Magazynowanie wodoru. Kataliza niskotemperaturowego wydzielania wodoru.
A. Dlaczego wodór?
B. Trochę historii.
C. Stan obecny zagadnienia.
D. Przyszłość.
E.
Najważniejsze problemy i wyzwania. Zalety magazynowania w fazie stałej.
F.
Jak może pomóc teoria?
(i) Właściwości fizyczne i chemiczne wodoru.
(ii) Kontrola temperatury rozkładu wodorków binarnych. Przewidywania modelu.
(iii) Rozszerzenie na wodorki ternarne.
(iv) Kataliza heterogeniczna; synteza mechanochemiczna i klasyczna.
G. Dowiedz się więcej.

THE DREAM

Combustion of fossil fuels & other:
Coal
Petrol /mineral oil/
 gas(oline)
Methane /natural gas/
Recycled tires, etc.
Renewable energies:
Solar energy
Wind energy
Geothermal energy
Hydroenergy
Nuclear energy:
Nuclear reactor
-
“Cold fusion”
Greenhouse gas (CO
2
)
Other pollutants (SO x
, NO x
Big politics etc.)
Oil plots, oil wars, etc.
Limited amount
Limited geopolitics
Landscape preservation issues
Radioactive pollutants
“Atomic bomb” risk

- Hydrogen is the lightest of the elements with an atomic weight of 1.
- Liquid hydrogen has a very small density of 0.07.
- The advantage is that H stores approximately 2.6 times the energy per unit mass as gasoline.
- The disadvantage is that it needs about 4 times the volume for a given amount of energy. a 15 gallon automobile gasoline tank contains 90 pounds of gasoline; the corresponding H tank would be 60 gallons, of weight of only 34 pounds
When hydrogen is burned in air the main product is water (some nitrogen compounds may also be produced and may have to be controlled
- Should greenhouse warming turn out to be an important problem, the key advantage of hydrogen is that carbon dioxide is not produced when hydrogen is burned.

Other ways:
- physisorption (glass, sponges etc.)
- liquid (price, volume, T<250 K tanks)
L. Schlapbach, A. Züttel,
Nature 414 , 353 (2001).
- compression (price, volume, permeability of containers, pressure now up to 800 bar)

1937
1986
2001
?

1999
USA C
51.0
ENERGY nuclear, hydroelectric, wind, solar, biomass, geothermal
CH
2.25
CH
4 other
3.2
15.2
30.0
CO
2
EMISSION 79.6
OUTPUT
RATE
/pounds
CO
2 per
1 kWh
2.12
1.92
1.31
4.7
15.0
0.00

1998
USA
C
TOTAL CO
2
EMISSION
36.4
CH
2.25
41.7
other
CH
4
20.8
DIRTY AND CLEAN ENERGY
31.3
15.9
23.8
16.0
13.0
CONTRIB. TO THE TOTAL
ENERGY GENERATION
C 68%
H 32%




Based on statistical data, and on prognosis of LH price,
H is to take 5% of global oil market in 2010

Global oil market is $ 700 bln/year

H is to take $ 35 bln/year

Tanks with MHS are thought to take $ 5 bln/year

Invention may be sold or licensed for
USA
Freedom /$ 150 mln incl.
$ 40 mln government share/
EUROPE
Fuchsia, Hystory,
Hymosses /$ 10 mln/
(fuel cells $ 340 mln!)
JAPAN
Protium /$ ??? mln/
WE-NET /$ 4 mln p.a./

16th century – F. B. Paracelsus (Swiss…) first described an air which bursts forth like the wind
1671 – Robert Boyle published a paper in which he described the reaction between iron filings and dilute acids which results in the evolution of gas
1766 – Henry Cavendish discovers “inflammable gas from metals”
(Lavoisier gives the name for it in 1783)
1783 – J. A. C. Charles suggests using hydrogen in balloons
Nov.25, 1793 – the first balloon is sent up from
British soil
1807 – Dalton’s theory of atoms is published; was the symbol used for hydrogen
May 6, 1937 – the Hindenburg tragedy
Jan. 28, 1986 – the Challenger space shuttle catastrophe
1980’s – numerous explosions in the diborane factories
1839 – William Robert Grove invents fuel cell
1960 ’s – NASA searches for energy supplies for the spacecraft
1998
–2000 Ballard Power Systems introduces 205 kW fuel cells being used in six buses in the U.S. (Chicago) and Canada (Vancouver)
May 1999 – the first public liquid–hydrogen filling station has been opened in at Munich Airport
Feb. 2001 – Eur. Comm. funds the FUCHSIA Project
Feb. 2001 – a six-month tour of a fleet of ten BMW
750hL liquid hydrogen powered sedans around the globe starts in oil–producing Dubai (UAE)
Aug. 2001 – the first solar-powered hydrogen production and fueling station in the Los Angeles area opened by
American Honda Motor Co.
2003 – Toyota Motor Co. is poised to be the first to offer a pure-hydrogen fuel cell vehicle to a limited public
2010/2020 – mass production of the fuel cell-powered vehicles is expected

