Prof. Greta R. Patzke

SATW: Journées de ReflexionYverdon, 31 October 2018

Artificial Photosynthesis:

Minds

Matter

Markets

Department of Chemistry

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Coal

52.8 Natural Gas

Oil

114

50.7

tinyurl.com/ycqn7fv9

746

471

275

Global reserves

Unburnable

Carbon budget for 2°C

Abbott, D. Proc. IEEE 2010, 98 (1), 42–66, Gesamtenergiestatistik, Tab. 24, VSE 2016, SFOE, Swiss Overall Energy Statistics 2017.

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Energy production (CH) 2016 Energy consumption (CH) 2017

Solar 85,000 TW

River Hydroelectric7 TW

Biomass7 TW

Geothermal44 TW

Wind72 TW

Human Energy Use (2013): 18 TW

x 0.06% = 50 TW

tinyurl.com/ycbymy3p

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Photosystem II

Protein: ca. 54'000 atomsInorganic core: {CaMn4O5}

Photosystem I

Protein: ca. 36'000 atomsIron-sulfur clusters

Y. Umena, K. Kawakami, J.-R. Shen, N. Kamiya, Nature 2011 (473) 55. I. Caspy, N. Nelson, Biochem. Soc. Trans. 2018 (46) 285.

2 H2O O2 + 4 e- + 4 H+ 2e- + 2H+ + NADP+ NADPH + H+

Synthetic PSII mimics (examples): E. Y. Tsui, R. Tran, J. Yano, T. Agapie, Nat. Chem. 2013 (5) 293; C. Zhang, C. Chen, H. Dong, J.-R. Shen, H. Dau, J. Zhao, Science 2015 (348) 690.

?

A. Indra, P. W. Menezes, M. Driess ChemSusChem 2015, 8, 776

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2 H2O 2 H2 + O2DG° = +237.3 kJ/mol

E°rev = 1.23 V

Solar energy directly to hydrogen - GW scale liquid fuels?

Strong water oxidation catalysts (WOCs):

2 H2O → O2 + 4 e- + 4 H+

CO2 reduction challenges:

→ 6 or more proton/electron transfers limit selectivity

→ Higher BOP costs for CO2 capture

→ Unlikely to make big dent in climate mitigation

1. Nature

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Outlook F. Evangelisti, R. Moré, F. Hodel, S. Luber, G. R. Patzke, J. Am. Chem. Soc. 2015 (137) 11076.

Stable & active {Mn4O4} cubane

WOCs: Challenge!

1st generation {CoII4O4} cubanes: Tetranuclearity & ligand environment

83% O2 yieldTON: 35

1. Nature

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Outlook F. Evangelisti, R. Moré, F. Hodel, S. Luber, G. R. Patzke, J. Am. Chem. Soc. 2015 (137) 11076.

Ln3+ ions = Ca2+ mimics

2nd generation {CoII3O4} cubanes:

Enhanced performance & mechanistic insight

Why did Nature pick the redox-inert Ca2+?

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C. Kisielowski, H. Frei, P. Specht, I. D.

Sharp, J. A. Haber, S. Helveg, Adv.

Struct. Chem. Imaging 2017 (2) 13.

Co3O4

F. Song, R. Moré, M. Schilling, G. Smolentsev, N. Azzaroli, T. Fox, S. Luber, G. R. Patzke*, J. Am. Chem. Soc. 2017 (139) 14198.

3rd generation CoII4O4-dpk cubane:

New molecular cut-outs of powerful solid catalysts

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K. Domen et al., ACS Catal. 2018 (8) 2782-2788.

A. Z. Weber et al., Energy Environ. Sci. 2018 (11) 115.

2 nm

We replaced toxic Cd in high performance QD photosensitizers!

New capping with sulfide ions:

Water soluble QDs!

S. Yu, X.-B. Fan, X. Wang, J. Li, Q. Zhang, A. Xia, S. Wei,

L.-Z. Wu, Y. Zhou, G. R. Patzke, Nat. Commun. 2018 (9) 4009.

