Presentazione di PowerPoint

1
Dottorato di Ricerca in Scienze Chimiche - ciclo
XIX
November 18th 2005
Microporous materials for hydrogen storage
Supervisor Prof. A. Zecchina
PhD Student Laura Regli
2
summary
3
early results
77K

• L. Regli et al. Phys. Chem. Chem. Phys. (2005)
  7 3197
• S. Bordiga et al. J. Phys. Chem. B (2005) 109
  18237

4
and considerations
Zeolite topology plays a key role. Lower amounts
of adsorbed H2 have been obtained for zeolite
characterized by equivalent surface area but
different topology.
It is important to verify the role of zeolitic
matrix.
Boro-SSZ-13
HKUST-1
Materials lighter than zeolites and with higher
surface areas are not more efficient than
zeolites. After conflicting results, it seems
that interpenetrated structures (smaller cages)
and/or materials with transition metal ions
(specific interaction sites) could be interesting.
5
HKUST-1
6
thermal stability
HKUST-1 crystalline structure is stable until
250C (523 K).
7
oxidation state of Cu XANES spectra
Copper is present in oxidation state 2.
Coordinative state of Cu(II) ions has been
modified upon thermal treatment edge intensity
decreases and pre-edge peak at 8985 eV moves
toward low energy.
After the treatment at 453 K H2O molecule binded
to copper is removed and Cu is free to iunteract
with probe molecules.
? C. Prestipino et al. Chem. Mater. Submitted
8
effect of CO XANES ed IR spectra
CO interacts with Cu(II).
? C. Prestipino et al. Chem. Mater. Submitted
9
H2 IR spectra and volumetric measurement
n(HH) 4161 cm-1
? C. Prestipino et al. Chem. Mater. Submitted
10
H2 in microporous materials
Surface area is the parameter which determines
adsorption in microporous materials.
11
High Porosity with Appropriate Pore size
Impregnation
Concatenation
Open Metal sites
12
BH3NH3
High amount of hydrogen 19.4 wt and
143.6 g/L (volume)
Some questions Is it able to release H2 when it
is heated? At what temperature? Is the process
reversible?
Baitalow F. et al., Thermoch. Acta 2002, 391, 159
Dixon D. A. et al., J. Phys. Chem. A 2005, 109,
5129 Gutowska A. et al., Angew. Chem. 2005, 117,
2
13
BH3NH3 IR spectra
110C BH3NH3 heat ? BH2NH2 H2
150C BH2NH2 heat ? BN 2 H2
14
BH3NH3 TPD measurement
Reaction occurs in two steps
110C
150C
IR data are confirmed!
15
BH3NH3 dispersed in zeolite why?
How to promote re-hydrogenation?
Hypothesis The dispersion of BH3NH3 in a high
surface area material should allow H2 evolution
at lower temperature Better control of H2
evolution avoiding the formation of BN
The idea is to try to stop the process of
dehydrogenation when BHNH is formed. It could be
easier to re-hydrogenate!
Materials
Silicalite
Na-Y
16
BH3NH3 dispersed in zeolite results
The decomposition occurs through two steps, but
at lower temperatures
No re-hydrogenation has been observed when BN is
formed
17
work in progress

• BH3NH3 Introduction of catalyst for
  hydrogenation, i.e. Pd, in order to obtain a
  composite material

• Introduction of pores in Nafion and
  Poly-4-styrene sulfonic acid (PSSA) membranes
  through acid-base reactions.