•
CH
4
+ 2 H
2
O

CO
2
+ 4 H
2
•
C–H bond activation
Hydrogen production
H
2
(gas)
• photoelectrochemical generation
(electrolysis of water), green energy
Hydrogen storage
• high–pressure cryogenic tanks chemical reactions
H
2
(compressed) H
2
(liquid) H (solid chemicals)
Hydrogen combustion
(Hybrid) engine H
2
/O
2
Fuel cell
Zero–emission vehicle

Effects for the planet of the increased water circulation = ???

Budowa Ogniwa Paliwowego (Fuel Cell).
ANODA /Pt Nafion® KATODA /Pt
Energia chemiczna

Energia elektryczna małe straty cieplne, duża wydajność w por. z cyklem Carnota

Rodzaje ogniw paliwowych H
2
/O
2
:
Alkaliczne (150–200 o C) – wymagają użycia bardzo czystego H
2 i O
2
Na kwas fosforowy (150–200 o C) – głównie średnie do dużych aplikacji stacjonarnych
Na stały tlenek (1000 o C) – ogniwa ekstremalnie wysokotemperaturowe, tolerują względnie zanieczyszczone paliwa wodorowe
Z membraną wymieniającą proton (Proton Exchange Membrane) lub polimerowo–elektrolitową (Polymer Electyrolyte) Fuel Cell (60–100 o C) – najbardziej rozwinięty rodzaj ogniw, największa ilość energii na jednostkę objętości ogniwa, najprawdopodobniej jedyny kandydat do zasilania środków transportu przyszłości
Na stopiony węglan (650 o C) – ogniwa wysokotemperaturowe, mogące używać bezpośrednio paliwa kopalnego, lub nawet CO
Protonowo–ceramiczne (700 o C) – używa bezpośrednio paliw kopalnych
Bezpośrednie ogniwa metanolowe (50–100 o C) – przyszłość w małych zastosowaniach moblinych
Zn/powietrze
– niski koszt, względna nieodwracalność, użycie w armii

Stacjonarne FC
Transport/bus FC
Przenosne FC Cell.Ph. FC
Laptop FC

Anchorage /Alaska/

• Yesterday:
• Today:
• Tomorrow:
Car of the future: BMW 750 hL presented during EURO 2000
BMW 750 hL (München 2000)
6 fuel-cell busses (Chicago & Vancouver 1999-2001) the first commercial Honda & Toyota (Japan & California 2002/3) cheap fuel cells, cheaper H
2
(US & Canada 2010)
Who does not pick up this subject NOW, most probably would not have chance to work on it at all.

(i) High storage capacity : minimum 6.5 wt % abundance of hydrogen and at least 65 g/l of hydrogen available from the material;
(ii) T dec
= 60–120 o C ;
(iii) Reversibility of the thermal absorption / desorption cycle: low temperature of hydrogen desorption and low pressure of hydrogen absorption (a plateau pressure of the order of few bars at room temperature), or an ease of nonthermal transformation between substrates and products of decomposition;
(iv) Low cost ;
(v) A nontoxic, nonexplosive , inert etc., storage medium.