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Turnover numbers up to 128’000

Activity for > 100 h, 31% IQY

→ Competitive with leading Cd-QDs

1. Nature

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OutlookS. Yu, X.-B. Fan, X. Wang, J. Li, Q. Zhang, A. Xia, S. Wei, L.-Z. Wu, Y. Zhou, G. R. Patzke, Nat. Commun. 2018 (9) 4009.

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Outlook 2009 DOE Technoeconomical Analysis of PEC Hydrogen Production.T. F. Jaramillo et al., Energy Environ. Sci. 2013 (6) 1983.

Si junction / membraneCobalt

CatalystNiMoZnCatalyst

++++

----

H2O2

H2OH+

«artificial leaf»

Overall solar-to-fuel efficiency 4.7%: (PV) · (WS)

(PV)= 7.7%, water splitting efficiency = 60%

D.G. Nocera, Acc. Chem. Res., 2012, 45, 767 & Sun Catalytix

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Three lab prototype designs:

I. PV immersed in electrolyte with catalyst electrodes on both sides

II. Only one side of PV part exposed to electrolyte (wire needed)

II. Complete separation of PV andelectrocatalytic elements

B. Turan, J.-P. Becker, F. Urbain, F. Finger, U. Rau, S. Haas, Nature Commun. 2016 (7) 12681.

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OutlookB. Turan, J.-P. Becker, F. Urbain, F. Finger, U. Rau, S. Haas, Nature Commun. 2016 (7) 12681.

64 cm2

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Outlook R. Van de Kroel, B. A. Parkinson, MRS Energy & Sustainab. 2017 (4) e13.

PEC PV-E

Lab

Tech

tinyurl.com/y8cfahwt

J. Su, L. Vayssieres, ACS Energy Lett. 2017 (1) 121.

tinyurl.com/ycgyp759

In & exsitu

SurfaceAnalytics

ESRF BM01 Swiss Norwegian Beamline: MNCN series M = Co, Co0.9Ni0.1, Ni, Mn, Cu

XAS fluorescence detector

Ramandetector

X-ray source

X-ray path for transmission

SPE connector Raman source

R. J. Müller, J. Lan, K. Lienau, R. Moré, C. A. Triana, M. Iannuzzi, G. R. Patzke, Dalton Trans. 2018 (47) 10759.

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Oxide formation?

Screen printed electrode (SPE):

Dropcasting ofCoNCN/Nafion ink

Operando Raman spectra of CoNCNat different applied voltages:

→ Oxide-related peaks absent

R. J. Müller, J. Lan, K. Lienau, R. Moré, C. A. Triana, M. Iannuzzi, G. R. Patzke, Dalton Trans. 2018 (47) 10759.

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MNCN series (M = Co, Co0.9Ni0.1, Ni, Mn, Cu):

→ Only CuNCN forms oxide layer operando

CuNCN: XANES (fluorescence) spectra & descriptors: 80 % CuO at 1.2 V

R. J. Müller, J. Lan, K. Lienau, R. Moré, C. A. Triana, M. Iannuzzi, G. R. Patzke, Dalton Trans. 2018 (47) 10759.

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1. Nature

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Outlook E. Koepf, I. Alxneit, C. Wieckert, A. Meyer, Appl. Energy 2017 (188) 620.

Solar Syngas from Oxides

1/δCeO2 1/δCeO2-δ + 0.5 O2(g)High T (1500 °C):

Lower T

CO & H2

Fischer-Tropsch fuelsTask: max. δ

oxygen vacancies (Vo..)

H2O(g) + 1/δCeO2-δ1/δCeO2 + H2(g)

CO2(g) + 1/δCeO2-δ1/δCeO2 + CO(g)

1000 °C

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• Engineering@ETH Zurich (Prof. Aldo Steinfeld)

W. C. Chueh, C. Falter, M. Abbott, D. Scipio, P. Furler, S. M. Haile, A. Steinfeld, Science 2010 (330) 1797.

OUR TASK:High performance oxide reactor for present heliostat

infrastructure

Solar Power through Oxide Materials

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STF (4kW) = 5.25%PV-Emax = 6.25%PECmax = 2%

D. Marxer, P. Furler, M. Takacs, A. Steinfeld, Energy Env. Sci. 2017 (10) 1142.

Ceria: Dopant Screening

Cm

Screening of all potential tetravalent dopants in

the PSE (Shannon radii)

