water splitting; homogeneous catalysis; hydrogen technology; water reducing catalysts; polyoxometalates; computational techniques; time resolved spectroscopy; reaction mechanisms
Rodenberg Alexander, Orazietti Margherita, Probst Benjamin, Bachmann Cyril, Alberto Roger, Baldridge Kim K, Hamm Peter (2015), Mechanism of photocatalytic hydrogen generation by a polypyridyl-based cobalt catalyst in aqueous solution., in Inorganic Chemistry
, 54(2), 646-57.
Ressnig Debora, Shalom Menny, Patscheider Jörg, Moré René, Evangelisti Fabio, Antonietti Markus, Patzke Greta R (2015), Photochemical and electrocatalytic water oxidation activity of cobalt carbodiimide, in J. Mater. Chem. A,
, 3(9), 5072-5082.
Bachmann Cyril, Probst Benjamin, Guttentag Miguel, Alberto Roger (2014), Ascorbate as an electron relay between an irreversible electron donor and Ru(II) or Re(I) photosensitizers., in Chemical Communications (Cambridge, England)
, 50(51), 6737-9.
Oberholzer Miriam, Probst Benjamin, Bernasconi Dominik, Spingler Bernhard, Alberto Roger (2014), Photosensitizing properties of Alkynylrhenium(I) complexes [Re(-C C-R)(CO)(3)(N boolean AND N)] (N boolean AND N=2,2 '-bipy, phen) for H-2 production, in EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
, (19), 3002-3009.
Kraack Jan Philip, Lotti Davide, Hamm Peter (2014), Ultrafast multi-dimensional attenuated total reflectance spectroscopy of adsorbates at metal surfaces, in J. Phys. Chem. Lett.
, (5 (13)), 2325-2329.
Liu Hongfei, Patzke Greta R (2014), Visible-light-driven water oxidation with nanoscale Co(3)O(4) : new optimization strategies., in Chemistry, an Asian journal
, 9(8), 2249-59.
Bachmann Cyril, Guttentag Miguel, Spingler Bernhard, Alberto Roger (2013), 3d element complexes of pentadentate Bipyridine-Piyridine-based ligand scaffolds: Structures and photocatalytic activities, in Inorganic Chemistry
, 52(10), 6055-61.
Guttentag Miguel, Rodenberg Alexander, Bachmann Cyril, Senn Anna, Hamm Peter, Alberto Roger (2013), A highly stable polypyridyl-based cobalt catalyst for homo- and heterogeneous photocatalytic water reduction., in Dalton transactions (Cambridge, England : 2003)
, 42(2), 334-7.
Car Pierre-Emmanuel, Spingler Bernhard, Weyeneth Stephen, Patscheider Jörg, Patzke Greta R. (2013), All-inorganic 1D chain-based architecture of a novel dimanganese-substituted Keggin polyoxotungstate, in c, Greta R. Patzkea,
, 52, 151-158.
Evangelisti Fabio, Güttinger Robin, Moré René, Luber Sandra, Patzke Greta R (2013), Closer to photosystem II: a Co4O4 cubane catalyst with flexible ligand architecture., in Journal of the American Chemical Society
, 135(50), 18734-7.
Liu Hongei, Patzke Greta R. (2013), Cobalt-Manganese Spinel Oxides as Visible-Light-Driven Water Oxidation Catalysts, in Kirihara Soshu, Hernandez-Ramirez Francisco, Mathur Sanjay, Widjaja Sujanto (ed.), John Wiley & Sons, Inc., Hoboken, New Jersey, 75.
Evangelisti Fabio, Car Pierre-Emmanuel, Blacque Olivier, Patzke Greta Ricarda (2013), Photocatalytic water oxidation with cobalt-containing tungstobismutates: Tuning the metal core, in Catalysis Science and Technology
, 3(12), 3117-3129.
Von Allmen Kim, Car Pierre-Emmanuel, Blacque Olivier, Fox Thomas, Müller Rafael P, Patzke Greta R (2013), Structure and properties of new gallium-containing polyoxotungstates with hexanuclear and tetranuclear cores, in Zeitschrift fur Anorganische und Allgemeine Chemie
, 640(5), 781-789.
