WYKŁAD III & IVMagazynowanie 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.

“I believe that one day hydrogen and oxygen, which together form water, will be used either alone or together as an inexhaustible source of heat and light”

(Jules Verne, The mysterious island, 1874)

THE DREAM

Why hydrogen?

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 (CO2)Other pollutants (SOx, NOx etc.)Big politicsOil plots, oil wars, etc.

Limited amountLimited geopoliticsLandscape 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

Pros and Cons

- 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.

Why storage in the solid state?

L. Schlapbach, A. Züttel, Nature 414, 353 (2001). Other ways:

- physisorption (glass, sponges etc.)

- liquid (price, volume, T<250 K tanks)

- compression (price, volume, permeability of containers, pressure now up to 800 bar)

Gaseous & liquid fuels vs solid fuels

?

1937 1986

2001

C CH4CH2.25 other

nuclear, hydroelectric, wind, solar, biomass, geothermal1999USA

30.015.251.0 3.2

79.6 4.7 15.0

ENERGY

CO2 EMISSION

OUTPUT RATE /pounds CO2 per 1 kWh

2.12 1.92 1.31 0.00

1998USA

41.7

C CH2.25 CH4

20.836.4

other

TOTAL CO2 EMISSION

31.3 15.9 23.8 16.0 13.0

C 68% H 32%

DIRTY AND CLEAN ENERGY

CONTRIB. TO THE TOTAL ENERGY GENERATION

Hubbert’s Law

GLOBAL ENERGY CRISIS AROUND 2010…2050

$$$ Value 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 $ 1 bln/year

USA

Freedom /$ 150 mln incl. $ 40 mln government share/

(fuel cells $ 340 mln!)

EUROPE

Fuchsia, Hystory, Hymosses /$ 10 mln/

JAPAN

Protium /$ ??? mln/

WE-NET /$ 4 mln p.a./

Some history16th 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

CLEAN HYDROGEN ECONOMY FOR THE FUTURE

Hydrogen production

H2 (gas)

• CH4 + 2 H2O CO2 + 4 H2

• C–H bond activation

• photoelectrochemical generation (electrolysis of water), green energy

H2 (compressed) H2 (liquid) H (solid chemicals)

Hydrogen storage

Hydrogen combustion

• high–pressure cryogenic

tanks

• chemical reactions

H2/O2 Fuel cell(Hybrid) engine

Zero–emission vehicle

Effects for the planet of the increased water

circulation = ???

Budowa Ogniwa Paliwowego (Fuel Cell).

Energia chemiczna Energia elektryczna

małe straty cieplne, duża wydajność w por. z cyklem Carnota

ANODA /Pt KATODA /PtNafion®

Rodzaje ogniw paliwowych H2/O2:

- Alkaliczne (150–200 oC) – wymagają użycia bardzo czystego H2 i O2

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

Stacjonarne FC

Przenosne FCLaptop FC

Cell.Ph. FC

Transport/bus FC

Anchorage /Alaska/

Car of the future: BMW 750 hL presented during EURO 2000

• Yesterday: BMW 750 hL (München 2000)

6 fuel-cell busses (Chicago & Vancouver 1999-2001)• Today: the first commercial Honda & Toyota (Japan & California 2002/3)• Tomorrow: cheap fuel cells, cheaper H2 (US & Canada 2010)

Who does not pick up this subject NOW, most probably would not have chance to work on it at all.

COMMANDEMENTS OF HYDROGEN STORAGE

(i) High storage capacity: minimum 6.5 wt % abundance of hydrogen and at least 65 g/l of hydrogen available from the material;

(ii) Tdec = 60–120 oC;

(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.