1. PdH
0.6
: 0.6 wt%, excellent reversibility, $ 1000/oz, >$1mln/1kg H
2. NaH: 4.2 wt%, good reversibility, T dec
> 425 o C
3. NaAlH
4
& TiO
2
: 5.5 wt%, T dec
> 125 o C, reversibility OK
4. MgH
2
: 7.6 wt%, T dec
> 330 o C, poor reversibility
5. “Li
3
Be
2
H
7
“: 8.7 wt %, T dec
> 300 o C, toxicity, cost
6. NaBH
4
/H
2
O
(l)
: 9.2 wt%, expensive Ru catalyst, no reversibility
7. AlH
3
: 10.0 wt %, very cheap Al, T dec
> 150 o C, no reversibility
8. H
2
O
(l)
: 11.1 wt%, liquid, thermal decomposition difficult
9. MeOH
(l)
: 12.5 wt%, toxic liquid, activation difficult
10. LiH: 12.6 wt%, T dec
> 700 o C
11. NH
3(l)
: 17.6 wt%, large N – H bond activation barrier
11. BeH
2
: 18.2 wt%, extremely toxic, T dec
> 250 o C, no reversibility
12. CH
4
: 25.0 wt%, gas, thermal activation very difficult
13. Carbon nanotubes: ??? Wt%, ???
Compare to Mg
2
NiH
4
: 3.6 wt% (ii, iii, iv, v)
(ii,iii, v)
(iii, iv, v)
(ii, iii, iv, v)
(i, iv, v)
(i, iii)
(i, ii, iv, v)
(i, iv, v)
(i, iii, iv, v)
(i, iv)
(i, iv, v)
(i, iv)
(i)
(i, iv)
(i, ii, iii, v?)

80
60
40
20
0
0
160
140
120
100
5 10 15 gravimetric H content [wt%]
20 25

Problems with setting of the position of H in the periodic table of chemical elements
H as H + :
• H’s I
P is similar to that for Cl.
• “Dimension” of proton is very different depending on the solvating agent; spectrum of energies of
H bond is very broad.
H as H 0 .
• It is a gaseous nonmetal. Has never been metallized in the solid state.
• H radical has enormous tendency for pairing.
Bonding energy is 436 kJ/mole, and it is slightly smaller than those of O
2
P
2
.
or
H as H
–
:
• Creates metal hydrides (H as hydride anion) much easier than other Group 1 elements.
• Dimension of H
– is very susceptible to the polarization properties of the metal, and most often it is in between of those for Cl
– and F
–
.
Difference of properties for three available oxidation states of H is the largest among all chemical elements at their typical oxidation states
(derivative of energy upon charge is large).

2
Reaction path for evolving H
2 from a H–containing material. Elongation of the M–H bonds occur along R
M–H coordinate, and the pairing of two H atoms in a H
2 molecule proceeds along the R
H–H coordinate. The actual reaction coordinate is a combination of these two.

E /eV
+13.60
0.0
-
0.75
+1
H
-
I /H
2 or H +1 /H
2
I
P
/kJ mol
–1
E
A
/kJ mol
–1
I
P
/kJ mol
–1
E
A
/kJ mol
–1
H
1312
Li
520.2
H
72.8
Li
59.6
H
1312
F
1681
H
72.8
F
328
Na
495.8
K
418.8
Rb
403.0
Cs
375.7
Na
52.8
K
48.4
Rb
46.9
Cs
45.5
Cl
1251.2
Br
1139.9
I
1008.4
At
920
Cl
349
Br
324.6
I
295.2
At
270.1 n
0
-
1
H +
H 0
H
–
Fig.2. The dependence of the electronic energy of the H n
species on the oxidation state of hydrogen, n. The hardness (the derivative of energy on the electron density) is schematically shown as dotted lines. Note that the hardness of H n
species strongly decreases in the direction:
H
I+
> H
0
> H
I–
.

