Nuevas formas de almacenamiento de energía renovable ... · 2. hnwoc-pr homogeneous phase 3. molec...
-
Upload
truongdiep -
Category
Documents
-
view
214 -
download
0
Transcript of Nuevas formas de almacenamiento de energía renovable ... · 2. hnwoc-pr homogeneous phase 3. molec...
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
LIGH INDUCED REDOX CATALYSIS AND DEVICES
1. INTRODUCTION
2. hn WOC-PR HOMOGENEOUS PHASE
3. MOLEC ELECTROANODES
4. MOLEC PHOTOANODES
5. COMPLETE DEVICES
6. CONCS & ACKS
hn CATALYSIS AND DEVICES
ARTIFICIAL PHOTOSYNTHESIS
WOC
4 H+ + 4 e- 2 H2
PRC
Iverson, T. M.; Maghlaoui, K.; Barber, J.; Iwata, S. Science, 2004, 303, 1831-1838
Berardi, S.; Francàs, L.; Gimbert-Suriñach, C.; Llobet, A. et al. Chem. Soc. Rev. 2014, 43, 7501
REPLACING FOSSIL FUELS BY SOLAR FUELS
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
3-C
REPLACING FOSSIL FUELS BY SOLAR FUELS
SOLAR DRIVEN WATER SPLITTING DEVICES
McKone, J. R.; Lewis, N. S.; Gray, H. B., Chem. Mater., 2014, 26, 403-414
ultimately
8-10-2007 7
2 H2O -> O2 + 2 H2 DGo > 0
1. Anode (Photo)
2. Water Oxidation Cat (WOC)
3. Proton Reduction Cat (PRC)
4. Cathode (Photo)
PEC FOR WATER SPLITTING / MAT-SCI MOL CHEM
Berardi, S.; Drouet, S.; Francàs, L.; Gimbert, C.; Guttentag, M.; Richmond, C.; Stoll, T.;
Llobet, A. Chem. Soc. Rev., 2014, web
5. PEM + Cell
1. INTRODUCTION
2. hn WOC-PR HOMOGENEOUS PHASE
3. MOLEC ELECTROANODES
4. MOLEC PHOTOANODES
5. COMPLETE DEVICES
6. CONCS & ACKS
hn CATALYSIS AND DEVICES
LIGHT INDUCED WOC
D SEA
Na2S2O8
Neudeck, S.; Meyer, F., Llobet, A., et al., J. Am. Chem. Soc., 2014, 136, 24-27.
WOC
8-10-2007 10
LIGHT INDUCED WO - FAST CATS
stablishing kinetics and thermodynamics and understanding how to manipulate them
- Enhance stability of VB+
- Reduce Back ET at VB+
- Enhance Stability of
Intermediate Cat species
FAST WO CATs
Berardi, S.; Llobet, A. et al., ChemSusChem, 2015, 8, 3688–3696.
Neudeck, S.; Meyer, F., Llobet, A., et al., J. Am. Chem. Soc., 2014, 136, 24-27.
LIGHT INDUCED WOC: MEC EFFECT
V = 2 mL; T = 25 °C.