EXAMPLES OF CHEMICAL HYDROGEN STORES

1. PdH0.6: 0.6 wt%, excellent reversibility, $ 1000/oz, >$1mln/1kg H

2. NaH: 4.2 wt%, good reversibility, Tdec > 425 oC

3. NaAlH4 & TiO2: 5.5 wt%, Tdec > 125 oC, reversibility OK

4. MgH2: 7.6 wt%, Tdec > 330 oC, poor reversibility

5. “Li3Be2H7“: 8.7 wt %, Tdec > 300 oC, toxicity, cost

6. NaBH4/H2O(l): 9.2 wt%, expensive Ru catalyst, no reversibility

7. AlH3: 10.0 wt %, very cheap Al, Tdec > 150 oC, no reversibility

8. H2O(l): 11.1 wt%, liquid, thermal decomposition difficult

9. MeOH(l): 12.5 wt%, toxic liquid, activation difficult

10. LiH: 12.6 wt%, Tdec > 700 oC

11. NH3(l): 17.6 wt%, large N – H bond activation barrier

11. BeH2: 18.2 wt%, extremely toxic, Tdec > 250 oC, no reversibility

12. CH4: 25.0 wt%, gas, thermal activation very difficult

13. Carbon nanotubes: ??? Wt%, ???

Compare to Mg2NiH4: 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?)

0

20

40

60

80

100

120

140

160

0 5 10 15 20 25

gravimetric H content [wt%]

vo

lum

etr

ic H

de

nsi

ty [

g/l]

MAIN CHEMICAL PLAYGROUND

Problems with setting of the position of H in the periodic table of chemical elements

H as H+: • H’s IP 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 H0.• 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 O2 or P2.

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).

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–.

H2 EVOLUTION REACTION PATHWAY

Reaction path for evolving H2 from a H–containing

material. Elongation of the M–H bonds occur along RM–H

coordinate, and the pairing of two H atoms in a H2

molecule proceeds along the RH–H coordinate. The actual

reaction coordinate is a combination of these two.

WHICH REDOX EQUILIBRIUM TO PLAY?

E /eV

+13.60

0.0 0.75

+1 0 1

n

Fig.2. The dependence of the electronic energy of the Hn 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 Hn species strongly decreases in the direction: HI+ > H0 > HI–.

HI/H2 or H+1/H2

IP

/kJ mol–1 EA

/kJ mol–1 IP

/kJ mol–1 EA

/kJ mol–1 H

1312 H

72.8 H

1312 H

72.8 Li

520.2 Li

59.6 F

1681 F

328 Na

495.8 Na

52.8 Cl

1251.2 Cl

349 K

418.8 K

48.4 Br

1139.9 Br

324.6 Rb

403.0 Rb

46.9 I

1008.4 I

295.2 Cs

375.7 Cs

45.5 At 920

At 270.1

H– H0

H+

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

1 1 H

2 He

2 3 Li

4 Be

5 B

6 C

7 N

8 O

9 F

10 Ne

3 11 Na

12 Mg

13 Al

14 Si

15 P

16 S

17 Cl

18 Ar

4 19 K

20 Ca

21 Sc

22 Ti

23 V

24 Cr

25 Mn

26 Fe

27 Co

28 Ni

29 Cu

30 Zn

31 Ga

32 Ge

33 As

34 Se

35 Br

36 Kr

5 37 Rb

38 Sr

39 Y

40 Zr

41 Nb

42 Mo

43 Tc

44 Ru

45 Rh

46 Pd

47 Ag

48 Cd

49 In

50 Sn

51 Sb

52 Te

53 I

54 Xe

6 55 Cs

56 Ba

71 Lu

72 Hf

73 Ta

74 W

75 Re

76 Os

77 Ir

78 Pt

79 Au

80 Hg

81 Tl

82 Pb

83 Bi

84 Po

85 At

86 Rn

7 87 Fr

88 Ra

103 Lr

104 Rf

105 Db

106 Sg

107 Bh

108 Hs

109 Mt

110 Uun

111 Uuu

112 Uub

113 Uut

114 Uuq

115 Uup

116 Uuh

117 Uus

118 Uuo

57 La

58 Ce

59 Pr

60 Nd

61 Pm

62 Sm

63 Eu

64 Gd

65 Tb

66 Dy

67 Ho

68 Er

69 Tm

70 Yb

89 Ac

90 Th

91 Pa

92 U

93 Np

94 Pu

95 Am

96 Cm

97 Bk

98 Cf

99 Es

100 Fm

101 Md

102 Nb

7 N

Niemetal

3 Li

Metal

5 B

Niemetal zmetalizowany pod wysokim p

85 At

Brak prób, teoretycznie w zasięgu metalizacji

1 H

Zmetalizowany tylko w fazie ciekłej

ATTEMPTS OF H METALLIZATION

H

• It should be easy to play the HI/H2 equilibrium;

• It is much more difficult to play the H+1/H2 one;

• It is quite difficult to play the 2H0/H2 equilibrium;

• It is the most difficult to play the (H+1,H–1)/H2 one.

