historic development - iciq.org · 8-10-2007 2 antoni llobet research group, iciq-uab nuevas formas...
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8-10-2007 2
Antoni Llobet Research Group, ICIQ-UAB
Nuevas formas de almacenamiento de energía renovable: fotosíntesis artificial
Buenos Aires, 22-26 de Octubre, 2018
MOLECULAR WATER OXIDATION CATALYSTS:
HISTORIC DEVELOPMENT
1. INTRODUCTION
2. DINUCLEAR COMPLEXES
3. MONONUCLEAR Ru-WOCs
4. INTRAMOLEC PT
5. LIGAND BASED OXIDATION WOCs
6. CONCS & ACKS
MOL WOCs HISTORIC
Maeda, K.; Domen, K. J. Phys. Chem. Lett., 2010, 1, 2655-2661
Fujishima, A.; Honda, K., Nature, 1972, 238, 37 - 38
NEW ENERGY CONVERSION SCHEMES
F-H eff./PS-II
44-C
WATER OXIDATION
Huynh, M. H. B.; Meyer, T. J. Chem. Rev., 2007, 107, 5004.
Masllorens, E.; Llobet, A. et al. J. Am. Chem. Soc., 2006, 128, 5306
2 H2O O=O + 4 H+ + 4 e-
PCET RXNS
… WO at a molecular level…
Eo = 1.23 V, vs NHE at pH = 0
8-10-2007 6
WOCs: MOLECULAR vs. OXIDES
Coehn, A.; Gläser, M. Zeits. Anorg. Chem., 1902, 33, 9-24.
Gestern, S. W.; Samuels, G. J.; Meyer, T. J. J. Am. Chem. Soc., 1982, 104, 4029
Molecular, 1982
Coord. Chem.
2 H2O
O2 + 4H+ + 4e-
Mol-WOCs
Ox-WOCs
1902
8-10-2007 7
OXIDE-WOCs: A HISTORICAL PERSPECTIVE
Coehn, A.; Gläser, M. Zeits. Anorg. Chem., 1903, 33, 9-24.
Hickling, A.; Hill, S. Disc. Faraday Soc., 1947, 1, 236-246
CoSO4 / pH = 1, 7 & 9 / Pt
O2-evol exp.; J = 1 A/cm2
at pH=14.0, 1N KOH
for Co at all J a deposit occurred
Co
Fe
Ni
0.61 V
0.63 V
1.04 V
Walther Nernst - Göttingen
- Founder of the Physicochemical Institute, 1895
- Noble Prize, 1920
CoOx formation - CoPi
1903 - Coehn&Gläser - Göttingen
1947 - Hickling&Hill - Liverpool Metal Electrodes
films
WERNER COMPLEXES AS Mol-WOCs
PT, ET, PCET,
BOND FORM&BREAK
> 14 ODERS OF
MAGNITUDE
Marcus:
1903
1913
1983
1992
MOLECULAR TOOLKIT
MOL WOCs OBJECTIVES
2 H2O O=O + 4 H+ + 4 e-
Eo = 1.23 V, vs NHE at pH = 0
TOF, h
TON
MOL WOCs OBJECTIVES
2 H2O O=O + 4 H+ + 4 e-
Eo = 1.23 V, vs NHE at pH = 0
Klauss, A.; Haumann, M.; Dau, H. Proc. Natl Acad. Sci. 2012, 109, 16035 -16040
PCET
O-O BF
Kok Cycle
TOF, h
TON
[Ru(tpm)(bpy)(OH2)]2+
Ru-AQUA COMPLEXES – HIGH OXIDATION STATES
Masllorens, E.; Llobet, A. et al. J. Am. Chem. Soc., 2006, 128, 5306
Rodríguez, M.; Romero, I.; Llobet, A. et al. Inorg. Chem., 2001, 40, 4150-4156
8-10-2007 12
POTENTIAL METAL BASED PATHWAYS FOR
O-O BOND FORMATION
Garrido-B., P.; Gimbert-S., C.; Matheu, R.; Sala, X.; Llobet, A. Chem. Soc. Rev., 2017,46, 6088
MOL WOCs OBJECTIVES
2 H2O O=O + 4 H+ + 4 e-
Eo = 1.23 V, vs NHE at pH = 0
Mol-WOCs
Ox-WOCs
KINETICSTHERMODYNAMICS
8-10-2007 14
MOL-WOCs - LONG TERM STABILITY
30-C
LONG TERM STABILITY
< 2 nm; DLS non-detectable
L
LOW Mw OXIDES
2.61 nm
Coehn, A.; Gläser, M. Zeit. Anorg. Chem., 1903, 33, 9-24.
