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

http://www.google.cat/url?sa=i&rct=j&q=SPARK&source=images&cd=&cad=rja&uact=8&ved=0ahUKEwip5pDhtcrLAhXItRoKHaRuA9oQjRwIBw&url=https://www.windowssearch-exp.com/images/search?q%3DLight%2BSparks%2BFrom%26FORM%3DRESTAB&psig=AFQjCNGSG9ycvqncLle6vd4OInnqbMdF-g&ust=1458396828698720


1. INTRODUCTION

2. hn WOC-PR HOMOGENEOUS PHASE

3. MOLEC ELECTROANODES

4. MOLEC PHOTOANODES

5. COMPLETE DEVICES

6. CONCS & ACKS

hn CATALYSIS AND DEVICES

http://www.google.cat/url?sa=i&source=images&cd=&docid=LWsRCD4h98T0hM&tbnid=OF3weCUF0rk-mM:&ved=0CAUQjRw&url=http://science.howstuffworks.com/environmental/green-tech/energy-production/artificial-photosynthesis.htm&ei=enkCUvLyDqHC0QXn3IH4Bg&psig=AFQjCNHIhb8PfRgc0XSs3navlAXlD9WCnQ&ust=1375980266847983


http://www.google.cat/url?sa=i&rct=j&q=nickel oxide structure&source=images&cd=&cad=rja&uact=8&ved=0CAcQjRw&url=http://www.webelements.com/compounds/nickel/nickel_oxide.html&ei=xHRlVZOgBYT2UOuxgYAH&bvm=bv.93990622,d.d24&psig=AFQjCNH2DFsM-uDVVlpOVOIxGkydVHxvfw&ust=1432798760458791






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




5. COMPLETE DEVICES

6. CONCS & ACKS










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

http://www.google.cat/url?sa=i&rct=j&q=fast&source=images&cd=&cad=rja&uact=8&ved=0ahUKEwj054D9vMPLAhUCvRQKHe4dC9sQjRwIBw&url=http://goaleurope.com/2011/11/28/innovation-eastern-europe-startup-cee-venture-capital-deloitte-500-emea-what-businesses-are-growing-fastest-in-eastern-europe/&bvm=bv.116636494,d.d24&psig=AFQjCNEiry1kUiy87tsx720hLd7Umghv2w&ust=1458158180658427

http://www.google.cat/url?sa=i&rct=j&q=fast&source=images&cd=&cad=rja&uact=8&ved=0ahUKEwj054D9vMPLAhUCvRQKHe4dC9sQjRwIBw&url=http://goaleurope.com/2011/11/28/innovation-eastern-europe-startup-cee-venture-capital-deloitte-500-emea-what-businesses-are-growing-fastest-in-eastern-europe/&bvm=bv.116636494,d.d24&psig=AFQjCNEiry1kUiy87tsx720hLd7Umghv2w&ust=1458158180658427

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



D

Na2S2O8

WOCSEA

8-10-2007 14



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



DSEA

Na2S2O8

WOC

8-10-2007 16

pH = 7.0


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



pH = 7.0


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




5. COMPLETE DEVICES

6. CONCS & ACKS










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 ON GRAPHENE



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




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


Coehn, A.; Gläser, M. Zeits. Anorg. Chem., 1902, 33, 9-24

I2M to WNA

http://www.google.cat/url?sa=i&rct=j&q=Ruthenium+(IV)+oxide&source=images&cd=&cad=rja&uact=8&ved=0ahUKEwiIlKGUvJ_JAhXCuhQKHWkYBAwQjRwIBw&url=https://de.wikipedia.org/wiki/Ruthenium(IV)-oxid&psig=AFQjCNFSvvUXFd7NWnzHgNB8C5ZxiM9S5A&ust=1448124961534183


Ru-BDA UNDER RESTRICTED MOBILITY


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




5. COMPLETE DEVICES

6. CONCS & ACKS










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



Ruprecursor

Ru-OH2

active species

Si/TiO2/C config.