18
acknowledgements
Prof. K. O. Kongshaug, Prof. K.P. Lillerud, Dr.
M. Bjørgen
University of Oslo - Norway
Prof. G. Guerra
Università di Salerno
Prof. S. Bordiga, Prof. A. Zecchina
Dr. C. Lamberti, Dr. F. Bonino, Dr. A. Damin, Dr
C. Prestipino
E. Groppo, J. G. Vitillo, D. Cocina, M. De La
Pierre
Università di Torino Chimica Fisica
19
Scuole e Congressi
23 marzo 2004 Politecnico di Milano Dip.
Strutturistica Giornate di studio di Metodi di
caratterizzazione dei materiali - Spettroscopie
vibrazionali 1821 Luglio 2004 Laboratoire
Catalyse et Spectrochimie ENSICAEN Post
Congress Summer School In Situ and Operando
Spectroscopy for Catalysis 19-24 Giugno 2005
Verbania-Pallanza VIII Seminario Italiano di
Catalisi Catalisi per la chimica fine una sfida
per i ricercatori, un vantaggio competitivo per
le industrie 13-16 Settembre 2004 Centro
Volta, Como III Workshop on Oxide Based
Materials 18-20 Maggio 2005 Centro Congressi
Lingotto, Torino Eco-efficiency Biennal,
International Congress og Young Scientist on
Hydrogen 18-22 Luglio 2005 Firenze XII
International Symposium on Relations between
Homogeneus and Heterogeneus Catalysis ISHHCXII
20
Poster Characterization of acidic properties of
H-SSZ-13 zeolite S. Bordiga, L. Regli, G. K. P.
Lillerud, M. Bjørgen presented at 14th
International Zeolite Conferences, Cape Town,
South Africa, April 25-30, 2004.  Acidity
properties of CHA-zeolites (SSZ-13 and SAPO-34)
a spectroscopic studyLaura Regli, Silvia
Bordiga, Adriano Zecchina, Morten Bjørgen and
Karl Petter Lillerud presented in Proceedings of
the 3rd International Workshop on Oxide Based
Materials Como, September 2004.  H2 Storage in
Microporous Materials a Comparison Between
Zeolites and MOFs L. Regli, S. Bordiga, J. G.
Vitillo, D. Cocina, C. Lamberti, G. Spoto, G.
Ricchiardi, A. Zecchina, M. Bjørgen and K. P.
Lillerud. Presented in ISHHC XII Firenze, 18-22
Luglio 2005. Presentazioni Orali Materiali
Innovativi per lo Stoccaggio e la Generazione di
Idrogeno, MISGI Materiali Innovativi per lo
Stoccaggio e la Generazione di Idrogeno
Università di Torino, Torino, 5 Luglio
2004.  Microporous Material for Hydrogen
Storage Eco-efficiency Biennal, International
Congress of Young Scientist on Hydrogen ,
Torino - Centro Congressi Lingotto, 18-20 Maggio
2005.
21
pubblicazioni
S. Bordiga, C. Lamberti, G. Ricchiardi, L. Regli,
F. Bonino, A. Damin, K.-P. Lillerud, M. Bjorgen,
A. Zecchina, Electronic and vibrational
properties of a MOF-5 metal organic framework
ZnO quantum dot behaviour, Chemm. Comm (2004)
2300-2301 S. Bordiga, L. Regli, D. Cocina, C.
Lamberti, M. Bjørgen, K.P. Lillerud Assessing the
Acidity of High Silica Chabazite H-SSZ-13 by FTIR
using CO as Molecular Probe A Comparison with
H-SAPO-34 J. Phys. Chem. B (2005) 109
2779-2784 L. Regli, S. Bordiga, A. Zecchina, M.
Bjorgen, K. P. Lillerud Acidity properties of
CHA-zeolites (SAPO-34 and SSZ-13)an FTIR
spectroscopic study Stud. Surf. Sci. Catal.
(2005) 155 471-480 S. Bordiga, J. G. Vitillo, G.
Ricchiardi, L. Regli, D. Cocina, A. Zecchina, B.
Arstad, M. Bjorgen, J. Hafizovic, K. P.
Lillerud, Interaction of Hydrogen with MOF-5 J.
Phys. Chem. B. (2005) 109 18237-18242 S. Bordiga,
L. Regli, A. Zecchina, M. Bjorgen, K. P. Lillerud
L. Regli, A. Zecchina, J. G. Vitillo, D. Cocina,
G. Spoto, C. Lamberti, K. P. Lillerud, U. Olsbye,
and S. Bordiga Hydrogen storage in Chabazite
zeolite frameworks Phys. Chem. Chem. Phys. (2005)
7 3197-3203 S.Bordiga, L. Regli, C. Lamberti. A.
Zecchina, M. Bjørgen and K. P. Lillerud FTIR
Adsorption Studies of H2O and CH3OH in the
Isostructural H-SSZ-13 and H-SAPO-34 Formation
of H-Bonded Adducts and Protonated Clusters J.
Phys. Chem. B (2005) 109 7724-7732 C. Prestipino,
L. Regli, J. G. Vitillo, F. Bonino, A. Damin, C.
Lamberti,, A. Zecchina, P. L. Solari, K. O.
Kongshaug, S. Bordiga Local structure of
framework Cu(II) in HKUST-1 metallorganic
framework spectroscopic characterization upon
activation and interaction with adsorbates Chem.
Mater. Submitted