A bio-inspired tandem cell for solar fuel production Andrea Barbieri ISOF CNR Dec. 16th, 2014 Coffee Talk @ ISOF 1
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 Talk @ ISOF 2
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 Talk @ ISOF 3
Scope of the work Dec. 16th, 2014 Coffee Talk @ ISOF 4
Istituto per la Sintesi Organica e la Fotoreattività Bologna (IT) Extraction and purification of PSI-LHCI from Cyanidioschyzon merolae Sucrose Gradient Separation of PSI 150 75 PsaA/PsaB 50 37 25 20 15 10 5 3 Dec. 16th, 2014 Coffee Talk @ ISOF Lhcr PsaC PsaK PsaJ PsaM/PsaI 5
Preparation of the samples Dec. 16th, 2014 Coffee Talk @ ISOF 6
Hydrogen evolution Dec. 16th, 2014 Coffee Talk @ ISOF 7
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 Talk @ ISOF 8
Steady state fluorescence (λ ex 580 nm) Intensity (a.u.) 1.0 0.8 0.6 0.4 A A1a A1b B1 PSI 0.2 0.0 550 600 650 700 750 800 850 Wavelength (nm) Dec. 16th, 2014 Coffee Talk @ ISOF 9
10000 Istituto per la Sintesi Organica e la Fotoreattività Bologna (IT) Fluorescence decay kinetic PSI (adsorbed) Fe 2 O 3 / FTO 1000 Counts 100 10 Std Dev 1 10 0-10 10 20 30 40 Time (ns) 10 20 30 40 Time (ns) Dec. 16th, 2014 Coffee Talk @ ISOF 10
Time resolved fluorescence Wavelength (nm) 800 750 700 PSI (PBS 7.4) 1.00 0.90 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 0 1 2 3 Time (ns) Dec. 16th, 2014 Coffee Talk @ ISOF 11
Time resolved fluorescence Wavelength (nm) 800 750 700 A1a (covalent binding) 1.00 0.90 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 0 1 2 3 Time (ns) Dec. 16th, 2014 Coffee Talk @ ISOF 12
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PS I core from cyanobacteria Melkozernov, A. N.; Barber, J.; Blankenship, R. E. Biochemistry 2006, 45, 331-345 Dec. 16th, 2014 Coffee Talk @ ISOF 14
PS I core from cyanobacteria Melkozernov, A. N.; Barber, J.; Blankenship, R. E. Biochemistry 2006, 45, 331-345 Dec. 16th, 2014 Coffee Talk @ ISOF 15
Average Lifetime 300 200 η PCE = 0.17% A A1a A1b B1 PSI < τ > (ps) 100 η PCE = 0.02% 0 650 700 750 800 Wavelength (nm) Dec. 16th, 2014 Coffee Talk @ ISOF 16
Conventional liquid-electrolyte DSSC Dec. 16th, 2014 Coffee Talk @ ISOF 17
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 36-38 ps coupled peripheral antennas 200-240 ps distortion of protein structure 620-640 ps uncoupled pigments 1.47-1.63 ns Dec. 16th, 2014 Coffee Talk @ ISOF 18
Adv. Funct. Mater. 2014, 24, 7467-7477 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 Talk @ ISOF 19
Acknowledgements Alessandra Degli Esposti Alessandro Venturini Barbara Ventura Lucia Flamigni Maria Pia Gullo Mila D Angelantonio Nicola Armaroli https://www.isof.cnr.it Dec. 16th, 2014 Coffee Talk @ ISOF 20
Istituto per la Sintesi Organica e la Fotoreattività Bologna (IT) Dec. 16th, 2014 Coffee Talk @ ISOF 21