JRP-RO-FR

PN-II-ID-JRP-RO-FR-2015-0025

- 25 Ro-Fr/14.12.2015 -

Metal doped metal-organic frameworks for energy storage

- MEMOS -

Romanian Principal investigator: Dr. Gabriela Blaniţă

French Principal investigator: Dr. Claudia Zlotea

Project financed by the Ministry of Education and Scientific Research through UEFISCDI

Program PN II: IDEI

Project type: Joint Research Project

Project Timespan: 01. 05. 2016 - 30.11. 2019

Romanian Team:

Institutul National de Cercetare-Dezvoltare pentru Tehnologii Izotopice si Moleculare - INCDTIM

Dr. Gabriela Blăniţă, Principal investigator (CV)

Dr. Dan Lupu, Team member

Dr. Diana Lazar, Team member

Dr. Oana Grad, Team member

Dr. eng. Maria Mihet, Team member

Dr. Monica Dan, Team member

Dr. Gheorghe Borodi, Team member

Dr. Ioana Grosu, Team member

eng. Ioan Misan, Team member

tehn. Sorina Ciupe, Team member

French Team:

Institute de Chimie et des Materiaux Paris-Est (ICMPE) Thiais, France

Dr. Claudia Zlotea, researcher CNRS, Principal investigator

Abdelmalek Malouche, PhD Student

Dr. Michel Latroche, director of research CNRS

Dr.Karine Provost, assistant professor

eng. Eric Leroy

eng. Julie Bourgon

Summary of the project:

The MEMOS project aims to extend the research frontiers towards novel multicomponent hybrids formed by 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) are promising 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 research that will allow the discovery of innovative materials in a field that stringently requires technological and material breakthroughs. To our knowledge, the mainstream of reports on such hybrids deals with 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.

Results:

There are various criteria that must be taken into account when choosing a MOF scaffold, such as: the textural properties, the thermal and chemical stabilities.

High specific surface area with adequate pore size distribution for hosting the metallic species, but also for the adsorption of molecular hydrogen is necessary. During the synthesis process and for the subsequent hydrogen (up)loading cycles, thermal ramps are frequently used and should not affect or weaken the crystal structure of MOF. Furthermore, the MOFs should be thermally stable and inert during the synthesis of MNPs.

Thus, MIL-100(Cr), MIL-100(Cr), MIL-100(Fe), UiO-66 and ZIF-8 were selected, synthesized and characterized by powder X-ray diffraction, nitrogen adsorption/desorption at 77.3 K, thermogravimetric analysis, hydrogen adsorption/desorption at 77.3 and 298 K and pressure up to 100 bar.

Hybrid materials based on metallic nanoparticles of Pd and Rh confined in MOFs were prepared and their structural, nanostructural and textural properties were studied. It is for the first time, to the best of our knowledge, that 1 nm Pd(5-20%) NPs were confined into a MOF. They are crystalline with the fcc structure of the bulk metal. Their hydrogen adsorption/desorption properties have been characterized by both laboratory and synchroton facilities.(http://pubs.rsc.org/en/content/articlelanding/2017/ta/c7ta07159k#!divAbstract).

We explored the cold high-pressure hydrogen storage at ~200K and 70MPa in high-pressure tank filled with MIL-101(Cr). Hydrogen adsorption/desorption isotherms for MIL-101(Cr) between 77 and 295K over an extended pressure range were measured in order to evaluate the gravimetric and volumetric storage capacities. The obtained values are within the present-day accepted DOE targets. The adsorbent presence increases dormancy more than twice as compared to the ultimate DOE targets. (https://www.sciencedirect.com/science/article/pii/S0360319918332981)

Hybrid materials, based on bimetallic nanoparticles confined in MIL-101(Cr)'s mesopores, were prepared, by suitable adaptation of the double solvent method, developed and used in the preparation of the previous prepared hybrid materials, based on monometallic nanoparticles. The criteria of selecting the bimetallic systems were the existence of a large miscibility gap with high critical temperatures (> 1000 K). Thus, the prepared bimetallic systems, based on Pd, Pt, Rh and Ir, were characterized from structural (X-ray diffraction), nano-structural (SEM, TEM) and textural (nitrogen adsorption/desorption at 77K) point of view. Their properties of hydrogen sorption were investigated by registration of pCT isotherms and thermal-desorption spectroscopy.