MISSLEADING
LDISSOCIATION
OXIDATION
MOL-WOCs LONG TERM STABILITY
8-10-2007 16
Mol-WOCs: HISTORICAL PERSPECTIVE
Gestern, S. W.; Samuels, G. J.; Meyer, T. J. J. Am. Chem. Soc., 1982, 104, 4029
Iverson, T. M.; Maghlaoui, K.; Barber, J.; Iwata, S. Science, 2004, 303, 1831-1838
Matheu, R., Llobet et al. J. Am. Chem. Soc., 2015, 137, 10786-10795
1982
the blue dimer
2004
X-ray OEC-PSII
2015
better than nature!
1.0 x 10-3 s-1
300-500 s-1
5.0 x 104 s-1
MOL-WOCs KINETICS SUMMARY
Llobet, A. et al. in “Molecular Water Oxidation Catalysts. Wiley, 2014
OEC-PSII
log
TOF
(s-1
)
Matheu, R., Ertem, Z.; Batista, V. S.; Llobet , A. et al. J. Am. Chem. Soc., 2015, 137, 10786-10795.
1. INTRODUCTION
2. DINUCLEAR COMPLEXES
3. MONONUCLEAR Ru-WOCs
4. INTRAMOLEC PT
5. LIGAND BASED OXIDATION WOCs
6. CONCS & ACKS
MOL WOCs HISTORIC
DINUCLEAR Ru COMPLEXES
Sens, C.; Llobet, A. et al., J. Am. Chem. Soc., 2004, 126, 7798;
Mola, J.; Rodríguez, M.; Llobet, A. et al. Angew. Chem. Int. Ed., 2008, 47, 5830
The blue dimer
[(bpy)2RuIII-O-RuIII(bpy)2]4+
OH2H2O
Bozoglian, F.; Romain, S.; Cramer, C.J.; Llobet, A. J. Am. Chem. Soc., 2009, 131, 15176
Romain, S.; Bozoglian, F.; Llobet, A. et al., J. Am. Chem. Soc., 2009, 131, 2768
Angeles-Boza, A. M.; Ertem, M. Z.; Llobet, A.; Cramer, C. J.; Roth, J. P. Chem. Sci., 2014, 5, 1141
I2M-intra
dormant
synthetic versatility
entropic control
8-10-2007 20
THE Ru-Hbpp COMPLEX: MER vs. FAC
trpy
tpym
8-10-2007 21
THE Ru-Hbpp COMPLEX: MER vs. FAC
trpy tpym
Maji, S.; Vigara, L., Cottone, F.; Llobet, A. et al. Angew. Chem. Int. Ed., 2012, 51, 5967-5970
8-10-2007 22
LIGAND DESIGN DIRECTS O-O BOND FORMATION PATH
Maji, S.; Vigara, L., Cottone, F.; Llobet, A. et al. Angew. Chem. Int. Ed., 2012, 51, 5967-5970
DINUCLEAR Ru COMPLEXES
tpym
Maji, S.; Vigara, L., Cottone, F.; Llobet, A. et al. Angew. Chem. Int. Ed., 2012, 51, 5967-5970
Neudeck, S.; Meyer, F., Llobet, A., et al., J. Am. Chem. Soc., 2014, 136, 24-27.