1
1 1
H
2 3
Li
3 11
Na
4 19
K
5 37
Rb
6 55
Cs
7 87
Fr
2
Sr
56
Ba
88
Ra
4
Be
12
Mg
20
Ca
38
3
21
Sc
39
Y
71
Lu
103
Lr
57
La
89
Ac
4
22
Ti
40
Zr
72
Hf
Rf
58
Ce
90
Th
Db
59
Pr
91
Pa
5
23
V
41
Nb
73
Ta
6
24
Cr
42
Mo
74
W
Sg
7
N
3
Li
5
B
85
At
1
H
7
25
Mn
43
Tc
75
Re
Bh
8
60
Nd
92
U
61
Pm
93
Np
Niemetal
62
Sm
94
Pu
Metal
26
Fe
44
Ru
76
Os
108
Hs
9
27
Co
45
Rh
77
Ir
109
Mt
63
Eu
95
Am
10 11 12 13 14 15 16 17 18
2
5 6 7 8
H
9
He
10
28
Ni
46
Pd
78
Pt
110
Uun
29
Cu
47
Ag
79
Au
111
Uuu
30
Zn
48
Cd
80
Hg
112
Uub
B
13
Al
31
Ga
49
In
81
Tl
113
Uut
C
14
Si
32
Ge
50
Sn
82
Pb
114
Uuq
N
15
P
33
As
51
Sb
83
Bi
115
Uup
O
16
S
34
Se
52
Te
84
Po
116
Uuh
F
17
Cl
35
Br
53
I
85
At
117
Uus
64
Gd
96
Cm
65
Tb
97
Bk
Zmetalizowany tylko w fazie ciekłej
66
Dy
98
Cf
Niemetal zmetalizowany pod wysokim p
67
Ho
99
Es
Brak prób, teoretycznie w zasięgu metalizacji
68
Er
100
Fm
69
Tm
101
Md
70
Yb
102
Nb
Ne
18
Ar
36
Kr
54
Xe
86
Rn
118
Uuo

Which species are to be involved in the charging/recharging process of the Hydrogene Storage Material?
H
–1 
H +1 + e
H
-
0
+ e
-

H 0
2 H 0

H
H +1 + H
-
1
2

H
2
(

H 0 = +0.75 eV)
(

H 0 = –13.60 eV)
(

H 0 = –4.52 eV)
(

H 0 = –17.37 eV)
(1a)
(1b)
(1c)
(1d)
•
It should be easy to play the H
-
I /H
2 equilibrium;
•
It is much more difficult to play the H +1 /H
2 one;
•
It is quite difficult to play the 2H 0 /H
2 equilibrium;
• It is the most difficult to play the (H +1 ,H
–1
)/H
2 one.

Standard enthalpies of formation

H f
0
[kJ/mol] of binary hydrides of the main group elements.
MH
Li
-116.3
Na
-56.5
K
-57.7
Rb
-52.3
Cs
-54.2
MH
Be
Mg
Ca
Sr
Ba
2
-18.9
-75.2
-181.5
-180.3
-177.0
MH
3
B
[1]
+36.4
Al
-46.0
+92
[1,2]
Ga
???
[3]
+118
[1,2]
In
???
[3]
+175
[1,2]
Tl
#
???
[3]
+245
[1,2]
MH
C
4
-74.6
Si
+34.3
Ge
+90.8
Sn
+162.8
Pb
+181.1
[2]
+251.5
[4]
MH
N
-45.9
P
+5.4
As
Sb
Bi
+230.6
3
+66.4
+145.1
[4]
MH
O
2
-285.8
S
-20.6
Se
+29.7
Te
+99.6
Po
+188.6
[4]
MH
F
-273.3
Cl
-92.3
Br
-30.3
I
+26.5
At
+104.8
[4]
[1]
[2]
Molecular dimer, M
2
Theoretical value.
H
6
.
[3]
Value for solid hydride is not known. This hydride certainly decomposes below 0 o
C, and a

H
(standard conditions) cannot be measured.
[4]
Extrapolated from experimental values.
f
0
value

Chemical rationale behind the metal/hydrogen avoided crossing curve.
Size, electric charge, orbital energy, hardness, and standard redox potential.
molecule R
0
/Å q(H)/e HOMO/eV
M n+ + n H
-
1