Which species are to be involved in the charging/recharging process of the Hydrogene Storage Material?

H–1 H0 + e (H0 = +0.75 eV) (1a)H+1 + e H0 (H0 = –13.60 eV) (1b)2 H0 H2 (H0 = –4.52 eV) (1c)H+1 + H1 H2 (H0 = –17.37 eV) (1d)

Standard enthalpies of formation Hf0 [kJ/mol] of binary hydrides

of the main group elements.

MH MH2 MH3 MH4 MH3 MH2 MH Li

-116.3 Be

-18.9 B[1]

+36.4 C

-74.6 N

-45.9 O

-285.8 F

-273.3 Na

-56.5 Mg

-75.2 Al

-46.0 +92[1,2]

Si +34.3

P +5.4

S -20.6

Cl -92.3

K -57.7

Ca -181.5

Ga ???[3]

+118[1,2]

Ge +90.8

As +66.4

Se +29.7

Br -30.3

Rb -52.3

Sr -180.3

In ???[3]

+175[1,2]

Sn +162.8

Sb +145.1

Te +99.6

I +26.5

Cs -54.2

Ba -177.0

Tl# ???[3]

+245[1,2]

Pb +181.1[2] +251.5[4]

Bi +230.6[4]

Po +188.6[4]

At +104.8[4]

[1] Molecular dimer, M2H6.

[2] Theoretical value.

[3] Value for solid hydride is not known. This hydride certainly decomposes below 0 oC, and a Hf0 value

(standard conditions) cannot be measured.

[4] Extrapolated from experimental values.

Mn+ + n H1 M + n/2 H2

Chemical rationale behind the metal/hydrogen avoided crossing curve. Size, electric charge, orbital energy, hardness, and standard redox potential.

–12.18-0.141.34BeH2

–10.10-0.241.73MgH2

–8.61-0.342.15 CaH2

–7.98-0.382.33SrH2

–12.18-0.141.34BeH2

–10.10-0.241.73MgH2

–8.61-0.342.15 CaH2

–7.98-0.382.33SrH2

molecule R0/Å q(H)/e HOMO/eV

250–1.970.59Be

327–2.360.86Mg

600–2.841.14 Ca

675–2.891.32Sr

250–1.970.59Be

327–2.360.86Mg

600–2.841.14 Ca

675–2.891.32Sr

atom Rcat/Å E0/V Tdec /oC

Ga+ > Ga0 > Ga–

[GaH2][BH4] < [GaH3]2 < LiGaH4

–35 oC, –15 oC, 50 oC

Electronegativity vs the total charge & substituents

B0 > B

[BH3]2 < LiBH4

+40 oC, +275 oC

Zn+2 > ZnI1+

[ZnH2] < [ZnHI]

+90 oC, +110 oC

Ga+3 > GaCl2+ > GaCl21+

[GaH3]2 < [GaClH2]2 < [GaCl2H]2

–15 oC, –15 oC, +50 oC

[AlH3] < Li[Al2H7–] < LiAlH4

150 oC, 160 oC, 165

MgH2 < Sr2[MgH6] < Ba2[MgH6]

327, 377, > 427 oC

[InH3] < InH4–

???, –30 oC

Zn+2 > Zn–2

[ZnH2] < K2[ZnH4]

+90 oC, +407 oC

As+5 > AsPh41+

[AsH5] < [AsPh4H]

