2269-16 workshop on new materials for renewable...
TRANSCRIPT
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2269-16
Workshop on New Materials for Renewable Energy
Xavier SALA
17 - 21 October 2011
UAB Barcelona
Spain
Molecular catalysts that oxidize water to dioxygen
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Molecular Catalysts that Oxidize Water to Dioxygen
Xavier Sala, UAB, Barcelona, Spain
ICTP, Miramare, Trieste, October 17th 2011
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OUTLINE
1. INTRODUCTION
2. Ru-based WOCs: from the Blue Dimer to mononuclear species
3. Iridium WOCs
4. All-inorganic POM complexes
5. First-row transition-metal based WOCs
8. FINAL REMARDKS AND CONCLUSIONS
6. Heterogeneous WOCs
7. WOCs in Photoelectrochemical cells (PECs)
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INTRODUCTION - Today’s Energy Situation
2004: 14.5 TW
2050: 30-60 TWGlobal Energy
Demandx 2.5
Year
Rel
ativ
e R
eser
ves
of F
ossi
l Fue
ls
Exhausting profiles of oil products (2004), Exxon-Mobile.
Solar Energy Utilization Workshop (2005) US-DOE, Washington DC.
Menzel, A. et al. Global Change Biology, 2006, 12, 1-8.
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2004: 14.5 TW
2050: 30-60 TWGlobal Energy
Demandx 2.5
Exhausting profiles of oil products (2004), Exxon-Mobile.
Solar Energy Utilization Workshop (2005) US-DOE, Washington DC.
Menzel, A. et al. Global Change Biology, 2006, 12, 1-8.
INTRODUCTION - Today’s Energy Situation
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INTRODUCTION – H2 as clean energy vector
High energy content/kg (3 x gasoline)
Highest heating value per mass of all chemical fuels
Combustion only releases energy and pure water (Clean & Carbon Free)
Water Splitting
Combustion
Transport &Storage
H2O
H2
H2
O2
ENERGY
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Eggert, A. et al. Chem. Eng. News, 2004, 82(41), 48-49
Freemantle, M. Chem. Eng. News, 2003, 81(3), 32-36
Where do we get H2 today?
96% 96% comes from fossil fuels
INTRODUCTION - Today’s H2 Sources
H2 Sources
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2 H2O hν
O2 + 2 H2
Sala, X.; Escriche, Ll.; Llobet, A. Angew. Chem. Int. Ed., 2009, 48, 2-13
INTRODUCTION - Water Splitting and PEC Cells
Light Harvesting Proton ReductionWater Oxidation
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Sala, X.; Escriche, Ll.; Llobet, A. Angew. Chem. Int. Ed., 2009, 48, 2-13
INTRODUCTION – Water Oxidation: bottleneck process
Light Harvesting Proton ReductionWater Oxidation
BOTTLENECK PROCESSBOTTLENECK PROCESS
2 H2O hν
O2 + 4 H+ + 4e-
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Forward ETBackward ET
INTRODUCTION – harmonic assembly and recombination
Light Harvesting Proton ReductionWater Oxidation
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INTRODUCTION – How Nature gets its energy ?
+ +
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3 CO2 + 3 H2O C3H6O3 + 3 O2
hν
INTRODUCTION – How Nature gets its energy ?
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PSII structure from T. Vulcanus at 1.9 Å resolution
Umena, Y.; Kawakami, K. et al. Science, 2011, 473, 55
INTRODUCTION – Can we get inspired by Nature ?
