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INSTITUTUL NAŢIONAL DE
CERCETARE DEZVOLTARE PENTRU TEHNOLOGII IZOTOPICE SI MOLECULARE Str. Donat 67-103, 400293, Cluj-Napoca, Romānia Tel: +40-264-584037; Fax: +40-264-420042 Email: itim@itim-cj.ro, web: www.itim-cj.ro |
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INSTITUTUL NAŢIONAL DE
CERCETARE DEZVOLTARE PENTRU TEHNOLOGII IZOTOPICE SI MOLECULARE Str. Donat 67-103, 400293, Cluj-Napoca, Romānia Tel: +40-264-584037; Fax: +40-264-420042 Email: itim@itim-cj.ro, web: www.itim-cj.ro |
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PN-II-RU-TE-2014-4-1326
- 143 din 01/10/2015 -
Formic acid/carbon dioxide, a couple for renewable catalytic hydrogen storage
- ADORHy -
Principal investigator: Dr. Gabriela Blaniţă
Project financed by the Ministry of Education and scientific Research through UEFISCDI
Program PN II: Human resources
Project type: TE (Research projects to stimulate the formation of young independent research teams)
Project Timespan: 1.10.2015 - 30.11.2017
Dr. Gabriela Blăniţă, Principal investigator (CV)
Dr. Diana Lazar, Team member
Dr. Camelia Grosan, Team member
Dr. Maria Coros, Team member
Dr. eng. Maria Mihet, Team member
Dr. Adriana Vulcu, Team member
Monica Dan, Team member (PhD Student)
eng. Ioan Coldea, Team member
tehn. Sorin Oltean, Team member
The growing need for energy requires development of new energy sources/carriers and more efficient utilization of energy. Hydrogen is the ideal energy carrier due to its natural abundance and non-polluting nature. The development of hydrogen storage technologies for mobile applications still requires overcoming some technical barriers. Different hydrogen storage paths have been envisaged: from the classical storage technologies, namely pressurization and cryogenic liquefaction, to the solid phase storage in metal hydrides, or physisorbed on a solid surface (metal-organic frameworks, covalent organic frameworks) and the organic liquid hydrogen carrier (LC) under ambient conditions.
Chemical hydrogen storage can become competitive if the storage material fmeets some requirements: high gravimetric and volumetric hydrogen content under ambient conditions, energy-efficient reversible charge and discharge, the absence of byproducts, long-term stability, low toxicity, easily available at a large scale and at a low price. The challenge is to find suitable organic carriers.
Formic acid is a promising candidate for reversible hydrogen storage. The aim of this project is to study formic acid decomposition/formation using a new type of catalysts: metallic nanoparticles confined in metal-organic frameworks, to exploit the nanoparticles confinement and the nanoscale properties for reactions of formic acid dehydrogenation and carbon dioxide reduction under mild conditions.
Preparation and characterization of MNPs@MOF type catalysts.
Study of MNPs@MOF catalytic properties for dehydrogenation of formic acid: determination of catalytic activity, selectivity for desired products, catalysts deactivation and regeneration, etc.
Study of MNPs@MOF catalytic properties for the reduction of carbon dioxide with hydrogen in order to produce formic acid: determination of catalytic activity, selectivity for desired products, catalysts deactivation and regeneration, etc.
Work package 1 (month 1-23)
Catalysts based on metallic nanoparticles confined in metal-organic frameworks (MOFs) and nanostructured carbons (NCs) were prepared. Their preparation process implied:
(i) Synthesis of metal-organic frameworks, preparation of nanostructured carbons and their characterization. High quality MOFs (MIL-101, MIL-100(Fe), UiO-66, HKUST-1) and nanostructured carbon (templated carbon, graphene) were synthesized/prepared and caracterizated by powder X-ray diffraction (PXRD), nitrogen adsorption/desorption at 77K, thermogravimetric analysis (TGA), Scanning Electron Microscopy (SEM).
(ii) Preparation and Characterization of catalysts. The supported Pd@MOF and Pd@NC catalysts were prepared through solution infiltration of palladium precursors followed by reduction with desirable reduction agents (NaBH4, citric acid etc) and/or with hydrogen. The catalysts are structurally characterized by: PXRD, N2 sorption/desorption at 77K, TGA, Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS).
Work package 2 (month 5-20)
The catalytic activities of the prepared hybrid materials were tested in formic acid (FA) dehydrogenation. The optimum reaction conditions (temperature, reaction time, reactant/catalyst ratio etc.) were determined. The influence of parameters such as reaction temperature, Pd:FA molar ratio, concentration of FA, catalyst reusability, formic acid : sodium formate (FA:SF) ratio were studied.
Work package 3 (month 17-26)
The catalytic activities of the selected hybrid materials were tested in carbon dioxide reduction. If they had catalytic activity, the aim was to determine the optimum reaction conditions (temperature, reaction time, reactant/catalyst ratio etc.).
Articles:
M. Mihet, M. Dan, L. Barbu-Tudoran, D. Lazar, G. Blanita, Controllable hydrogen generation by formic acid decomposition on a novel Pd/templated carbon catalyst, Applied Catal. A, under review;
O. Grad, M. Mihet, M. Dan, G. Blanita, T. Radu, C. Berghian-Grosan, M.D. Lazar, Au/reduced graphene oxide composites: eco-friendly preparation method and catalytic applications for formic acid dehydrogenation, J. Mater. Sci. 2019, 54, 6991-7004. https://link.springer.com/article/10.1007/s10853-019-03394-y
Conferences:
C. Grosan, A. Vulcu, G. Blanita, G. Borodi, The 11th International Symposium of The Romanian Catalysis Society Simpozion - RomCat 2016, 6-8 June 2016, Timişoara, Romania.
M. Mihet, D. Lazar, G. Borodi, G. Blanita, Hybrid materials based on MOFs for hydrogen production from formic acid, Progress in Cryogenics and Isotopes Separation 2016, 19-21 October 2016, Călimăneşti, Romania.
M. Mihet, A. Vulcu, O. Grad, M. Dan, L. Barbu-Tudoran, G. Borodi, D. Lazar, G. Blanita, MOF-based catalysts for hydrogen production from formic acid, The 5th International Conference on Multifunctional, Hybrid and Nanomaterials, 6-10 March 2017, Libon, Portugal; http://www.hybridmaterialsconference.com/
M. Mihet, |D. Lazar, G. Blanita, Catalytic dehydrogenation of formic acid on Pd/templated carbon, The 13th European Congress on Catalysis, 27-31 August 2017, Florence, Italy; http://www.europacat2017.eu/
O. Grad, M. Mihet, M. Coros, M. Dan, L. Barbu-Tudoran, G. Borodi, G. Blanita, MOF-based catalysts for hydrogen production from formic acid, The 11th International Conference Processes in Isotopes and Molecules, 27-29 September 2017, Cluj-Napoca, Romania; http://pim.itim-cj.ro/
M. Dan, A. Vulcu, M. Mihet, D. Lazar, G. Blanita, Graphene-based catalysts for efficient hydrogen generation from formic acid, The 11th International Conference Processes in Isotopes and Molecules, 27-29 September 2017, Cluj-Napoca, Romania; http://pim.itim-cj.ro/
D. Lazar, D. Lupu, G. Blanita, I. Coldea, Hydrogen storage-an essential step in future hydrogen economy, Workshop on green energy, 24-26 October 2017, INCDTIM, Cluj-Napoca, Romania.