WNA
I2M-bimolec
Lopez, I.; Ertem, M. Z.; Batista, V.; Llobet, A. et al., Angew. Chem. Int. Ed. 2014, 53, 205-210
Simultaneous
//
pathways
8-10-2007 24
Fukuzumi, S.; Mandal, S.; Nam, W.; Llobet, A. et al., J. Am. Chem. Soc., 2012, 134, 9906-9909
WATER OXIDATION vs. OXYGEN REDUCTION
8-10-2007 25
WATER OXIDATION vs. OXYGEN REDUCTION
Fukuzumi, S.; Mandal, S.; Nam, W.; Llobet, A. et al., J. Am. Chem. Soc., 2012, 134, 9906-9909
8-10-2007 26
WATER OXIDATION vs. OXYGEN REDUCTION
Fukuzumi, S.; Mandal, S.; Nam, W.; Llobet, A. et al., J. Am. Chem. Soc., 2012, 134, 9906-9909
8-10-2007 27
WATER OXIDATION vs. OXYGEN REDUCTION
Co
Fukuzumi, S.; Mandal, S.; Nam, W.; Llobet, A. et al., J. Am. Chem. Soc., 2012, 134, 9906-9909
8-10-2007 28
WATER OXIDATION WITH Co
Rigsby, M. L.; Mandal, S.; Nam, W.; Llobet, A.; Stahl, S. S. et al., Chem. Sci., 2012, 3, 3058-3062
8-10-2007 29
WATER OXIDATION WITH Co
Gimbert-Suriñach, C. Dooshaye, M.; Llobet, A. et al., J. Am. Chem. Soc., 2016, 138, 15291-15294
8-10-2007 30
WATER OXIDATION WITH Co
Gimbert-Suriñach, C. Dooshaye, M.; Llobet, A. et al., J. Am. Chem. Soc., 2016, 138, 15291-15294
8-10-2007 31
WATER OXIDATION WITH Co
Gimbert-Suriñach, C. Dooshaye, M.; Llobet, A. et al., J. Am. Chem. Soc., 2016, 138, 15291-15294
8-10-2007 32
WO/OR SUMMARY WITH Co
Fukuzumi, S.; Mandal, S.; Nam, W.; Llobet, A. et al., J. Am. Chem. Soc., 2012, 134, 9906-9909
WATER OX
OXYGEN RED
X-RAY STRUC
X-RAY STRUC
Rigsby, M. L.; Mandal, S.; Nam, W.; Llobet, A.; Stahl, S. S. et al., Chem. Sci., 2012, 3, 3058-3062
Gimbert-Suriñach, C. Dooshaye, M.; Llobet, A. et al., J. Am. Chem. Soc., 2016, 138, 15291-15294
1. INTRODUCTION
2. DINUCLEAR COMPLEXES
3. MONONUCLEAR Ru-WOCs
4. INTRAMOLEC PT
5. LIGAND BASED OXIDATION WOCs
6. CONCS & ACKS
MOL WOCs HISTORIC
8-10-2007 34
MONONUC COMPLEXES AND WNA MEC.
Thummel & Meyer J. Am. Chem. Soc., 2005, 127, 12802 & 2008, 130 16462.
Berlinguette, C. P. et al., J. Am. Chem. Soc., 2010, 132, 16094.
Vigara, L.; Dau, H.; Haumann, M.; Cramer, C. J.; Llobet, A. et al. Chem. Sci., 2012, 3, 2576
= O16
= O18
= O232
= O234
= O236
8-10-2007 35
THE “ROLLER COASTER” MECHANISM
Ox. State
0
-1
-2
Color
O
O
O
Thummel & Meyer J. Am. Chem. Soc., 2005, 127, 12802 & 2008, 130 16462.
Berlinguette, C. P. et al., J. Am. Chem. Soc., 2010, 132, 16094.
Vigara, L.; Dau, H.; Haumann, M.; Cramer, C. J.; Llobet, A. et al. Chem. Sci., 2012, 3, 2576
8-10-2007 36
MONONUC COMPLEXES AND WNA MEC.
O-O BF TS / APT MEC
Thummel & Meyer J. Am. Chem. Soc., 2005, 127, 12802 & 2008, 130 16462.
Berlinguette, C. P. et al., J. Am. Chem. Soc., 2010, 132, 16094.
Vigara, L.; Dau, H.; Haumann, M.; Cramer, C. J.; Llobet, A. et al. Chem. Sci., 2012, 3, 2576
Ox. State
0
-1
-2
Color
O
O
O
8-10-2007 37
Lopez, I.; Ertem, M. Z.; Batista, V. S.; Llobet, A. et al., Angew. Chem. Int. Ed. 2014, 53, 205-210
RuV=O group
weakens the trans Ru-N bond
“trans-influence” X-Ray Structure
[RuIV(trpy)(5,5’-F2-bpy)(O)]2+
Ru-O = 1.85 Å
Ru-Ntrans = 2.14 Å
Ru-Ncis(av) = 2.06 Å
MONONUC COMPLEXES AND WNA MEC.
Intrinsic Instability Of High Oxidation States
is one site really enough? LONG TERM STABILITY
8-10-2007 38
40.000 TN
TJM ACIE 2011
MONONUC COMPLEXES AND WNA MEC.