Ni Lubin, Patzke Greta Ricarda (2012), 1D- and 2D-architectures via self-assembly of the novel sandwich-type polyoxometalate [Zn 2Sb 2(B-α-ZnW 9O 34) 2] 14-, in CrystEngComm
, 14(20), 6778-6782.
Ni Lubin, Patscheider Jörg, Baldridge Kim K, Patzke Greta R (2012), New perspectives on polyoxometalate catalysts: Alcohol oxidation with Zn/Sb-polyoxotungstates, in Chemistry - A European Journal
, 18, 13293-13298.
Car Pierre-Emmanuel, Guttentag Miguel, Baldridge Kim K, Alberto Roger, Patzke Greta R (2012), Synthesis and characterization of open and sandwich-type polyoxometalates reveals visible-light-driven water oxidation via POM-photosensitizer complexes, in Green Chemistry
, 14(6), 1680-1688.
The storage of light energy in chemical bonds is by far the most promising and sustainable strategy to solve our worldwide energy and climate problems. Not only is solar energy inexhaustible, its general use would also drastically reduce global CO2 emission. Water is an equally ubiquitous resource so that artificial photosynthesis based on water splitting is the ideal carbon-neutral way out of the fossile fuel dilemma. Water reduction catalysts (WRCs) promote hydrogen production, whereas water oxidation catalysts (WOCs) facilitate the challenging oxidative half reaction leading to O2 evolution. Extensive synthetic, mechanistic and optimization work is now required to develop WRC/WOC catalyst systems that produce solar fuels at a competitive price. Cheap, replaceable and non-toxic WRC/WOC couples would offer distinct operational advantages over photoelectrolytic water splitting, such as single step and low cost processes without preliminary generation of electricity. Whereas an increasing number of studies report on the integration of WRCs and WOCs into heterogeneous water splitting systems, visible light driven homogeneous overall water splitting with WRC/WOC pairs has not been reported to date. This research goal is particularly worthwhile, because bio-inspired homogeneous catalysts are exceptionally promising due to their manifold structural tuning options that can render artificial photosynthesis approaches close to the robustness, self-repair options and high performance of the natural photosystems. Therefore, the present Sinergia proposal is located at the forefront of overall water splitting research: we integrate preparative, physico-chemical and theoretical expertise into the quest for the first homogeneous WRC/WOC catalytic system. Our ultimate Sinergia goal is a unified concept for water splitting through robust, stable and economically viable homogeneous catalysts. The synthetic part (projects 1 and 2) is thus focused on the development of easily accessible homogeneous WRCs and WOCs based on abundant metals (e.g. Mn, Fe, Co and combinations thereof). Special emphasis will be placed on water-stable WRC complexes and bio-inspired polyoxometalate-based WOCs with Mn cores. Project 3 is focused on the investigation of the catalytic WRC/WOC half reactions with advanced in situ time-resolved IR spectroscopy. This will provide highly sought-after insight into the operational mechanisms of these catalysts that is required for their informed design. In parallel, theoretical models of WRCs/WOCs in solution will be developed in project 4 to optimize the synthetic strategy with a grid approach and to correlate the spectroscopic results with calculated water reduction/oxidation pathways. The most challenging Sinergia task is the quest for the “missing chemical links” between WRCs and WOCs, namely common photosensitizers and electron shuttles. Intense in situ studies of the underlying reaction pathways will provide the requested mechanistic insight to bring the homogeneous water splitting concept to life through the systematic development of recyclable and robust electron transfer agents. Such pioneering investigations would add new directions to Swiss research programs on renewable energy sources, such as the Swiss Hydrogen Association HYDROPOLE, and our individual collaborations in this direction can be strengthened and focused with a Sinergia framework. In this way, we aim to place Swiss research on sustainable hydrogen technology at the forefront of current European research activities (e.g. FCH JU of the European Research Commission).