3 CO2 + 3 H2O C3H6O3 + 3 O2
hν
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Umena, Y.; Kawakami, K. et al. Science, 2011, 473, 55
Loll, B.; Kern, J.; Saenger, W.; Zouni, A.; Biesiadka, J. Nature, 2005, 438, 1040
Messinger, J.; Zouni, A.; Yachandra, V. K. et al. Science, 2006, 314, 821
2 H2O O-O + 4 H+ + 4 e-
INTRODUCTION – Oxygen evolving complex PSII
Low MW Structural/Functional Models
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Electrochemical equivalents (controlled potential electrolysis)
(M(II)-OH2)2 (M(IV)-O)2
HH 22O O OO 22 + 4 H+ 4 H ++ + 4 e+ 4 e --
CPECPE(M(II)-OH2)2
INTRODUCTION – Oxidizing equivalents and O2 measuring
Chemical equivalents (preferently OSET)
Ce(IVCe(IV))
WOC-ground
WOC-active
W O CW O C a c t i v ea c t i v eHH 22O O OO 22 + 4 H+ 4 H ++ + 4 e+ 4 e --
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Photochemical equivalents (photosensitizers)
P*P*
Rup = Co = [Co(NH3)5Cl]n+
Ruc = WOC (reduced form)RuAC = WOC (active form)
Sala, X.; Escriche, Ll.; Llobet, A. in Molecular Sola Fuels (Chapter 4), RSC Publishing 2011, in press.
INTRODUCTION – Oxidizing equivalents and O2 measuring
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INTRODUCTION – Oxidizing equivalents and O2 measuring
[Ru]
Blanc
Differential pressure manometry
On-line Mass spectrometry
Total gas evolved Gas composition
Gas Chromatography
O2 quatification
(M(II)-OH2)2 (M(IV)-O)2
HH 22O O OO 22 + 4 H+ 4 H ++ + 4 e+ 4 e --
(M(II)-OH2)2
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INTRODUCTION – Oxidizing equivalents and O2 measuring
Clark electrodes
O2 selective
gas phaseLiquid phase
Fluorescence Probes
(M(II)-OH2)2 (M(IV)-O)2
HH 22O O OO 22 + 4 H+ 4 H ++ + 4 e+ 4 e --
(M(II)-OH2)2
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INTRODUCTION – Common reaction mechanisms
Romain, S.; Vigara, L.; Llobet, A. Acc. Chem. Res. 2009, 42 1944-1953.
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OUTLINE
1. INTRODUCTION
2. Ru-based WOCs: from the Blue Dimer to mononuclear species
3. Iridium WOCs
4. All-inorganic POM complexes
5. First-row transition-metal based WOCs
8. FINAL REMARDKS AND CONCLUSIONS
6. Heterogeneous WOCs
7. WOCs in Photoelectrochemical cells (PECs)
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Ru-BASED WOCs – The Ru=O Group and WO
LRuII-OH2 LRuIII-OH LRuIV=O-H+-e- -H+-e-
X 2
4 H+ + 4 e- 2 H-H
2 H2O hν O2 + 2 H2
2 H2O O-O + 4 H+ + 4 e-
Meyer,T.J. et al. Inorg. Chem. 1984, 23, 1845
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H2O-IIRu RuII-OH2BL
BL: Bridging Ligand
Electronic Coupling between Ru
Interactions Through Space
Ru-BASED WOCs – Dinuclear Ru-OH2 complexes
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4-5 MC
[(bpy)2RuV-O-RuV(bpy)2]4+
OO
- 4H+, - 4e-
O-O
Gestern, S. W.; Samuels, G. J.; Meyer, T. J. J. Am. Chem. Soc., 1982, 104, 4029
Gilbert, J. A.; Eggleston, D. S.; Meyer, T. J. et al. J. Am. Chem. Soc., 1985, 107, 3855
[(bpy)2RuIII-O-RuIII(bpy)2]4+
OH2H2O
Ru-BASED WOCs: the Blue Dimer
Ce(IV):WOC 100:1pH = 1 buffer
Ce(IVCe(IV))