Tetravalent dopants

• Reversible oxygen vacancies

• Ce3+ is larger than Ce4+

Initial redox cycle Oxidation

R. Jacot, R. Moré, R. Michalsky, A. Steinfeld, G. R. Patzke, J. Mater. Chem A 2017 (5) 19901.

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Ceria Dopant Optimization Strategy

VMoW

Cm

TbW

Zr

First selection(thermal stability)

→ Hf-, Zr- & Nb doped ceria remains stable after prolonged TGA cycling

Before 50 cycles After 50 cycles

→ Homogeneous dopant distribution: Key factor! 1. Nature

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OutlookR. Jacot, J. M. Naik, R. Moré, R. Michalsky, A. Steinfeld, G. R. Patzke, J. Mater. Chem. A 2018, 6, 5807.

Zr

Hf

Nb

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www.sunfire.deCO2 & Water electrolysis (solid oxide cell stacks)

www.skytree.eu

CO2 capture from airwww.climeworks.com

www.dimensionalenergy.net

Solar thermal CO2 conversion to methanol

www.opus-12.com

CO2 electrolysis to CO for on-site generation

www.catalytic-innovation.com

Water oxidation for corrosion resistance

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(4) Final capital investment & life cycle analysis for PV?

T. Bolsen, J. N. Druckman, F. Lomax Cook, Chem 2016 (1) 515.

S. Ardo et al., Energy Environ. Sci. 2018, DOI: 10-1039/c7ee03639f.

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Outlook S. Sheehan et al., Chem 2018, DOI: 10.1016/j.chempr.2017.06.003

ACS Catal. 2013 (3) 1486.

2. Nanoscale & Solid Catalysts

In situ formation monitoring &

Analytical tracking

1. Molecular Catalysts

Principles of Photosystem II

H2 evolution with Quantum Dots

3. Concentrated Solar Power

Doped ceria vs. perovskites

Cooperation: Prof. Aldo Steinfeld, ETH Zurich

25 °C

1500 °C

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tinyurl.com/y8m27mak

Karl-Heinz Ernst (EMPA)H2 Formation and CO2 Reduction

David TilleyPhotoelectrocatalysisMolecular Approaches to Renewable Energies

Andreas Borgschulte (EMPA)trMOKEAdvanced Analytical Technologies

Jürg OsterwalderCatalysts on SurfacesUltrafast Electron Dynamics and Scattering

Roger AlbertoWater Reduction Catalysts & PhotosensitizersMetals in Medicine / Molecular Imaging

Greta R. PatzkeWater Oxidation CatalystsSolids, Oxoclusters & Molecules

Peter HammUltra-fast Spectroscopy & MechanismsFemto Second and 2D-IR Spectroscopy

Jürg Hutter Sandra LuberElectronic Structures and Reaction Pathways of WOC/WRCAdvanced Electronic Structure Methods

Devices

Theory

Catalysts Mechanisms

UZH Priority Program: www.lightchec.uzh.ch

Acknowledgements

www.lightchec.uzh.ch

GROUP:

Dr. Fabian von RohrDr. Carlos TrianaDr. Sima HeidariDr. Christos MavrokefalosJingguo LiFangyuan SongSimona ContiRobin GüttingerKarla LienauRafael MüllerEsmael BalaghiLukas ReithMadhusudhan JarplaYonggui ZhaoDevi Prasad A SGiann WiprächtigerKeyuan MaDorota WalickaCatherine Witteveen

UZH Special Research Program:LightChEC: Profs. Roger Alberto, Jürg Osterwalder,Peter Hamm, Jürg Hutter, David Tilley, Sandra Luber, Karl-Heinz Ernst, PD Dr. Andreas Borgschulte

Prof. Dr. Aldo Steinfeld (ETH Zurich)PD Dr. Davide Bleiner (Empa Dübendorf)Prof. Dr. Richard Walton (University of Warwick/UK)Dr. Shan Yu, Prof. Ying Zhou (Southwest Petrolum U/Chengdu)

https://tinyurl.com/y7799dc2