Also, were investigated the potential catalytic properties of monometallic composites of type M@MOF in (i) Suzuki-Miyaura coupling reaction and (ii) dehydrogenation of formic acid, which is another way to storage hydrogen.

Dissemination:

Articles:

1. Abdelmalek Malouche, Gabriela Blanita, Dan Lupu, Julie Bourgon, Jaysen Nelayah, Claudia Zlotea, Hydrogen absorption in 1 nm Pd clusters confined in MIL-101(Cr), J. Mater. Chem A 2017, 5, 23043-23052

2. G. Blanita, Hidrogenul, alternativa durabilă la combustibilii fosili, Market Watch 2018, 203, 20-21.

3. A. Malouche, C. Zlotea, P. Á. Szilágyi, Interactions of hydrogen with Pd@MOF composites, ChemPhysChem 2019, 20, 1282-1295 (https://onlinelibrary.wiley.com/doi/abs/10.1002/cphc.201801092)

4. D. Lupu, I. Coldea, I. Misan, D. Lazar, G. Blanita, Hydrogen storage potential in MIL-101 at 200K, Int J Hydrogen Energy 2019, 44(25), 12715-12723 (https://www.sciencedirect.com/science/article/pii/S0360319918332981?via%3Dihub)

Other type of articles (institute/group introduction, popularization science) :

1. G. Blanita, Hidrogenul, alternativa durabila la combustibilii fosili, Market Watch 2018, 203, 20-21)

Patent application:

1. G. Blanita, D. Lupu, O. Grad, I. Mi?an, I. Coldea, D. Lazar, G. Borodi, M. Dan, INCDTIM assignee, Green synthesis of MIL-101(Cr), Romanian patent application A 2017 010027, 5^th December 2017, RO 132757 A0.

Conferences:

1. A. Malouche, C. Zlotea, G. Blanita, D. Lupu, Proprietes de sorption d'hydrogene du MIL-101 (Cr) dope avec des clusters de Pd, 3^eme REUNION PLENIERES du GdR 3652 du CNRS HySPaC, 16^th -18^th may 2017, Limoges, France.

2. C. Zlotea, A. Malouche, G. Blanita, D. Lupu, Enhanced hydrogen storage in metal-doped MOFs, HYPOTHESIS XII, 28-30 April 2017, Syracuse, Italy - keynote speaker

3. C. Zlotea, Y. Oumellal, A. Malouche, G. Blanita, D. Lupu, Supported nanoscaled metals for energy storage and conversion, 14^th International Conference on Nanosciences & Nanotechnologies (NN17), 4-7 July 2017, Thessaloniki, Greece.

4. A. Malouche, C. Zlotea, G. Blanita, D. Lupu, Exploring the hydrogen interaction with Pd clusters supported within MIL-101(Cr) pores, AEM2017-3^rd International Conference on Hydrogen Energy, 11-13 September 2017, University of Surrey, Guildford, England.

5. I. Coldea, I. Misan, G. Blanita, D. Lazar, D. Lupu, High pressure Hydrogen adsorption on MIL-101, 11^th International Conference Processes in Isotopes and Molecules, 27-29 September 2017, Cluj-Napoca, Romania.

6. C. Zlotea, A. Malouche, G. Blanita, D. Lupu, The interaction of hydrogen with nanosized Pd clusters, 11^th International Conference Processes in Isotopes and Molecules, 27-29September 2017, Cluj-Napoca, Romania.

7. A. Malouche, C. Zlotea, G. Blanita, D. Lupu, Exploring the hydrogen interaction with Pd clusters supported within MIL-101(Cr) pores, International Conference on "Novel nanomaterial: engineering and properties" ICON2 2017, INSTN and Synchrotron Soleil, 18-20 October 2017, Saint-Aubin, France.

8. C. Zlotea, A. Malouche, G. Blanita, D. Lupu, Hydrogen absorption in 1 nm Pd clusters embedded into porous MIL-101 (Cr), 1^st International MOMENTOM Congress, Universite Paris-Saclay, 23-24 September 2017, Paris, France.