Lopez, I.; Ertem, M. Z.; Batista, V. S.; Llobet, A. et al., Angew. Chem. Int. Ed. 2014, 53, 205-210
8-10-2007 39
PARALLEL SIMULTANEOUS CAT CYCLES
GATE
MONONUC COMPLEXES AND WNA MEC.
from Self-Repair to Self-Improved
Lopez, I.; Ertem, M. Z.; Batista, V. S. ; Llobet, A. et al., Angew. Chem. Int. Ed. 2014, 53, 205-210
O-Ru-O 145o
[RuII(bda)(pic)2] in H2O
Ru(II)-bda DYNAMIC BEHAVIOR
Matheu, R.; Haumann, M.; Batista, V.; Llobet, A. et al. Chem. Eur. J. 2018, in press
8-10-2007 41
VT-NMR / XAS / DFT
H2O
PEARSON HS-AB
H-BONDING BELT
k-N2O
k-NO2
Matheu, R.; Haumann, M.; Batista, V.; Llobet, A. et al. Chem. Eur. J. 2018, in press
Ru(II)-bda DYNAMIC BEHAVIOR
8-10-2007 42
O-Ru-O 145o
[RuII(bda)(pic)2]
Ce(IV)
Duan, L.; Llobet, A.; Sun, L. et al. Nat. Chem. 2012, 4, 418-423
The 18 e- Rule & 2-Coord Sphere Effects
[RuIV(OH)(bda-k-N2O2)(pic)2]+
RuIV-d4
Catalysis at Ru(V)
Ru-bda HIGH OXIDATION STATES
Duan, L.; Mandal, S.; Bozoglian, F.; Privalov, T.; Llobet, A.; Sun, L. Nat. Chem. 2012, 4, 418-423
4-Me-py
TOF = 6 s-1
Ru-bda WATER OXIDATION KINETICS
Duan, L.; Mandal, S.; Bozoglian, F.; Privalov, T.; Llobet, A.; Sun, L. Nat. Chem. 2012, 4, 418-423
Richmond, C. J.; Matheu, R.; Llobet, A. et al. Chem. Eur. J., 2014, 20, 17282-17286
Adaptive Ligand / 7-CN / Supramolec Int / pH = 1.0
s-DONATION / CN-7 / p-STACKING
I2M
TOF = 6 s-1
Duan, L.; Mandal, S.; Bozoglian, F.; Privalov, T.; Llobet, A.; Sun, L. Nat. Chem. 2012, 4, 418-423
Richmond, C. J.; Matheu, R.; Llobet, A. et al. Chem. Eur. J., 2014, 20, 17282-17286
Ru-bda SUPRAMOLECULAR EFFECTSI2M
TOF = 6 s-1 TOF > 1000 s-1
Richmond, C. J.; Matheu, R.; Poater, A.; Cavallo, L.; Llobet, A. et al. Chem. Eur. J., 2014, 20, 17282
Wang, L.; Duan, L.; Sun, L. et al., Chem. Commun. 2014, 50, 12947-12950
SUPRAMOLECULAR WOCs
TS-struc.
2
TOF > 1000/s (100 times higher)
Ru-bda SUPRAMOLECULAR EFFECTS
1. INTRODUCTION
2. DINUCLEAR COMPLEXES
3. MONONUCLEAR Ru-WOCs
4. INTRAMOLEC PT
5. LIGAND BASED OXIDATION WOCs
6. CONCS & ACKS
MOL WOCs HISTORIC
THE Ru(II)-tda COMPLEX
Matheu, R., Ertem, Z.; Batista, V. S.; Llobet , A. et al. J. Am. Chem. Soc., 2015, 137, 10786-10795.
INTRAMOLECULAR H+ TRANSFER
THE Ru(IV)-tda ADAPTATIVE COMPLEX
USELESS
RuIV-d4
Matheu, R., Ertem, Z.; Batista, V. S.; Llobet , A. et al. J. Am. Chem. Soc., 2015, 137, 10786-10795.
THE GENERATION OF Ru-tda-OH COMPLEX
INTRAMOLECULAR H+ TRANSFER
Matheu, R., Ertem, Z.; Batista, V. S.; Llobet , A. et al. J. Am. Chem. Soc., 2015, 137, 10786-10795.
