1.10.2015 - 30.11.2017
Dr. Gabriela Blăniţă,
Principal investigator (CV)
eng. Maria Mihet,
Dan, Team member (PhD
Oltean, Team member
Summary of the project:
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.
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.
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
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
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
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
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
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
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.
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.
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.
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;
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;
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;
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,
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.