M + n/2 H
2 atom R cat
/Å E 0 /V T dec
/ o C

Electronegativity vs the total charge & substituents
B 0 > B Ga + > Ga 0 > Ga
–
Zn +2 > Zn
–2
[BH
3
+40 o
]
2
< LiBH
C, +275 o
4
C
[GaH
2
][BH
4
] < [GaH
3
]
2
< LiGaH
4
–35 o C, –15 o C, 50 o C
[AlH
3
] < Li[Al
2
H
7
–
] < LiAlH
4
150 o C, 160 o C, 165
[InH
3
???
] < InH
, –30 o C
4
–
MgH
2
[ZnH
2
+90
< Sr
2
[MgH o
] < K
2
[ZnH
C, +407 o C
4
]
6
] < Ba
2
[MgH
327, 377, > 427 o C
6
]
[GaH][BH
4
]
2
< [GaH
2
][BH
4
] < [GaH
3
]
2
< LiGaH
4
–73 o C, –35 o C, –15 o C, +50 o C
Na
2
[BeH
4
] > [BeH
2
] > Be[BH
4
]
2
+380 o C, +250 o C, +25 o C
Ga +3 > GaCl 2+ > GaCl
2
1+
[GaH
3
]
2
< [GaClH
2
]
2
< [GaCl
2
H]
2
–15 o C, –15 o C, +50 o C
Zn +2 > ZnI 1+
[ZnH
2
] < [ZnHI]
+90 o C, +110 o C
[Bi 5+ ] > [BiCl
4
1+ ] unknown, [BiCl
4
1+ ][H 1– ] known as
H 1+ Bi III Cl
4
As +5 > AsPh
4
1+
[AsH
5
] < [AsPh
4
H]
???
, obtained

M
2
Na, & Sr
2
M
2
Pd 0 H
2
M=Li,
Pd II H
4
M=K,
Rb, Cs (1.625–
1.64 Å )
M
2
Pt II H
4
K, Rb, Cs
M=Na,
(MH)
2
Pt II H
4
M=Sr, Ba
M
2
Pt IV H
6
M=K,
Rb, Cs
Pd 0 H
4
(1.674–1.676 Å) d d d
10
8
6
= Au
= Au
= Au
1+
3+
5+
[AuCl
[AuCl
[AuF
6
–
2
–
4
–
]
]
]
800
700
600
Li +
Ba 2+ , Sr 2+
Ca 2+
500
Na +
400
Er 3+
300
Mg 2+
Y 3+
Be 2+ , Pu 3+
200
U 3+
Al 3+
100
0
V 2+
Ga
Zn 2+
B 3+
P 3+
3+ Cd 2+
Sn 4+
Sb 3+
-100
H
2
/2H
-
H 0
·
/H
-
Hg 2+
-200
-3.5
-2.5
-1.5
-0.5
0.5
1.5
E
0
/ V
BaRuH
9
Cs
3
RuH
10
RuH
7
& vs
Mg
2
FeH
6
FeH
2 vs
M
2
PtH
6
PtH
4
… vs
[M III H
4
1– ],
M=Cr, Eu, Yb
[CdH
????????
[HgH
[PtH
6
]
4
2–
4
2–
]
]

Predictions of the T dec vs E
0 relationship for binary hydrides
Hydride Redox pair E
0
/V T dec
/ o
C Hydride Redox pair E
0
/V T dec
/ o
C
ScH
ZrH
PaH
[1]
3
[1,3]
ThH
HfH
4
4
[1]
4
[1]
4
[5]
YbH
TaH
UH
TiH
3
[2]
5
[1]
4
3
[1]
Sc
Th
IV
Hf
Zr
Pa
III
IV
IV
IV
/Sc
0
/Th
/Hf
/Zr
0
/Pa
0
0
III
EuH
InH
PH
5
3
[1]
[1]
3
[2]
VH
WH
4
3
[1]
H
Eu
In
III
III
3
PO
V
4
III
/H
/V
WO
2
/Eu
/In
3
II
/W
0
II
PO
3
0
PaH
5
PaO(OH)
2
+
/Pa
-
0.35 15
-
0.338 15
-
0.276 11
IV
-
0.255 10 MoH
-
0.119 1
-
0.1 0
AsH
5
H
3
TeH
4
AsO
Te
4
IV
/HAsO
2
+0.560 -68
/Te
0
+0.57 -69
SbH
NpH
6
5
[1]
AtH
5
Sb
H
2
2
O
5
NpO
2
/SbO
+
+0.605 -75
MoO
+
4
/MoO
/Np
IV
HAtO/At
0
2
+0.646 -82
+0.66
+0.7
-84
-91
NbH
5
[2]
Yb
Ta
U
Ti
Nb
2
III
V
/Yb
/Ta
IV
/U
III
III
/Ti
O
5
0
II
/Nb
II
II
-
2.03 239 WH
-
1.83 185 TiH
-
1.70 156 SH
-
1.55 127
-
1.46 113 UH
6
[1,2]
[1]
6
4
[4]
WO
NpH
6
4
[1]
TiO
HSO
Np
UO
3
4
IV
/W
-
2
/H
/Np
2
2+
/Ti
2
2
O
III
SO
III
/U
IV
5
-
0.029
3
+0.1
-5
+0.16 -21
+0.18
+0.27
-15
-22
-31
-
1.05
-
0.81
-0.52
-
0.37
-
0.1
63
43
25
16
0
BiH
TlH
3
3
PoH
2
[1]
UH
SH
5
4
[4]
Bi
Po
UO
H
2
Tl
III
II
2
III
+
/Bi
0
/Po
/U
SO
3
/Tl
0
0
IV
/S
0
+0.317
+0.37
+0.38
+0.50
+0.72
-36
[6]
-42
-44
-59
-95
[1]
Species isolated in the noble gas matrixes.
[2]
Organophosphine–stabilized hydrides have been obtained.
[3]
Mixed–valence hydrides exist (Th
4
H
15
, Yb
3
H
8
, Eu
[4]
Theoretical predictions of kinetic stability exist.
3
H
7
).
[5]
Mentioned as a reactant in one study.
[6]
Recently isolated at –55 o
C; fast decomposes at –40 o
C .
T dec
= –31.396 x 3 – 41.078 x
– 75.231 x – 7.3957
2
R 2 = 0.9777