9. D. Lupu, I. Coldea, I. Misan, D. Lazar, G. Blanita, Hydrogen storage potential of MIL-101 at 200K, European hydrogen energy conference 2018 EHEC2018, 14-16 March 2018, Malaga, Spain.
10. O. Grad, M. Dan, D. Lazar, D. Lupu, G. Blanita, Greening metal-organic frameworks synthesis, 7^th EuChemMS Chemistry Congress, 26-30 August 2018, Liverpool, UK.
11. O. Grad, M. Mihet, M. Coros, M. Dan, L. Barbu-Tudoran, D. Lazar, G. Blanita, AuPd nanoparticles supported on reduced graphene oxide for dehydrogenation of formic acid, 7^th EuChemMS Chemistry Congress, 26-30 August 2018, Liverpool, UK.
12. A Malouche, O Grad, D Lupu, C Zlotea, G Blanita, The interaction of hydrogen with nanosized Pd clusters embedded in MIL-101(Cr), 12^th International Conference on Physics of Advanced Materials, 22-28 September 2018, Heraklion, Greece.
13. O. Grad, M. Dan, L. Barbu-Tudoran, D. Lazar, G. Blanita, Scalable green synthesis of chromium(III) terephthalate metal-organic framework, 12^th International Conference on Physics of Advanced Materials, 22-28 September 2018, Heraklion, Greece.
14. C. Zlotea, A. Malouche, O. Grad, D. Lupu, G. Blanita, Interacțiunea hidrogenului cu compozite de tip Pd@MOF, Zilele Academice Clujene - Sectiunea Chimie, 18-19 octombrie, Cluj-Napoca, Romania.
15. C. Zlotea, A. Malouche, D. Lupu, O. Grad, G. Blanita, The interaction of hydrogen with nanosized Pd clusters, EnergEn 2018, 24 - 26October, Băile Govora, Romania.
16. C. Zlotea, A. Malouche, G. Blanita, D. Lupu, Synthèse de nanoparticules métalliques monodisperses confinées dans les pores des MOFs et leur interaction avec l'hydrogène, Conférence MATERIAUX 2018, 19-23 Novembre, Strasbourg, France.
17. O. Grad, M. Mihet, M. Coros, M. Dan, M.D. Lazar, G. Blanita, Reduced graphene oxide modified with noble metal nanoparticles for formic acid dehydrogenation, ROMCAT 2019 - 12th International Symposium of the Romanian Catalysis Society, 5-7 June 2019, Bucharest, Romania.
18. M. Mihet, G. Blanita, M. Dan, L. Barbu-Tudoran, M.D. Lazar, Pt/UiO-66 catalysts for methanation of carbon dioxide, ROMCAT 2019 - 12th International Symposium of the Romanian Catalysis Society, 5-7 June 2019, Bucharest, Romania.
19. A. Malouche, C. Zlotea, G. Blanita, D. Lupu, Synthesis of monodispersed metal nanoparticles confined within the pores of MOFs and their interaction with hydrogen, ICH2P-2019 - The International Conference on Hydrogen Production, 15-17 May 2019, Cluj-Napoca, Romania.
20. A. Celeste, A. Malouche, F. Borondics, B. Joseph, C. Zlotea, F. Capitani, Pressure response of the metal-organic framework MIL-101 filled with metal nanoparticles, EHPRG2019 - 57th European High Pressure Research Group Meeting on High Pressure Science and Technology, Prague, Czech Republic, 1- 6 September 2019.
21. C. Zlotea, A. Malouche, W. Liu, A. Celeste, Hydrogen interaction with noble metal nanoparticles : size and composition effects, E-MRS 2019 - Fall Meeting, Warsaw, Poland 16-19 September 2019.
22. A. Celeste, A. Malouche, F. Borondics, B. Joseph, C. Zlotea, F. Capitani, Metal doped MIL-101 under pressure, WIRMS 2019 - 10th International Workshop on Infrared Microscopy and Spectroscopy with Accelerator Based Sources, Ubatuba, Brasil, 23-24 September 2019.
23. O. Grad, G. Borodi, M. Dan, D. Lazar, D. Lupu , G. Blanita, MIL-101(Cr)'s synthesis by green chemistry PIM 2019 - 12th International Conference Processes in Isotopes and Molecules, 25-27 September 2019, Cluj-Napoca, Romania.