???, obtained

Na2[BeH4] > [BeH2] > Be[BH4]2

+380 oC, +250 oC, +25 oC

[GaH][BH4]2 < [GaH2][BH4] < [GaH3]2 < LiGaH4

–73 oC, –35 oC, –15 oC, +50 oC

[Bi5+] > [BiCl41+]

unknown, [BiCl41+][H1–] known as H1+BiIIICl4

-200

-100

0

100

200

300

400

500

600

700

800

-3.5 -2.5 -1.5 -0.5 0.5 1.5

E0 / V

Td

ec /

oC

H2/2H H0 /H

Na+

Li+

Er3+

Ca2+

Be2+, Pu3+

Mg2+

Zn2+

Al3+

V2+

Ga3+

Sn4+

Hg2+

Sb3+

Ba2+, Sr2+

Y3+

U3+

B3+P3+

Cd2+

BaRuH9 & Cs3RuH10 vs RuH7

Mg2FeH6 vs FeH2

M2PtH6 vs

PtH4

…

[MIIIH41–],

M=Cr, Eu, Yb

[CdH42–]

????????

[HgH42–]

[PtH6]

M2Pd0H2 M=Li, Na, & Sr2Pd0H4

(1.674–1.676 Å)

M2PdIIH4 M=K, Rb, Cs (1.625–1.64 Å )

M2PtIIH4 M=Na,

K, Rb, Cs

(MH)2PtIIH4

M=Sr, Ba

M2PtIVH6 M=K,

Rb, Csd10 = Au1+ [AuCl2

–]d8 = Au3+ [AuCl4

–]d6 = Au5+ [AuF6

–]

Predictions of the Tdec vs E0 relationship for binary hydrides

Tdec = –31.396 x3 – 41.078 x2 – 75.231 x – 7.3957

R2 = 0.9777

Hydride Redox pair E0 /V Tdec /oC Hydride Redox pair E0 /V Tdec /

oC ScH3

[1] ScIII/Sc0 2.03 239 WH6[1,2] WO3/W2O5 0.029 -5

ThH4[1,3] ThIV/Th0 1.83 185 TiH4

[1] TiO2/TiIII +0.1 -15 HfH4

[1] HfIV/Hf0 1.70 156 SH6[4] HSO4

/H2SO3 +0.16 -21

ZrH4[1] ZrIV/Zr0 1.55 127 NpH4 NpIV/NpIII +0.18 -22

PaH4[5] PaIV/PaIII 1.46 113 UH6

[1] UO22+/UIV +0.27 -31

YbH3 YbIII/YbII 1.05 63 BiH3 BiIII/Bi0 +0.317 -36[6] TaH5

[2] TaV/Ta0 0.81 43 PoH2 PoII/Po0 +0.37 -42 UH4

[1] UIV/UIII -0.52 25 UH5[1] UO2

+/UIV +0.38 -44 TiH3

[1] TiIII/TiII 0.37 16 SH4[4] H2SO3/S

0 +0.50 -59 EuH3

[1] EuIII/EuII 0.35 15 AsH5 H3AsO4/HAsO2 +0.560 -68 InH3

[1] InIII/In0 0.338 15 TeH4 TeIV/Te0 +0.57 -69 PH5

[2] H3PO4/H3PO3 0.276 11 SbH5 Sb2O5/SbO+ +0.605 -75 VH3 VIII/VII 0.255 10 MoH6

[1] H2MoO4/MoO2 +0.646 -82 WH4

[1] WO2/W0 0.119 1 NpH5 NpO2

+/NpIV +0.66 -84 PaH5 PaO(OH)2

+/PaIV 0.1 0 AtH HAtO/At0 +0.7 -91 NbH5

[2] Nb2O5/NbII 0.1 0 TlH3 TlIII/Tl0 +0.72 -95

[1] Species isolated in the noble gas matrixes. [2] Organophosphine–stabilized hydrides have been obtained. [3] Mixed–valence hydrides exist (Th4H15, Yb3H8, Eu3H7). [4] Theoretical predictions of kinetic stability exist. [5] Mentioned as a reactant in one study. [6] Recently isolated at –55 oC; fast decomposes at –40 oC.

Tdec vs Hdec for some binary and ternary hydrides

R2 = 0.974

R2 = 0.996-150

-100

-50

0

50

100

150

200

250

300

350

-150 -50 50 150

delta Hdec

Td

ec

binary Group 13hydrides

ternary Alhydrides

predictions ofE0 for In, Tl

Aspects of catalysis in hydrogen storage

Energy

Reaction coordinate

MHx

M + x/2 H2

A)

B)

C)

D)

Reaction path for H2 evolvingfrom different MHS.