T dec vs

H dec for some binary and ternary hydrides
350
R
2
= 0.974
300
250
200 binary Group 13 hydrides ternary Al hydrides predictions of
E0 for In, Tl
150
-150
100
50
0
-50
-50
50
-100
-150 delta H dec
R
2
= 0.996
150

Energy
D)
MH x
Aspects of catalysis in hydrogen storage
A)
Reaction path for H
2 evolving from different MHS.
M + x/2 H
2
C)
B)
A) Thermodyn. unstable MHS with low activation barrier and low T dec
; stores H irreversibly;
B) Thermodyn. stable MHS with high activation barrier and high T dec
; stores H reversibly;
C) Thermodyn.
slightly stable
MHS with intermediate
T dec
; stores H irreversibly;
D) target : catalytically– enhanced thermodyn.
slightly stable MHS with low T dec
; stores hydrogen reversibly.
Vertical arrows symbolize activation barrier for the decomposition process.
Reaction coordinate

Experimental pathway
Hydrogen Store Catalyst
Mechanochemical synthesis
(high-energy ball-milling)
Target: doped MHS
Wet (classical) synthesis
Price=?
thermodynamics kinetics
T dec
=? (TGA) H
2 reabsorption (PCI) Lifetime=? (PCI)
Goal fulfilled
Efficient
Low–temperature
Reversible
Terrorist–proof
Solid Hydrogen
Store

Electronegativity perturbation vs the H…H coupling equilibrium
------------------------------------------------------------------
CH
4
: Gas, T melt
= –183 o C, T dec
= +680 o C
NH
4
+ BH
4
–
: Solid, T dec
= –40 o C
------------------------------------------------------------------
Cyclohexane is thermally stable liquid
[GaH
2
NH
2
]
3 decomposes at +150 o C to GaN and H
2
------------------------------------------------------------------
Benzene C
6
H
6
:

H f
°gas = +82.93 kJ mol –1
Borazine N
3
B
3
H
6
:

H f
°gas = –510.03 kJ mol –1
------------------------------------------------------------------

Conclusions
1. One should preferably play the H
-
I /H
2 equilibrium (metal hydrides)
2. Use light weight hydrides of strongly electropositive elements
(thermodynamically reversible) as a main hydrogen store.
3. Play on the electronegativity of a metal center by use of various ligands (including additional hydride ligands).
4. Use compounds of more electronegative metals as catalyst of H
2 evolution. Tune T dec
.
5. Provide that catalyst is not irreversibly reduced by hydrogen store, and by corresponding metal product.
6. Attempt play on the (H +1 ,H
–1
)/H
2 equilibrium if price of hydrogen store is very low (irreversibility does not matter) and if environment pollution is small. Forget the plasma induced H 0 reabsorption.
7. Try to solve the problem asap.

