A bio-inspired tandem cell for solar fuel production

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1 A bio-inspired tandem cell for solar fuel production Andrea Barbieri ISOF CNR Dec. 16th, 2014 Coffee ISOF 1

2 ESF-EUROCORES EuroSolarFuel Background and Objectives The Molecular Science for a Conceptual Transition from Fossil to Solar Fuels (EuroSolarFuels) programme intends to accelerate the research on solar fuels on a pan-european scale. Scientific Goal The aim of EuroSolarFuels is to develop molecular science to produce a CO 2 lean solar fuel to accomplish the grand challenge of phasing out fossil fuels. Photobiological solar fuel production in green algae and/or cyanobacteria Artificial photosynthesis in molecular systems Solar fuel production in nanostructured and semiconductor-based systems Dec. 16th, 2014 Coffee ISOF 2

3 The SOLARFUELTANDEM project MODULAR DESIGN OF A BIO-INSPIRED TANDEM CELL FOR DIRECT SOLAR-TO-FUEL CONVERSION Main objective Design of a bio-inspired nanostructured organic-inorganic hetero-junction tandem cell for solar to fuel conversion Specific Objectives Functional characterization of the synthetic catalysts and assembled modules using steady-state and time-resolved optical spectroscopy methods. Molecular modeling of synthetic catalysts and reaction mechanisms for water oxidation / reduction using DFT and TD-DFT methods. Photostability tests under controlled irradiation condition on single catalyst components and interfaced cell modules. Dec. 16th, 2014 Coffee ISOF 3

4 Scope of the work Dec. 16th, 2014 Coffee ISOF 4

5 Istituto per la Sintesi Organica e la Fotoreattività Bologna (IT) Extraction and purification of PSI-LHCI from Cyanidioschyzon merolae Sucrose Gradient Separation of PSI PsaA/PsaB Dec. 16th, 2014 Coffee ISOF Lhcr PsaC PsaK PsaJ PsaM/PsaI 5

6 Preparation of the samples Dec. 16th, 2014 Coffee ISOF 6

7 Hydrogen evolution Dec. 16th, 2014 Coffee ISOF 7

8 List of the samples Name Substrate Connection A PSI / Fe 2 O 3 / FTO Physically adsorbed A1a, A1b PSI / Fe 2 O 3 / FTO Covalently bound B1 PSI / Fe 2 O 3 / AAO membrane Covalently bound F1 Fe 2 O 3 / FTO PSI PBS 7.4 Dec. 16th, 2014 Coffee ISOF 8

9 Steady state fluorescence (λ ex 580 nm) Intensity (a.u.) A A1a A1b B1 PSI Wavelength (nm) Dec. 16th, 2014 Coffee ISOF 9

10 10000 Istituto per la Sintesi Organica e la Fotoreattività Bologna (IT) Fluorescence decay kinetic PSI (adsorbed) Fe 2 O 3 / FTO 1000 Counts Std Dev Time (ns) Time (ns) Dec. 16th, 2014 Coffee ISOF 10

11 Time resolved fluorescence Wavelength (nm) PSI (PBS 7.4) Time (ns) Dec. 16th, 2014 Coffee ISOF 11

12 Time resolved fluorescence Wavelength (nm) A1a (covalent binding) Time (ns) Dec. 16th, 2014 Coffee ISOF 12

13 !"#$%&'(!"#$%&#'%!()'*)+%+&,!$-)'!&.%!/0)120!2+203,#,!)$!&.%!$04)-%,(%+(%!5%(23,6! 72'*0%!!! 8!*,!! " 8!*,!! # 8!*,!! $ 8!*, 90)120%" " % ) %& & :;!<!:! )'" %' & :C!<!B! )'# %' & :?!<!B! *+, %( & F! &!G7H!*.3,#(2003!25,)-1%5!)+!I% = J :!K!ILJ6! '!G7H!()M20%+&03!1)4+5!&)!I% = J :!K!ILJ6! (! G7HF"NOH!,4*%-()'*0%P!#+!GQ7R!# )*!S!;:D!+'6! Dec. 16th, 2014 Coffee ISOF 13

14 PS I core from cyanobacteria Melkozernov, A. N.; Barber, J.; Blankenship, R. E. Biochemistry 2006, 45, Dec. 16th, 2014 Coffee ISOF 14

15 PS I core from cyanobacteria Melkozernov, A. N.; Barber, J.; Blankenship, R. E. Biochemistry 2006, 45, Dec. 16th, 2014 Coffee ISOF 15

16 Average Lifetime η PCE = 0.17% A A1a A1b B1 PSI < τ > (ps) 100 η PCE = 0.02% Wavelength (nm) Dec. 16th, 2014 Coffee ISOF 16

17 Conventional liquid-electrolyte DSSC Dec. 16th, 2014 Coffee ISOF 17

18 Conclusions A robust red algal PSI associated with its light harvesting antenna (LHCI) have been immobilized on a semiconducting hematite surface and this photoelectrode has been utilized for the fabrication of a bio-hybrid DSSC. The photophysical behaviour of the PSI-LHCI complex in solution and immobilized on the hematite surface has been characterized by time-resolved fluorescence spectroscopy. The fluorescence decay kinetic is characterized by a sum of 3 to 4 exponential components: energy trapping ps coupled peripheral antennas ps distortion of protein structure ps uncoupled pigments ns Dec. 16th, 2014 Coffee ISOF 18

19 Adv. Funct. Mater. 2014, 24, Department of Plant Molecular Biology, Faculty of Biology, University of Warsaw Advanced Technology Research & Application Center, Mersin University Van t Hoff Institute for Molecular Sciences, Univ. Amsterdam Joanna Kargul Tomasz Krupnik Julian David Janna Olmos Kasim Ocakoglu Ersan Harputlu Saadet Yildirimcan Joost N. H. Reek Bart van den Bosch Dec. 16th, 2014 Coffee ISOF 19

20 Acknowledgements Alessandra Degli Esposti Alessandro Venturini Barbara Ventura Lucia Flamigni Maria Pia Gullo Mila D Angelantonio Nicola Armaroli Dec. 16th, 2014 Coffee ISOF 20

21 Istituto per la Sintesi Organica e la Fotoreattività Bologna (IT) Dec. 16th, 2014 Coffee ISOF 21

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