hn 1 Sun; l > 400 nm
pH = 7.0
D
10 mM Na2S2O8
WOC
SEA
0.2 mM Ru-bpy
0.2 mM Ru-Cat
1 sun
8-10-2007 12
LIGHT INDUCED WOCs KINETICS
TRANSIENT ABSORBANCE
SPECTROSCOSPY - TAS
Francas, L., Matheu, R.; Durrant, J, Llobet, A., et al., ACS Catal. 2017, 7, 5142−5150
8-10-2007 13
Francas, L., Matheu, R.; Durrant, J, Llobet, A., et al., ACS Catal. 2017, 7, 5142−5150
LIGHT INDUCED WOCs KINETICS
D
Na2S2O8
WOCSEA
8-10-2007 14
Francas, L., Matheu, R.; Durrant, J, Llobet, A., et al., ACS Catal. 2017, 7, 5142−5150
LIGHT INDUCED WOCs KINETICS
D
Na2S2O8
WOC
SEA0 20 40 60 80 100
0
5
10
15
20
25
30
Qu
an
tum
yie
ld
O2 (
%)
[RuII-tda] (mM)
0
200
400
600
800
1000
1200
TO
N @
1h
O2 evolution vs. t10 mM
0.2 mM Ru-bpy
1-16 mM Ru-Cat
Quantum yield, ɸO2
TONs (Ru)
1 sun
8-10-2007 15
Francas, L., Matheu, R.; Durrant, J, Llobet, A., et al., ACS Catal. 2017, 7, 5142−5150
LIGHT INDUCED WOCs KINETICS
DSEA
Na2S2O8
WOC
8-10-2007 16
pH = 7.0
LIGHT INDUCED WOCs KINETICS
kET = 1.4·107 M-1 s-1
TA decays at 460 nm (λex = 500 nm)
20 µM RuP, 10 mM S2O82-
[RuIV=O] 2 µM
0.4 µM
0 nM
1 µM
160 nM
80 nM
Francas, L., Matheu, R.; Durrant, J, Llobet, A., et al., ACS Catal. 2017, 7, 5142−5150
Francas, L., Matheu, R.; Durrant, J, Llobet, A., et al., ACS Catal. 2017, 7, 5142−5150
pH = 7.0
LIGHT INDUCED WOCs KINETICS
8-10-2007 18
2 H2O -> O2 + 2 H2 DGo > 0
1. Anode (Photo)
2. Water Oxidation Cat (WOC)
3. Proton Reduction Cat (PRC)
4. Cathode (Photo)
PEC FOR WATER SPLITTING / MAT-SCI MOL CHEM
Berardi, S.; Drouet, S.; Francàs, L.; Gimbert, C.; Guttentag, M.; Richmond, C.; Stoll, T.;
Llobet, A. Chem. Soc. Rev., 2014, web
5. PEM + Cell
D
SED
PRC
Gimbert, C.; Stoll, T.; Palomares, E.; Llobet, A. et al., J. Am. Chem. Soc., 2014, 136, 7655-7661
pH = 4.1
5.9 10–5 M
7.5 10–5 Mhn 1 Sun
l > 400 nm
Co COMP. & LIGHT INDUCED PRC
1. INTRODUCTION
2. hn WOC-PR HOMOGENEOUS PHASE
3. MOLEC ELECTROANODES
4. MOLEC PHOTOANODES
5. COMPLETE DEVICES
6. CONCS & ACKS
hn CATALYSIS AND DEVICES
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
Cu-BASED MOLECULAR ELETROANODES
Garrido-Barros, P.; Batista, V. S.; Llobet, A. et al., J. Am. Chem. Soc., 2017, 139, 12907–12910
1st OX
2nd OX
Cu-BASED MOLECULAR ELETROANODES
Garrido-Barros, P.; Batista, V. S.; Llobet, A. et al., J. Am. Chem. Soc., 2017, 139, 12907–12910
1st OX
2nd OX
Cu-BASED MOLECULAR ELETROANODES ON GRAPHENE
Garrido-Barros, P.; Batista, V. S.; Llobet, A. et al., J. Am. Chem. Soc., 2017, 139, 12907–12910
Garrido-Barros, P.; Batista, V. S.; Llobet, A. et al., J. Am. Chem. Soc., 2017, 139, 12907–12910
Increasing p-deloc.
Increases TOFmax6.2 s-1
128 s-1
320 s-1
540 s-1
TOFmax
Cu-BASED MOLECULAR ELETROANODES ON GRAPHENE
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 CATALYSISI2M
TOF = 6 s-1 TOF > 1000 s-1
8-10-2007 27
Ru-BDA ON SOLID SUPPORTS
6
TOFmax = 30 s-1 TOFmax = 1.9 s-1
pH = 7.0
CONSEQUENCES OF Ru-BDA UNDER RESTRICTED MOBILITY
Duan, L.; Llobet, A.; Sun, L. et al. Nat. Chem. 2012, 4, 418-423
Matheu, R.; Llobet, A. et al., ACS Catal. 2015, 5, 3422-3429
8-10-2007 28Duan, L.; Llobet, A.; Sun, L. et al. Nat. Chem. 2012, 4, 418-423
Ru-BDA ON SOLID SUPPORTS
6
TOFmax = 30 s-1 TOFmax = 1.9 s-1
pH = 7.0
CONSEQUENCES OF Ru-BDA UNDER RESTRICTED MOBILITY
Matheu, R.; Llobet, A. et al., ACS Catal. 2015, 5, 3422-3429
Matheu, R.; Llobet, A. et al., ACS Catal. 2015, 5, 3422-3429
E vs. NHE at pH = 7.0Engineering perspective
Building devices
RuO2
XAS
SOLID STATE ANODES FOR CAT WO
I2M
loose: pi-pi int/bimol int
CONSEQUENCES OF Ru-BDA UNDER RESTRICTED MOBILITY
Coehn, A.; Gläser, M. Zeits. Anorg. Chem., 1902, 33, 9-24
I2M to WNA
Ru-BDA UNDER RESTRICTED MOBILITY
Matheu, R.; Llobet, A. et al., ACS Catal. 2015, 5, 3422-3429
TOFi = 300 s-1 (1.0 pmol/cm2)
TONs > 45.000GC-RuO2
XAS, XANES, EXAFS
GIANT ECAT WAVE - INTRAMOLEC 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
Creus, L.; Matheu, R.; Llobet, A. et al. Angew. Chem. Int. Ed. 2016, 55, 15382-15386.