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Water NucleophilicAttack
Intermolecular O-O Coupling
O-O Coupling Pathways
Intramolecular O-O Coupling
LRu-O
OH
H
+
WNA Intra-I2MInter-I2M
T. J. Meyer et al., Inorg. Chem. 2003, 42, 8140.
A. Llobet et al., Acc. Chem. Res. 2009, 42, 1944.
Ru-BASED WOCs: O-O bond formation in the Blue Dimer
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Binstead, R. A.; Chronister, C. W.; Meyer, T. J., et al. J. Am. Chem. Soc., 2000, 122, 8464
Yamada, H.; Siems, W. F.; Koike, T.; Hurst, J. K. J. Am. Chem. Soc., 2004, 126, 9786
WNA Inter-I2M
Ru-BASED WOCs: O-O bond formation in the Blue Dimer
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Cape, J. L.; Hurst, J. K. J. Am. Chem. Soc., 2008, 130, 827-829
Ru-BASED WOCs: O-O bond formation in the Blue Dimer
Non-innocent ligands
= O16
= O18
= O232
= O234
= O236
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[(bpy)2RuIII-O-RuIII(bpy)2]4+
OH2H2O
[(bpy)2RuV-O-RuV(bpy)2]4+
OO
- 4H+, - 4e-
Gestern, S. W.; Samuels, G. J.; Meyer, T. J. J. Am. Chem. Soc., 1982, 104, 4029
O-O4-5 MC
LRuII-OH2 LRuIII-OH LRuIV=O-H+-e- -H+-e-
X 2
Ce(IV):WOC 100:1pH = 1 buffer
Ru-BASED WOCs: the Blue Dimer vs. Hbpp complexes
Ce(IVCe(IV))
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[(trpy)RuII-(bpp)-RuII(trpy)]3+
H2O OH2
Sens, C., Llobet, A. et al., J. Am. Chem. Soc., 2004, 126, 7798
O-O4-5 MC
[(bpy)2RuV-O-RuV(bpy)2]4+
OO
Hbpp
trpy
LRuII-OH2 LRuIII-OH LRuIV=O-H+-e- -H+-e-
O-O18 MC
2 X
N
NN
N NHN N
Ce(IV):WOC 100:1pH = 1 buffer
Ru-BASED WOCs: the Blue Dimer vs. Hbpp complexes
Ce(IVCe(IV))
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Ru-BASED WOCs: reaction mechanism in Ru-Hbpp complexes
Intra-I2M
Romain, S.; Sala, X.; Llobet, A. et al. J. Am. Chem. Soc. 2009, 131, 2768-2769Bozoglian, F.; Romain, S.; Cramer, C.; Gagliardi, L.; Llobet, A. et al. J. Am. Chem. Soc. 2009,131, 15176
Optimized conditions
TON = 570
Ce(IVCe(IV))= O16
= O18
= O232
= O234
= O236
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TON = 4.700
Ru-BASED WOCs: other key dinuclear systems
TON = 10.400
TOF = 72 min-1
Deng, G.; Thummel, R. et al. Inorg. Chem. 2008, 47, 1835Xu, Y.; Akermark, B.; Sun, L. et al. Inorg. Chem. 2009, 48, 2717
TON = 600
Ce(IVCe(IV))
Optimized conditions
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Ru-BASED WOCs: other key dinuclear systems
P*P*Rup =
Co = [Co(NH3)5Cl]n+
TON = 60
TOF = 6 min-1
Xu, Y.; Akermark, B.; Sun, L. et al Angew. Chem. Int. Ed. 2010, 49, 8934Xu, Y.; Akermark, B.; Sun, L. et al. Chem Commun 2010, 46, 6506
[Ru(bpy)3] as Rup
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Ru-BASED WOCs: mononuclear systems
Ru(II)-N6 Metal coord. expansion
Deng, G.; Thummel, R. et al. Inorg. Chem. 2008, 47, 1835
Ce(IVCe(IV))
Real catalytic species
Duan, L.; Sun, L. et al. ChemSusChem 2011, 4, 238.
