INSTITUTUL NAŢIONAL DE CERCETARE DEZVOLTARE PENTRU TEHNOLOGII IZOTOPICE SI MOLECULARE

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PN-II-RU-PD-2012-3-0377 (PD 24/26.04.2013)

 

AlH3 nanoconfinement in porous structures for hydrogen storage

 

Project director: Dr. Gabriela Blaniţă

Mentor of Project director: Dr. Dan M. Lupu

 

 

Project financed by the Ministry of Education, Research and Innovation through CNCSIS

Program PN II: Human resources

Project type: Postdoctoral project

 

 

Project Timespan: 2013 - 2015

 

 

Project Team:

Dr. Gabriela Blăniţă, Project Manager (CV)

Dr. Dan Lupu, Mentor (CV)

 

 

Summary of the project:

Hydrogen is the ideal energy carrier in a future carbon-free energy system due to its natural abundance and non-polluting nature. The main concern of hydrogen use as a fuel is efficient storage. Hydrides are one of the main options of hydrogen storage in solid-state. Among them, aluminum hydride is very promising because has 148 g/L volumetric hydrogen density, more than double that of liquid hydrogen, and 10.1% gravimetric hydrogen capacity. Its decomposition occurs in a single step reaction, in the 60-150°C range, depending on form and structure, with a large dissociation pressure. Alane's decomposition reaction, favorable thermodynamically (ΔH=7 kJ/mol H2), is limited by kinetics. Unfortunately, this reaction is not easily reversed: extremely high H2 pressures (8.9 GPa and 600°C) are needed for re-hydriding of Al powder to AlH3. The vault key of alane utilization as hydrogen storage materials is development of a regeneration process, ideally in on-board approach, avoiding the high hydriding pressure of Al and formation of stable by-products. Nanotechnology could bring the solution. The project goal is to exploit the pore confinement and nanoscale properties for reversibility of dehydriding/hydriding reaction of alane.

 

 

Main objectives / Activities:

1) Investigation of alane nanoconfinement over reversibility of its decomposition reaction.


Nanotechnology is expected to generate new opportunities for fundamental innovations in hydrogen storage technology. There are great opportunities for the designig of hydrides at the nanoscale (nanosizing and nanoconfinement) and further potential for changes in hydrogen storage in and on solids. Nanoconfinement hinders growth and agglomeration of the nanoparticles by the compartmentalization within the scaffold template.

The attributes of matrices needed to ensure large mass fraction of nanoconfined hydrides and narrow size distribution of it are high surface area, large pore volume and regular framework. Metal-organic frameworks (MOF) and nanostructured carbon (TC) were chosen as nanoporous matrices because they possess crystalline lattice with long-range order.

High quality (high surface area, large pore volume) microporous (HKUST-1 and UiO-66) and mesoporous metal-organic framework were synthesized and characterized (PXRD, FT-IR, nitrogen adsorption/desorption at 77K, hydrogen adsorption/desorption at 77 and 298K).

Nanostructured carbons were synthesized by template carbonization technique using a template that allows pore-structure control. Their characterizations were made by PXRD, FT-IR, RAMAN, nitrogen adsorption/desorption at 77K and hydrogen adsorption/desorption at 77 and 298K.

α-AlH3 was used because is recognized as the most stable phase and at least two forms, β and γ, decompose via α-form. AlH3 was confined in pores of nanoporous matrices by impregnating via adduct and drying techniques. The obtained composites were characterized by powder X-ray diffraction, nitrogen sorption measurements at 77K, FT-IR, MAS NMR. Thermal decomposition behavior of pristine and nanoconfined AlH3 was studied by temperature programmed desorption analysis under argon pressure and by isothermal desorption kinetics measurements in a Sievert type device under hydrogen pressure.

2) Research of the metal catalysts effect on reversibility of nanoconfined alane hydriding/dehydriding.


AlH3 was confined in pores of palladium doped nanoporous matrices (MOF, template carbon) by impregnating via adduct and drying techniques. The obtained composites were characterized by powder X-ray diffraction, nitrogen sorption measurements at 77K. Thermal decomposition behavior of pristine and nanoconfined AlH3 was studied by temperature programmed desorption (TPD) analysis under argon pressure and by isothermal desorption kinetics measurements in a Sievert type device under hydrogen pressure.

 

 

Results:

Articles:

G. Blanita, G. Borodi, D. Lazar, A.-Ra. Biris, L. Barbu-Tudoran, I. Coldea, D. Lupu, Microwave assisted non-solvothermal synthesis of metal-organic frameworks, RSC Advances, 2016,6, 25967-25974 (http://pubs.rsc.org/en/content/articlelanding/2016/ra/c5ra26097c#!divAbstract)

 

Attended conferences:

G. Blanita, G. Borodi, D. Lazar, I. Coldea, D. Lupu, Nanoporous ordered structures as scaffolds for hydride nanoconfinement, The XXth edition of the "Progress in Cryogenics and Isotopes Separation" Conference, 23-24 Octomber 2014, Calimanesti-Caciulata, Romania (http://www.icsi.ro/conference/index_en.php).

G. Blăniţă, D. Lazar, G. Borodi, I. Misan, I. Coldea, D. Lupu, Nanostructured porous carbon for hydrogen storage, Processes in Isotopes and Molecules - PIM 2013, 25-27 September 2013, INCDTIM Cluj-Napoca, Romania (http://pim.itim-cj.ro/).

G. Blanita, G. Borodi, D. Lazar, M. Mihet, D. Lupu, Hybrid materials for hydrogen storage, Processes in Isotopes and Molecules - PIM 2013, 23-25 September 2015, INCDTIM Cluj-Napoca, Romania(http://pim.itim-cj.ro/).

N.P. Stadie*, G. Blanita, D. Lupu, P. Kerpen, A. Borgschulte, A. Züttel, Tuning H2/CO2 and H2/CH4 selectivity in pelletized metal-organic framework HKUST-1, Fundamental Aspects of Hydrogen Interaction with Materials and Novel Energy Applications, Gordon Research Conference on Hydrogen-Metal Systems, 12-17 July 2015, Stonehill College, Eaton, UK(https://www.grc.org/programs.aspx?id=11602).

G. Blanita, Hydrogen storage in MOFs, The XXXIVth edition of Conference "Modern Science and Energy" - SME 2015, 13-15 May 2013, Cluj-Napoca, Romania (http://conferinta.aiir-transilvania.ro/sites/default/files/fisiere-articol/PROGRAM%20SME%202015_0.pdf).

 

Collaboration:

Dr. Claudia Zlotea, Institut de Chimie et des Materiaux Paris-Est-UMR 7182, CNRS;

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