E vs. NHE at pH = 7.0
SOLID STATE ANODES: GC-MWCNT WITH WOCs
1,18 million TONs
NO DEACTIVATION
Ru-TDA UNDER TRANSLATIONAL RESTRICTED MOBILITY
WNA
1. INTRODUCTION
2. hn WOC-PR HOMOGENEOUS PHASE
3. MOLEC ELECTROANODES
4. MOLEC PHOTOANODES
5. COMPLETE DEVICES
6. CONCS & ACKS
hn CATALYSIS AND DEVICES
Sun, K.; Lewis, N. S. et al., Phys. Chem. Let., 2015, 6, 592-598
Hu, S.; Lewis, N. S. et al., Science, 2014, 344, 1005-1009
30 mA/cm2 x 1000 h = 108.000 C/cm2
pH = 14.0; Cat, 10 mC/cm2
54 secRu-abc, TOF = 5.0x104 s-1
pH = 12.0
TON = 2.7 x 106
in 41.6 days
Si-BASED PHOTOANODES
7
photocurrent-onset potentials of
−180 ± 20 mV Ref. to Eoeq for O2(g),
Sun, K.; Lewis, N. S. et al., Phys. Chem. Let., 2015, 6, 592-598
Hu, S.; Lewis, N. S. et al., Science, 2014, 344, 1005-1009
30 mA/cm2 x 1000 h = 108.000 C/cm2
pH = 14.0; Cat, 10 mC/cm2
54 secRu-abc, TOF = 5.0 x 104 s-1
pH = 12.0
TON = 2.7 x 106
in 41.6 days
WOCs: MOLECULAR vs. OXIDES
7
Matheu, R.; Llobet, A.; Lewis, N. S. et al., J. Am. Chem. Soc., 2017, 139, 11345-11348
MOLECULAR Si PHOTOANODES
Si/TiO2/C config.
buried junction device
MOLECULAR Si PHOTOANODES
Matheu, R.; Llobet, A.; Lewis, N. S. et al., J. Am. Chem. Soc., 2017, 139, 11345-11348
Ruprecursor
Ru-OH2
active species
Si/TiO2/C config.
buried junction device
hn - 240 mVcathodic shift
MOLECULAR Si PHOTOANODES
Matheu, R.; Llobet, A.; Lewis, N. S. et al., J. Am. Chem. Soc., 2017, 139, 11345-11348
Ruprecursor
Ru-OH2
active species
BORON-DOPEP
p+-Si electrodes
pH = 7.0
MOLECULAR Si PHOTOANODES
Chronoamp. @ 1 mA/cm2
Matheu, R.; Llobet, A.; Lewis, N. S. et al., J. Am. Chem. Soc., 2017, 139, 11345-11348
pH = 7.0
Faradaic Eff > 90%
TON > 60.000
1. INTRODUCTION
2. hn WOC-PR HOMOGENEOUS PHASE
3. MOLEC ELECTROANODES
4. MOLEC PHOTOANODES
5. COMPLETE DEVICES
6. CONCS & ACKS
hn CATALYSIS AND DEVICES
SOLAR DRIVEN WATER SPLITTING DEVICES
McKone, J. R.; Lewis, N. S.; Gray, H. B., Chem. Mater., 2014, 26, 403-414
ultimately
TRIPLE JUNCTION ORGANIC SOLAR CELL
Max. Eff. h = 8.7 %
Conversion Efficiency
@ 1.70-1.75 V
12
RuO2
Gimbert, C.; Martorell, J.; Llobet, A. et al., ACS Catal. 2016, 6, 3310-3316
TRIPLE JUNCTION ORGANIC SOLAR CELL
pH = 7.0
NiMoZn/RuO2 (nmol/cm2)
STH eff 5.5-6.0 % with filtered UV light
RECORD HIGH FOR OPV
Gimbert, C.; Llobet, A. et al., ACS Catal. 2016, 6, 3310-3316
pH = 7.0
NiMoZn/RuO2 (nmol/cm2)