TON = 450 (22h)
TON = 89 (22h)
CPECPE
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Ru-BASED WOCs: mononuclear systems
Concepcion, J. J.; Meyer, T. J. et al. J. Am. Chem. Soc. 2008, 130, 16462Concepcion, J. J.; Meyer, T. J. et al. J. Am. Chem. Soc. 2010, 132, 1545
Ce(IVCe(IV))
= O16
= O18
= O232
= O234
= O236
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Ru-BASED WOCs: mononuclear systems
TON = 2000
TOF 2500 min-1Ce(IVCe(IV))
Duan, L.; Sun, L. et al. Chem. Eur. J. 2010, 16, 4659Duan, L.; Sun, L. et al. Inorg. Chem. 2010, 49, 209
TON = 100
TOF 3.7 min-1P*P*
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Ru-BASED WOCs: mononuclear systems
Duan, L.; Sun, L. et al. J. Am. Chem. Soc. 2009, 131, 10397.Nyhlén, J.; Akermark, B.; Sun, L. Privalov, T. et al. Angew. Chem. Int. Ed. 2010, 49, 1773
Metal coordination expansion to 7
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Ru-BASED WOCs: mononuclear systems- (Ru=O)2
Ce(IVCe(IV))
Sala, X.; Gagliardi, L.; Cramer, C.; Llobet, A. et al. Angew. Chem. Int. Ed. 2010, 49, 7745.
N
RuIII
N
N O
O
N
cis
TON = 6
TOF = 1.2 min-1
N NN N =
O2 labelling +
O(n+4)+
M
O
H
HWNA
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Ru-BASED WOCs: mononuclear systems
P*P*Ce(IVCe(IV))
Röser, S.; Farràs, P.; Llobet, A. et al. ChemSusChem 2011, 49, 1773
CPECPE
In-Hppp, X = CHIn-Hbpp, X = N
Out-Hppp, X = CHOut-Hbpp, X = N
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OUTLINE
1. INTRODUCTION
2. Ru-based WOCs: from the Blue Dimer to mononuclear species
3. Iridium WOCs
4. All-inorganic POM complexes
5. First-row transition-metal based WOCs
8. FINAL REMARDKS AND CONCLUSIONS
6. Heterogeneous WOCs
7. WOCs in Photoelectrochemical cells (PECs)
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TON = 10.000 (5 days)
TOF = 1.39 min-1
Albrecht, M. et al. ACIE 2011, 4, 238.
Iridium WOCs: active and robust
TON = 2760 (≈ one week)
TOF = 0.27 min-1
“Abnormal” Carbene
Bernhard, S. et al. ACIE 2008, 130, 210. Crabtree, J.; Brudvig, G. W. et al. JACS 2009, 131, 8730and JACS 2010, 132, 16017.
TON = > 1500 (5.5h)
TOF = 54 (init.) to 0.1 min-1
TON = > 1500 (5.5h)
TOF = 0.1 min-1
Ce(IVCe(IV))
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OUTLINE
1. INTRODUCTION
2. Ru-based WOCs: from the Blue Dimer to mononuclear species
3. Iridium WOCs
4. All-inorganic POM complexes
5. First-row transition-metal based WOCs
8. FINAL REMARDKS AND CONCLUSIONS
6. Heterogeneous WOCs
7. WOCs in Photoelectrochemical cells (PECs)
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All-inorganic POM WOCs: ruthenium
Sartorel, A.; Bonchio, M. et al. J. Am. Chem. Soc. 2008, 130, 5006.Geletii, Y. V.; Hill, C. Angew. Chem. Int. Ed. 2008, 47, 3896
Ce(IVCe(IV))TON = highly stable, no deactivation
TOF = 7.5 min-1
Cuban like [Ru4O4(OH)2(H2O)4(γ-SiW10O36)2]10-
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All-inorganic POM WOCs: ruthenium
Sartorel, A.; Llobet, A.; Bo, C.; Bonchio, M. et al. J. Am. Chem. Soc. 2009, 131, 16051
Ce(IVCe(IV))
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All-inorganic POM WOCs: ruthenium
Puntoriero, F.; ; Bonchio, M.; Campagnia, S. et al. Chem. Commun. 2010, 46, 4725.Orlandi, M.; Bonchio, M.; Scandola, S. Chem. Commun. 2010, 46, 3152.
P*P*
P* collects a broad range of the EM spectra
Fast Hole Scavenging of the Ru-POM
= 0.3
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All-inorganic POM WOCs: cobalt
Yin, Q.; Hill, C. et al. Science 2010, 328, 342Huang, Z.; Hill, C.; Lian, T. et al. J. Am. Chem. Soc. 2011, 133, 2068
Cuban like, B-type [Co4(H2O)2(α-PW9O34)2]10-
[Ru(bpy)[Ru(bpy)33]]3+3+
P*P*
TON = very stable
TOF = ≥ 300 min-1 (init.)
