Nanobio-Interfaces for Photocatalytic Solar Hydrogen (NIPSH): Rethinking the Paradigm of “Bio-Instability” Host Mentor: Fellow: Home Mentor:
Dr. Artur Braun, Empa Dr. Krisztina Schrantz, University of Szeged Prof. András Dombi, University of Szeged
Project Code: Duration: Field:
10.013 18 months Chemistry (20303) Artur Braun
Goals
Krisztina Schrantz
András Dombi
Photocatalysis is a well established water & air purification technology for clean environment. Its main purpose is the use of photocatalytic properties of metal oxides for the destruction of harmful organic waste. It has turned out, however, that organic matter on metal oxides can also have very beneficial effect. This had been shown at Empa in the case of bio-functionalized photoelectrodes for solar water splitting. We wanted to explore the delicate balance where a biofilm can survive the harsh chemical conditions on a metal oxide and yet deliver a very good solar cell performance. The basic idea in this work was to create bio-interfaces combining a conventional semiconductor metal oxide, hematite, with organics involved in photosynthesis, to enhance the water splitting into H2 and O2. This environmentally benign energy can be a sustainable solution for the energy supply of mankind without fossil fuels. Integration of light-harvesting proteins on semiconductor surfaces can improve the performance of photoelectrodes. Therefore we used Phycocyanin (PC) which captures light in cyanobacteria and funnels it to the reaction center for photosynthesis. A way to immobilize PC on a nanostructured hematite surface to obtain higher photocurrent with long term stability is reported. Solar hydrogen generation was followed in situ.
Timeliness of the topic
Results
Surface functionalization of hematite
Hematite anode
Self-organized PC-melanin (a) and melanin (b) strains on hematite (SEM)
Photoelectrochemical Performance
Photocurrent density in phosphate buffer, pH 7.2, with 1 V external bias
Bio-interfaces: Increasing publication trend
Electronic structure of hematite
A novel photo-electrochemical cell was constructed by the Fellow, and can be connected to the gas chromatograph and potentiostat, and the produced H2 can be quantified operando/in situ, during the photoelectrochemical measurement. On-line PEC cell
Fe3p resonant valence band XPS
Impact
- Invitation of Host mentor for presentation at CRG BESSY-II Review Meeting in Berlin in 2012, based on the Fellow’s synchrotron campaigns. - 2 follow-up projects with VELUX and COST. - Swiss Management position in COST TD1102 - Several publications on artificial photosynthesis - Invitation for FET-OPEN H2020 Bio-project. - New collaboration with Empa Laboratory for Bio-Interfaces in St. Gallen.
Perspectives Host and Home institutions continued collaboration with joint work and publishing results, and a further Sciex project was funded. The Fellow gained valuable experience in the field of photo-electrochemistry, which she can implement in her work at the University of Szeged. The HOST Mentor was able to continue method development with pioneering new experiments. The field of bio-organic and cell-based artificial photosynthesis is now increasing world wide with remarkable involvement of elite research institutes.
Phycocyanin immobilization: Tyrosinase catalyzes the reaction from L-tyrosinase into melanin. When PC is added to L-tyrosine solution, tyrosinase can integrate PC due to surface exposed tyrosine side chains into the melanin structure which will then react with the activated hematite surface.
We received continued funding for the Sciex Fellow from the VELUX Foundation, shared with the Laboratory for Biomaterials, Research Group of Dr. J. Ihssen, Empa St. Gallen, with whom we started collaboration in the field of protein engineering.
Scheme of the differently tagged variants of HisCPC produced in this study
Publications: 1. A. Braun, Q. Chen, D. Flak, G. Fortunato, K. Gajda-Schrantz, M. Grätzel, T. Graule, J. Guo, T.-W. Huang, Z. Liu, A. Popelo, K. Sivula, H. Wadati, P. P. Wyss, L. Zhang, J. Zhu ChemPhysChem13(12), 2937-2944, 2012 2. D. K. Bora, E. A. Rozhkova, K. Schrantz, P. Wyss, A. Braun, T. Graule, E. C. Constable Advanced Functional Material 2012. 22(3): p. 490-502. 3. K. Gajda-Schrantz, S. Tymen, F. Boudoire, R. Toth, D. K. Bora, W. Calvet, M. Grätzel, E. C. Constable and A. Braun Physical Chemistry Chemical Physics, 15: (5) pp. 1443-1451 (2013) 4. D. K. Bora, E. C. Constable, W. Drube, S. Erat, X. Feng, G. Fortunato, N. Gaillard, K. Gajda-Schrantz, M. Graetzel, J. Guo, Y. Hu, S. Mukherjee, D. D. Sarma, S. Thiess, R. Toth, H. Wang, J. Zhu, A. Braun, Journal of Electron Spectroscopy and Related Phenomena, 190: pp.93-105 (2013) 5. M. Baia, K. Gajda-Schrantz, S. Shen, E. Stathatos International Journal of Photoenergy 2013: pp. 1-3., Editorial 6. A Braun, F. Boudoire, D. K. Bora, G. Faccio, Y. Hu, A. Kroll, B. S. Mun, S. T. Wilson, Biological components and bio-electronic interfaces of water splitting photo-electrodes for solar hydrogen production, Chem. Eur. J. 2015, 21(11), 4188-4199. 7. G. Faccio, K. Schrantz, J. Ihssen, F. Boudoire, Y. Hu, B. S. Mun, D. K. Bora, L. Thoeny-Meyer, A. Braun, Charge transfer between photosynthetic proteins and hematite in bio-hybrid photoelectrodes for solar water splitting cells, Nano Convergence 2015, 2:9. 8. J. Ihssen, A. Braun, G. Faccio, K. Gajda-Schrantz, L. Thöny-Meyer; Light harvesting proteins for solar fuel generation in bioengineered photoelectrochemical cells; Current Protein and Peptide Science, 2014, 15 (4),374-384. 9. A Thapper, S. Styring, G. Saracco, A. W. Rutherford, B. Robert, A. Magnuson, W. Lubitz, A. Llobet, P. Kurz, A. Holzwarth, S. Fiechter, H. de Groot, S. Campagna, A. Braun, H. Bercegol, V. Artero; Artificial Photosynthesis for Solar Fuels – an Evolving Research Field within AMPEA, a Joint Programme of the European Energy Research Alliance, Green 2013; 3(1): 43 –57. 10. D. K. Bora, A. Braun, K. Gajda-Schrantz in “Bioconjugated and bio-hybrid electrodes for solar fuels by photo-electrochemical water splitting”, Book "From Molecules to Materials-Pathways to Artificial Photosynthesis" Elena A. Rozhkova and Katsuhiko Ariga. Springer International Publishing (Verlag) 978-3-319-13799-5 (ISBN), 2015.
This research in bio-organic artificial photosynthesis led the Host Mentor to be invited for an AMPEA EERA-NET scoping meeting for artificial photosynthesis at the Max Planck Insitute for Chemical Energy Conversion in 2012, and to organize an MRS Symposium in 2013. Sciex Fellow Dr. Schrantz was Guest Editor of special issue „Progress and Perspectives in VisibleLight-Driven Photocatalysis” for the International Journal of Photoenergy. http://www.hindawi.com/journals/ijp/si/501047/cfp/
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