Hydrogen storage in carbon: graphite, fullerenes, nanotubes.
Non–reproducible claims of: i) Up to 13 wt % H in single wall nanotubes
( Nature 1997 , 386 , 377; Science 1999 , 286 ,
1127, Carbon 1999 , 37 , 1649) ii) Up to 20 wt % H in alkali metal–doped nanotubes ( Science 1999 , 285 , 91).
Problems: i) Lack of homogenity ii) Low active material content iii) High price of C nanotubes (CNT) iv) Simple graphitic sheets & doped graphite: low H storage efficiency v) Fullerenes: irreversible storage C
60
H
44
.
Modification: inorganic nanotubes
4 wt % H at 9 bar in ‘collapsed BN_NTs
( J. Amer. Chem. Soc. 2002 , 124 , 14550).

(Photo)electrolysis of water h
 bateria słoneczna inne odnawialne E elektryczność
H
H
2
2
O
O
2 h

TiO
2
:C – 10 times better efficiency of photoelectrolytic
Utsira (Norway) 2003
Similar projects: splitting of water than pure i) windy islands of
TiO
2
(Nature, 2002 ) northern
Scotland, ii) sunny costs of
H
2
O
Florida, iii) and geothermal energy (Iceland – model hydrogen energy-based EU society!)

Activation of C–H, C–C, H–H and N

N bonds.
:
Oxidative & non–oxidative C–H bond activation:
M n+ [L] + H–CH
3

M (n+2)+ [L](CH
3
–
)(H
–
), same for H–C
6
H
5
M n+ [L](
:
H
–
) + H–CH=CH
2

M n+ [L](C
2
H
5
–
), M=Ru,Rh,Ta etc.
similar scheme for the C–C and
H–H bonds vide: agostic interactions
C=O & C

O bond activation:
O=C=O
 –O–(C=O)–
|C

O|
 –(C=O)–
Review on C–H activation:
Nature 417 (2002) 507–514

heterolytic activation homolytic activation

Complexes of molecular H–H.

Complexes of molecular N

N.

Find out more – Be up to date!
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• http://www.hubbertpeak.com/midpoint.htm
• http://www.trenton.edu/~energy/altfuel/Hydrogen.htm
• http://www.oilcrisis.com/laherrere/opec95.htm
• http://www.eia.doe.gov/oiaf/ieo/index.html
• http://www.energy.gov/dataandprices/index.html
• http://www.cato.org/pubs/pas/pa-280.html
Hydrogen production & storage:
• http://www.eren.doe.gov/hydrogen/basics.html
• http://www.eren.doe.gov/RE/hydrogen.html
• http://www.ornl.gov/ORNL/Energy_Eff/power-h2.html
• http://www.clean-air.org/ahafaq.html
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• http://refining.dis.anl.gov/oit/toc/h2proc_8.html
• http://www.hydrogen.org/Wissen/NHF97.htm#4. Hydrogen Storage
• http://naftp.nrcce.wvu.edu/techinfo/altfuels/H2/Hydrogen.html
• http://ceh.sric.sri.com/Public/Reports/743.5000/
• http://home.powertech.no/magneh/meyer/hydrogen.htm
• http://www.e-sources.com/hydrogen/storage.html
• http://www.h2eco.org/
Press & news:
• http://www.hfcletter.com/
• http://www.h2fc.com/defaultNS4.html
• http://www.cnn.com/2000/NATURE/09/15/hydrogen.car/
• http://www.csmonitor.com/2002/0131/p13s01-stss.html
• http://www.chemweb.com/alchem/articles/1023977425407.html

Find out more – cd.
Scientific programs:
• http://www.ca.sandia.gov/CRF/03_hydrogen.html
• http://www.nrel.gov/nrel_research.html
• http://www.bham.ac.uk/FUCHSIA/home.htm
• http://www.spacefuture.com/archive/liquid_hydrogen_industry_a_key_for_space_tourism.shtml
• http://www.eren.doe.gov/
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Companies:
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• http://www.genesis.rutgers.edu/Partners/millenium.html
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• http://www.multishop.pp.ru/dmoz/Science/Technology/Energy/Hydrogen
• http://www.uscar.org/pngv/
• http://www.herahydrogen.com/flash.html
• http://www.ballard.com/tD.asp?pgid=32&dbid=0
Fuel cells:
• http://inventors.about.com/library/weekly/aa090299.htm?once=true&
• http://rhlx01.rz.fht-esslingen.de/projects/alt_energy/storage/fuelcell/fuelcell.html
Conferences:
• http://www.grc.uri.edu/programs/2001/hydrmet.htm