TON and TOF highly pH dependant
TON = ≥ 220
= 0.15
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All-inorganic POM WOCs: cobalt
Stracke, J. J.; Finke, R. G. et al. J. Am. Chem. Soc. 2011, 133, 14872
CPECPE
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OUTLINE
1. INTRODUCTION
2. Ru-based WOCs: from the Blue Dimer to mononuclear species
3. Iridium WOCs
4. All-inorganic POM complexes
5. First-row transition-metal based WOCs
8. FINAL REMARDKS AND CONCLUSIONS
6. Heterogeneous WOCs
7. WOCs in Photoelectrochemical cells (PECs)
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First row transition-metal based WOCs: manganese
Limburg, J.; Crabtree, R. H.; Brudvig, G. W. et al. Science 1999, 283, 1524Yagi, M. et al. J. Am. Chem. Soc. 2004, 126, 8084 and Chem. Commun. 2010, 46, 8594
TON = 4 (6h)
TOF = 0.01 min-1
Crabtre and Brudvig et al.
TON = 17 (6h)
TOF = 0.05 min-1
Yagi, et al.
P*P*Ce(IVCe(IV))
TON = 4 (17h)
TOF = 0.003 min-1
Yagi, et al.
HClOHClO
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First row transition-metal based WOCs: manganese
Dismukes, G. C.; Spiccia, L. et al. Acc. Chem. Res. 2009, 42, 1935.Brimblecombe, R.; Dismukes, G. C.; Spiccia, L. et al. J. Am. Chem. Soc. 2010, 132, 2802.
P*P*
TON = 40 (1h)
TOF = 0.66 min-1
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First row transition-metal based WOCs: iron
Bernhard, S.; Collins, T. et al. J. Am. Chem. Soc. 2010, 132, 10990.
TON = 11
TOF = 78 min-1
Fast and Cheap
Ce(IVCe(IV))
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First row transition-metal based WOCs: iron
Lloret, J.; Costas, M. et al. Nat. Chem. 2011, 3, 807.
TONmax = ≥ 1.050
TOFmax = 3,7 min-1Ce(IVCe(IV))
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First row transition-metal based WOCs: iron
Lloret, J.; Costas, M. et al. Nat. Chem. 2011, 3, 807.
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OUTLINE
1. INTRODUCTION
2. Ru-based WOCs: from the Blue Dimer to mononuclear species
3. Iridium WOCs
4. All-inorganic POM complexes
5. First-row transition-metal based WOCs
8. FINAL REMARDKS AND CONCLUSIONS
6. Heterogeneous WOCs
7. WOCs in Photoelectrochemical cells (PECs)
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Heterogeneous WOCs: covalent attachment
GraftingAnchoring
EncapsulationPhysisorptinon Electrostatic
M
L
L
L
LM
L
L
L
M
L
L
L Soli
d Su
ppor
t
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Heterogeneous WOCs: covalent attachment
M
L
L
L
LM
L
L
L
M
L
L
L Soli
d Su
ppor
t
Solid Support=
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Heterogeneous WOCs: covalent attachment
Meyer, T. J. et al. JACS 2007, 129, 2446. Meyer, T. J. et al. JACS 2009, 131, 15580.
Meyer, T. J. et al. ACIE 2009, 48, 9473. Sala and Llobet et al. ChemSusChem 2009, 2, 321.
