacities at room temperature. To ensure the success of the project, we propose a French-Romanian collaboration between two laboratories well recognized in the field of hydrogen storage materials: Institut de Chimie et des Matériaux Paris-Est (ICMPE CNRS France) and National Institute for Research and development of isotopic and molecular technologies (INCDTIM Roumanie).

The project is divided into 3 main tasks:
1) The first task corresponds to the synthesis of MOFs with tuneable textural properties,
2) The second task is the doping of MOFs with mono- et bimetallic nanoparticles,
3) The third task is focused on the hydrogen storage properties of both pristine MOFs and corresponding multicomponent composites.

First, we have optimised the synthetic conditions for monometallic composites based on Pd.
Once the synthesis optimised, we have preformed the characterisations of structural, nanostructural and textural properties of Pd@MIL-101 composites as function of metal doping (5-20 wt% Pd). We have prepared ultra-small Pd nanoparticles well dispersed into the pores of MIL-101 with controlled size of around 1 nm, irrespective of the amount of metal doping. To the best of our knowledge, this is the first time that ultra-small Pd nanoparticles are prepared for such high metal loadings.
Then, we have studied the hydrogen sorption properties of Pd nanoparticles by solid-gas laboratory method and X-ray absorption spectroscopy at SOLEIL synchrotron.
We have highlighted, for the first time, that such ultra-small Pd nanoparticles of 1 nm absorb hydrogen at normal pressure and temperature conditions and form solid solutions with hydrogen instead of hydride phase as bulk Pd and 2 nm Pd nanoparticles. This can be understood as a strong decrease of the critical temperature of bi-phasic domain in Pd-H phase diagram below room temperature.

We will extend the synthesis first, to other monometallic composites (based on Rh) and second to bimetallic compositions. The porous solid MIL-101 will be mainly used since its physiochemical properties are well known and we have gain now a good mastery of its use as porous solid for doping with Pd. Other MOFs are also envisaged such as, MIL-100 (Cr) and MIL-100 (Fe) (microporous).

1 submitted manuscript
3 oral communications at national and international conferences

The MEMOS project aims to extend the research frontiers towards novel multicomponent hybrids (bimetallic nanoparticles embedded into porous solids of Metal-Organic-Frameworks) for solid-state hydrogen storage.
Due to their high surface area, porous Metal-Organic-Frameworks (MOFs) show promise in the hydrogen storage field mainly at cryogenic temperature. Metal nanoparticles (MNPs) also have interesting properties for hydrogen storage due to their small particles size. Nevertheless, their combination at nanoscale level is a very recent and pioneering undertaken that will allow the discovery of innovative materials in a field that stringently requires technological and material breakthroughs. To our knowledge, the mainstream of studies on such hybrids deals with heterogeneous catalysis.
For hydrogen storage, these hybrids have the advantage of combining hydrogen absorption into MNPs and adsorption on the surface of MOFs. However, for practical hydrogen storage applications at room temperature, the enthalpy of hydrogen adsorption on porous materials must be increased. The exciting benefit of hybrid materials is the possibility of tailoring hydrogen adsorption enthalpy by synergistic effects. Indeed, two independent publications have recently reported an increase of the enthalpy of adsorption for two different hybrids based on monometallic nanoparticles.
The main originality of the project is the synthesis of multicomponent hybrids based on bimetallic nanoparticles encapsulated into MOFs for increasing the energetic of hydrogen adsorption. If gravimetric storage capacity of such hybrids might be decreased by adding MNPs as compared to pristine MOFs, the volumetric capacity can be greatly enhanced by using compressed pellets.
A considerable synthetic effort will be committed to prepare the mutlicomponent hybrids and to control the textural properties of the porous hosts together with the chemical composition and particles size distribution of bimetallic nanoparticles. Thorough characterization of these hybrids will be performed to determine their fundamental and hydrogen sorption properties. The effect of compaction on the hydrogen storage properties will also addressed. In-depth characterisations of the most promising hybrids will be performed by the help of large scale facilities.
The proposed 36 months collaboration will gather, for the first time, one French CNRS laboratory Institut de Chimie et des Matériaux Paris-Est (ICMPE) and one Romanian laboratory National Institute for Research and development of isotopic and molecular technologies (INCDTIM) around one common objective: the synthesis and characterisation of new hybrids with improved hydrogen storage capacity at room temperature via increased enthalpy of H2 adsorption. Our approach is purely academic and the success of this international project needs financial support for recruiting PhD and Master students, upgrading and maintaining the equipments, ensuring staff mobility between the two laboratories along with other operating costs. This new consortium will bring complementary competences for the success of this project that will open new directions towards the design of multifunctional nanomaterials since these materials may witness a wide range of potentialities from catalysis to optoelectronics. We strongly believe that in the near future, these hybrids will respond to the industrial needs for innovating nanomaterials.

Project coordination

Claudia ZLOTEA (Institut de Chimie et des Matériaux de Paris-Est)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.


INCDTIM National Institute for Research and Development of Isotopic and Molecular Technologies
ICMPE Institut de Chimie et des Matériaux de Paris-Est

Help of the ANR 229,503 euros
Beginning and duration of the scientific project: February 2016 - 36 Months

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