buried junction device

hn - 240 mVcathodic shift



Ruprecursor

Ru-OH2

active species

BORON-DOPEP

p+-Si electrodes

pH = 7.0


Chronoamp. @ 1 mA/cm2


pH = 7.0

Faradaic Eff > 90%

TON > 60.000

1. INTRODUCTION




5. COMPLETE DEVICES

6. CONCS & ACKS










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

http://www.google.cat/url?sa=i&rct=j&q=icfo&source=images&cd=&cad=rja&uact=8&ved=0CAcQjRxqFQoTCKX8jZaSlcYCFYm4FAodqVYAPQ&url=http://www.photonics4life.eu/P4L/About-Photonics4Life/Members-Partners/ICFO-The-Institute-of-Photonic-Sciences&ei=-5KAVeWSFInxUqmtgegD&bvm=bv.96041959,d.d24&psig=AFQjCNGBeLdRqV5z99D6hnXD0mV6CBF0Hw&ust=1434575984176244

http://www.google.cat/url?sa=i&rct=j&q=icfo&source=images&cd=&cad=rja&uact=8&ved=0CAcQjRxqFQoTCKX8jZaSlcYCFYm4FAodqVYAPQ&url=http://www.photonics4life.eu/P4L/About-Photonics4Life/Members-Partners/ICFO-The-Institute-of-Photonic-Sciences&ei=-5KAVeWSFInxUqmtgegD&bvm=bv.96041959,d.d24&psig=AFQjCNGBeLdRqV5z99D6hnXD0mV6CBF0Hw&ust=1434575984176244

https://3dprint.com/1666/scientists-3d-print-new-solar-panels-which-work-best-when-cloudy/


http://www.energyharvestingjournal.com/articles/2212/progress-with-flexible-photovoltaics



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


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.

http://www.google.cat/url?sa=i&rct=j&q=killing+to+birds+in+one+stone&source=images&cd=&cad=rja&uact=8&ved=0ahUKEwjrtfbbuorSAhUFPRoKHVB_D8IQjRwIBw&url=https://www.linkedin.com/pulse/20141107151659-116527518-old-sayings-that-might-need-updating-killing-two-birds-with-one-stone&psig=AFQjCNHv-ZvywUU4n6n4h8G2kamgJNW0aA&ust=1486985433365153

http://www.google.cat/url?sa=i&rct=j&q=killing+to+birds+in+one+stone&source=images&cd=&cad=rja&uact=8&ved=0ahUKEwjrtfbbuorSAhUFPRoKHVB_D8IQjRwIBw&url=https://www.linkedin.com/pulse/20141107151659-116527518-old-sayings-that-might-need-updating-killing-two-birds-with-one-stone&psig=AFQjCNHv-ZvywUU4n6n4h8G2kamgJNW0aA&ust=1486985433365153

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

http://www.google.cat/url?sa=i&rct=j&q=OK&source=images&cd=&cad=rja&uact=8&ved=0CAcQjRw&url=https://es.wikisource.org/wiki/Archivo:Symbol_OK.svg&ei=Z8GCVfviCMLcUfHbgpgG&bvm=bv.96041959,d.d24&psig=AFQjCNHd9yKQWzYhp67ojqms1TwZXchXWg&ust=1434718945367590




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




5. COMPLETE DEVICES

6. CONCS & ACKS










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




http://fotw.fivestarflags.com/images/e/es-ct.gif

http://fotw.fivestarflags.com/images/e/es-ct.gif

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http://www.google.cat/url?sa=i&rct=j&q=chineese+flag&source=images&cd=&cad=rja&uact=8&ved=0CAcQjRxqFQoTCM2Q3cPJgMkCFcu7FAody3kHLQ&url=http://www.clker.com/clipart-7277.html&bvm=bv.106923889,d.d24&psig=AFQjCNH8kT8d1JghN-uwRZgFhAxhuU-GTA&ust=1447063428206093

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

http://mcnl.ewha.ac.kr/wiki/index.php/File:Ewha-womans-logo.gif

http://mcnl.ewha.ac.kr/wiki/index.php/File:Ewha-womans-logo.gif

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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”

nuevas formas de almacenamiento de energía renovable ... · 2. hnwoc-pr homogeneous phase 3. molec...

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