INTRAMOLECULAR H+ TRANSFER
Matheu, R., Ertem, Z.; Batista, V. S.; Llobet , A. et al. J. Am. Chem. Soc., 2015, 137, 10786-10795.
FOWA FOR Ru-tda
MOL-WOCs KINETICS SUMMARY
OEC-PSII
log
TOF
(s-1
)
Llobet, A. in “Molecular Water Oxidation Catalysts. Wiley, 2014
Sala, X.; Llobet, A. et al. Angew. Chem. Int. Ed., 2009, 48, 2842
Sala, X.; Llobet, A. et al. Acc. Chem. Res. 2014, 47, 504-516
NANO SECOND TIME SCALE AT H-2020
OEC-PSII
log
TOF
(s-1
)
Llobet, A. in “Molecular Water Oxidation Catalysts. Wiley, 2014
Sala, X.; Llobet, A. et al. Angew. Chem. Int. Ed., 2009, 48, 2842
Sala, X.; Llobet, A. et al. Acc. Chem. Res. 2014, 47, 504-516
8-10-2007 54
1. INTRODUCTION
2. DINUCLEAR COMPLEXES
3. MONONUCLEAR Ru-WOCs
4. INTRAMOLEC PT
5. LIGAND BASED OXIDATION WOCs
6. CONCS & ACKS
MOL WOCs HISTORIC
Biswas, A. N.; Que , L. et al. J. Am. Chem. Soc., 2015, 137, 2428
A MODEL FOR PARTIAL LIGAND OXIDATION
partially oxidized ligand
model
CuIII/II
Ph·+/0
Cu-BASED WOCs w. REDOX ACTIVE LIGANDS
- tetra-anionic ligand strong bonds / small reorganizational energy/
TOFi = 50 s-1 (pH = 12.5)
TOFi = 4 s-1 (pH = 11.5)
SOMO spin distribution
Garrido-Barros, P.; Funes-Ardoiz, I.; Maseras, F.; Llobet, A. et al., J. Am. Chem. Soc., 2015, 137, 6758
CuIII/II
Ph·+/0
Cu-BASED WOCs w. REDOX ACTIVE LIGANDS
Garrido-Barros, P.; Drouet, S.; Llobet, A. et al., J. Am. Chem. Soc., 2015, 137, 6758
- tetra-anionic ligand strong bonds / small reorganizational energy/TOFi = 50 s-1 (pH = 12.5)
TOFi = 4 s-1 (pH = 11.5)
SOMO spin
distribution
Garrido-Barros, P.; Batista, V. S.; Llobet, A. et al., J. Am. Chem. Soc., 2017, 139, 12907–12910
REDOX NON-INOCENT LIGAND CONTROLS OVERPOT
Record Low Overpotential for FR-TM
Garrido-Barros, P.; Funes-Ardoiz, I.; Maseras, F.; Llobet, A. et al., J. Am. Chem. Soc., 2015, 137, 6758
8-10-2007 59
1. INTRODUCTION
2. DINUCLEAR COMPLEXES
3. MONONUCLEAR Ru-WOCs
4. INTRAMOLEC PT
5. LIGAND BASED OXIDATION WOCs
6. CONCS & ACKS
MOL WOCs HISTORIC
CONCLUSIONS
1. OXIDATIVELY ROBUST LIGANDS
2. EASY ACCESS TO HIGH OXIDATION STATES
3. LIGAND DESIGN: TRANS-EFF/INTRAMOLEC PT
4. LIGAND BASED OXIDATIONS FOR WOCs
5. MECHANISTIC PERFORMANCE; O-O BF
M. Z. Ertem
C. Cramer
L. Gagliardi
A. Poater
L. Cavallo W. Nam
S. Fukuzumi
ACKNOWLEDGMENTS
L. Sun
T. Privalov
M. Haumann; H. Dau
C. Bo
F. Maseras
E. PalomaresM. Z. Ertem
V. Batista
F. MeyerM. Lanza
Y. Shi
ICIQ Foundation, Catalonia
Consolidated Catalan Research Groups
MINECO Spain, General Science Pgr.
Severo Ochoa, Pgr.
PRF Program, ACS USA
FINANCING
SOLAR-H2, Energy Prg. UE
ERA-CHEM, MARIE CURIE
WORLD CLASS UNIV., Seoul, Korea
Fundació “La Caixa”