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Heterogeneous WOCs: electropolymerization
POLYPYRROL BACKBONE
Mola, J.; Sala, X.; Llobet, A. et al. Angew. Chem. Int. Ed. 2008, 47, 5830
CPECPE
Ce(IVCe(IV))TON = 250 (18 in homog. Phase)
TOF = 0.1 min-1 (1 homog. Phase)
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Heterogeneous WOCs: electrostatic interaction
GraftingAnchoring
EncapsulationPhysisorptinon Electrostatic
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Heterogeneous WOCs: electrostatic interaction
Toma, F. M.; Prato, M.; Bonchio M. et al. Nat. Chem. 2010, 2, 826
MWCNT
[Ru4O4(OH)2(H2O)4(γ-SiW10O36)2]10-
TOF = 0.6 min-1 (1.17 V vs. NHE)
5.1 min-1 (1.42 V vs. NHE) CPECPE
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OUTLINE
1. INTRODUCTION
2. Ru-based WOCs: from the Blue Dimer to mononuclear species
3. Iridium WOCs
4. All-inorganic POM complexes
5. First-row transition-metal based WOCs
8. FINAL REMARDKS AND CONCLUSIONS
6. Heterogeneous WOCs
7. WOCs in Photoelectrochemical cells (PECs)
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WOCs in Photoelectrochemical cells (PECs)
Sala, X.; Escriche E.; Llobet A. et al. Angew. Chem. Int. Ed. 2009, 48, 2842
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WOCs in Photoelectrochemical cells (PECs)
Youngblood, W. J.; Mallouk, T. E. et al. J. Am. Chem. Soc. 2009, 131, 923 and Acc. Chem. Res. 2009, 42, 1966.
TON = 16 (per dye molecule)
Small bias needed
= 0.09
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Youngblood, W. J.; Mallouk, T. E. et al. J. Am. Chem. Soc. 2009, 131, 923 and Acc. Chem. Res. 2009, 42, 1966.
WOCs in Photoelectrochemical cells (PECs)
Forward ETBackward ET
Backward ET one order faster
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First row transition-metal based WOCs: manganese
Dismukes, G. C.; Spiccia, L. et al. Acc. Chem. Res. 2009, 42, 1935.Brimblecombe, R.; Dismukes, G. C.; Spiccia, L. et al. J. Am. Chem. Soc. 2010, 132, 2802.
TON = 13 (per cluster molecule)
TOF = 0.83 min-1
No bias needed
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First row transition-metal based WOCs: manganese
Hocking R. K..; Spiccia, L. et al. Nat. Chem. 2011, 3, 461.
Mn2+ Mn(III/IV) – oxide phase
photoreduction
2H2OO2
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WOCs in Photoelectrochemical cells (PECs)
Li, L.; Sun, L. et al. Chem. Commun. 2010, 46, 7307
TON = 16
TOF = 0.45 min-1
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OUTLINE
1. INTRODUCTION
2. Ru-based WOCs: from the Blue Dimer to mononuclear species
3. Iridium WOCs
4. All-inorganic POM complexes
5. First-row transition-metal based WOCs
8. FINAL REMARDKS AND CONCLUSIONS
6. Heterogeneous WOCs
7. WOCs in Photoelectrochemical cells (PECs)
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LRu-O
OH
H
+
- The Nature of the Ru=O moieties in the corresponding active oxidation state
- The role of Bridging Ligand (e-coupling/through-space interactions)
cis-[Ru(bpy)2(OH2)2]2+
in,in-[{Ru(Trpy)(OH2)}2(μ-bpp)]3+
[Ru4(μ-O)4(μ-OH)2(H2O)4(γ-SiW10O36)2]10+
WNA
Intra-I2M
Active Ox. State Mechanism
VI
IV
V
WNA
Intra-I2M
WNA
[Ru(dcb)(pic)2(OH)]+ IV Inter-I2MInter-I2M
WOCs MECHANISTIC SUMMARY
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1 2
3
5
4
6
78
1 23
5
4
6 7
8
1. Meyer, JACS-1982; 2. Llobet, JACS-2004; 3. Thummel, IC-2008; 4. Hill&Bonchio JACS-ACIE-2008; 5. Albrecht-
Crabtree-Brudvig, ACIE-2010-JACS-2009; 6. Hill, Science-2010
WOCs KINETICS SUMMARY
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Xavier Sala, UAB, Barcelona, Spain
ICTP, Miramare, Trieste, October 17th 2011
Molecular Catalysts that Oxidize Water to Dioxygen