A) Thermodyn. unstable MHS

with low activation barrier and low Tdec; stores H irreversibly;

B) Thermodyn. stable MHS with high activation barrier and high Tdec; stores H reversibly;

C) Thermodyn. slightly stable MHS with intermediate Tdec; stores H irreversibly;

D) target : catalytically–enhanced thermodyn. slightly stable MHS with low Tdec; stores hydrogen reversibly.

Vertical arrows symbolizeactivation barrier for thedecomposition process.

Experimental pathway

Hydrogen Store Catalyst

Target: doped MHS

Mechanochemical synthesis (high-energy ball-milling)

Wet (classical) synthesis

Tdec=? (TGA) H2 reabsorption (PCI) Lifetime=? (PCI)

thermodynamics kinetics

Price=?

Goal fulfilled

Efficient Low–temperature

Reversible Terrorist–proof Solid Hydrogen

Store

------------------------------------------------------------------

CH4: Gas, Tmelt = –183 oC, Tdec = +680 oC

NH4+BH4

–: Solid, Tdec = –40 oC

------------------------------------------------------------------

Cyclohexane is thermally stable liquid

[GaH2NH2]3 decomposes at +150 oC to GaN and H2

------------------------------------------------------------------

Benzene C6H6: Hf°gas = +82.93 kJ mol–1

Borazine N3B3H6: Hf°gas = –510.03 kJ mol–1

------------------------------------------------------------------

Electronegativity perturbation vs the H…H coupling equilibrium

Conclusions

1. One should preferably play the HI/H2 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 H2 evolution. Tune Tdec.

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)/H2 equilibrium if price of hydrogen store is very low (irreversibility does not matter) and if environment pollution is small. Forget the plasma induced H0 reabsorption.

7. Try to solve the problem asap.

Hydrogen storage in carbon: graphite, fullerenes, nanotubes.

Modification: inorganic 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 homogenityii) Low active material content iii) High price of C nanotubes (CNT)iv) Simple graphitic sheets & doped graphite:

low H storage efficiencyv) Fullerenes: irreversible storage C60H44.

4 wt % H at 9 bar in ‘collapsed BN_NTs (J. Amer. Chem. Soc. 2002, 124, 14550).

(Photo)electrolysis of water

bateria słoneczna

h

elektryczność

H2O

H2 O2

inne odnawialne E

H2Oh

TiO2:C – 10 times better efficiency of photoelectrolytic splitting of water than pure TiO2 (Nature, 2002)

Utsira (Norway) 2003

Similar projects: i) windy islands of

northern Scotland,

ii) sunny costs of Florida,

iii) and geothermal energy (Iceland – model hydrogen energy-based EU society!)

Activation of C–H, C–C, H–H and NN bonds.

:Mn+[L] + H–CH3 M(n+2)+[L](CH3–)(H–), same for H–C6H5

Oxidative & non–oxidative C–H bond activation:

Mn+[L](:H–) + H–CH=CH2 Mn+[L](C2H5–), M=Ru,Rh,Ta etc.

similar scheme for the C–C and H–H bonds

vide: agostic interactions

C=O & CO bond activation:

O=C=O –O–(C=O)–

|CO| –(C=O)–

Review on C–H activation: Nature 417

(2002) 507–514

homolytic activation

heterolytic activation

Complexes of molecular H–H.

Complexes of molecular NN.

Find out more – Be up to date!Hubbert’s peak & energy consumption:• 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• http://www.etde.org/html/hyd/hydhome.html• http://starfire.ne.uiuc.edu/~ne201/1995/archer/hydro.html• 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

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/• http://www.bbsrc.ac.uk/science/initiatives/supergen.html• http://www-ew.ike.uni-stuttgart.de/ewproject/ewktr821e.htm

Companies:• http://www.jmcusa.com/mh1.html• http://www.ergenics.com/• http://www.ovonic.com/• http://www.shell.com/home/Framework?siteId=hydrogen-en• http://www.genesis.rutgers.edu/Partners/millenium.html• http://www.azhydrogen.com/mg_25.html• http://www.ballard.com/• 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

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