STH eff 5.5-6.0 % with filtered UV light
RECORD HIGH FOR OPV
TOFi = 3.7 s-1
TONs > 20.000
TRIPLE JUNCTION ORGANIC SOLAR CELL
Gimbert, C.; Llobet, A. et al., ACS Catal. 2016, 6, 3310-3316
8-10-2007 45
SOLAR TO HIGH VALUE ADDED PRODUCTS
WOC
4 H+ + 4 e- 2 H2
PRC
Berardi, S.; Francàs, L.; Gimbert-Suriñach, C.; Llobet, A. et al. Chem. Soc. Rev. 2014, 43, 7501
INSPIRED but not CONSTRAINED
OSA WATER
SPLITTING
Farras, P., Garrido P.; Llobet, A. et al., Green Chem., 2016, 18, 255-260.
Farras, P., Llobet, A. et al., Green Chem., 2016, 18, 255-260.
1. Clean and with no inorganic oxidants or peroxides
2. H2 to Energy. World prod. ethylene oxide: 20 million tons/y // 2500 tons of hydrogen/day -> 2700 MWh/day.
OSA PHOTO ECHEM SYNTHESIS CELL
10
PHOTOANONDES AND CATS FOR PES CELL
Farras, P., Llobet, A. et al., Green Chem., 2016, 18, 255-260
Di Giovanni, C.; Llobet, A. ,Chem. Eur. J., 2014, 20, 3898-3902
8-10-2007 48
OSA PEC WATER SPLITTING
*
Ru-CatSubs Ox Ru-Phot/Hetero-G
hn vis
400 nm filter
Eapp = 0.3 V
Vs. NHE
H-Red
Farras, P., Llobet, A. et al., Green Chem., 2016, 18, 255-260
ANODEFTO/TiO2-P-bpy-Ru (G = 8.8 x 10-8 mol cm-2)CAT, 0.01 mMStyrene, 20 mM
CATHODEPt mesh
Eapp = 0.3 V vs. NHE
hn 1 Sunl > 400 nm
pH 1.0, 0.1 M LiClO4/HClO4 (V = 9 mL)
6.1 mmol of H2 (92 % faradaic eff)
7% subs. conv. to styrene epoxide(70 TN/0.8 ks-1 TOF)
pH = 1.0
36 ks = 10h
OSA PEC WATER SPLITTING
Farras, P., Garrido, P.; Llobet, A. et al., Green Chem., 2016, 18, 255-260.
8-10-2007 50
1. INTRODUCTION
2. hn WOC-PR HOMOGENEOUS PHASE
3. MOLEC ELECTROANODES
4. MOLEC PHOTOANODES
5. COMPLETE DEVICES
6. CONCS & ACKS
hn CATALYSIS AND DEVICES
8-10-2007 51
1. Design of efficient WOCs homogeneous phase
2. Mechanistic understanding of rxn pathways
4. Anchor cats in solid surfaces (mechs&deact)
3. Deactivation pathways
5. Light induced catalysis and Photoanodes
6. Devices for light induced WS and OSA-WS
hn CATALYSIS AND DEVICES
M. Z. Ertem
C. Cramer
L. Gagliardi
N. S. Lewis
W. Nam
S. Fukuzumi
ACKNOWLEDGMENTS
L. Sun
T. Privalov
D. Moonshiram
C. Bo
F. Maseras
E. PalomaresM. Z. Ertem
V. BatistaF. Meyer
M. Lanza
Y. Shi
ICIQ Foundation, Catalonia
Consolidated Catalan Research Groups
MINECO, General Science Pgr.
Severo Ochoa, Pgr.
PRF Program, ACS USA
FINANCING
SOLAR-H2, Energy Prg. UE
ERA-CHEM, MARIE CURIE
CARISMA COST ACTION
WORLD CLASS UNIV., Seoul, Korea
Fundació “La Caixa”