LightChEC: Solar Light to Chemical Energy Conversion
The URPP LightChEC is a joint project between the Department of Chemistry and Department of Physics of the University of Zurich and the EMPA in Dübendorf. The objectives of the project are the discovery and development of new molecules, materials and processes for the direct storage of solar light energy in chemical bonds. The LightChEC research program is structured in seven interdisciplinary research topics, which are each lead by a different research group.
The objective of our research within the UFSP is to provide mechanistic insight into how novel catalyst molecules and photosensitizers, developed within the UFSP for the homogeneous water splitting route, might perform when adsorbed on a solid surface. For this purpose, a small set of model systems will be established, including at least one for each type (WRC, WOC, PS), and characterized in terms of adsorption geometry and bonding, charge redistribution upon photoexcitation and excited state life times. Such knowledge will assist in designing strategies for building a heterogeneous system required for a continuously operating visible-light-driven water splitting process.
The heterogeneous route to a solar-light-driven water splitting process, where catalyst molecules and photosensitizers are immobilized on a suitable solid substrate, is technologically compelling because the water reduction and oxidation steps can be spatially separated, thus avoiding unwanted recombination reactions and facilitating separation of the produced gaseous hydrogen and oxygen. Since catalytic activity and selectivity are strongly related to the molecular structure and the accessibility of the active sites to the reactant molecules, structural investigations of adsorbed catalyst molecules are of interest for understanding the mechanism. We apply rigorous surface science methods, including low-energy-electron diffraction (LEED), scanning tunneling microscopy (STM) and x-ray photoelectron diffraction (XPD) in order to study the bonding geometry of adsorbed molecules in vacuo. Fig. 1 shows the multitechnique instrument available in our laboratory.
Several other factors influence strongly the catalyst performance upon attachment to a surface, like energy shifts and rehybridization of molecular orbitals and charge redistribution and charge dynamics upon photoexcitation. Such effects are studied by means of ultraviolet photoelectron spectroscopy (UPS) and its angle-dependent variant (ARPES), as well a by time-resolved photoemission and two-photon photoemission. Such fundamental studies are complemented by measurements of the activity for water splitting, where such surfaces, prepared under highly controlled conditions, are brought into water and exposed to visible light. These studies are carried out with novel water reduction and water oxidation catalysts, developed within the URPP LightChEC, and eventually also including photosensitizers. In close collaboration with the synthetic chemists, strategies will be developed for obtaining stable surface bonding of the catalyst molecules and maximum activity and photostability.
- Prof. Jürg Osterwalder
- Dr. Roberta Totani
- Lisa Grad
- Wolf-Dietrich Zabka
- Fabio Cossalter
- Benjamin Tobler
- Atomically dispersed hybrid nickel-iridium sites for photoelectrocatalysis
Nature Comm. 8, 1341 (2017)
→ DOI: 10.1038/s41467-017-01545-w
- From two- to three-dimensional alumina: Interface templated films and formation of γ−Al2O3(111) nuclei
Phys. Rev. B 96, 155420 (2017)
→ DOI: 10.1103/PhysRevB.96.155420
- Atomically Resolved Band Bending Effects in a p-n Heterojunction of Cu2O and a Cobalt Macrocycle
Nano Letters 17, 6620 (2017)
→ DOI: 10.1021/acs.nanolett.7b02486
- The impact of metalation on adsorption geometry, electronic level alignment and UV-stability of organic macrocycles on TiO2(110)
Nanoscale, 9, 8756 (2017)
→ DOI: 10.1039/c7nr02317k
- From porphyrins to pyrphyrins: Adsorption study and metalation of a molecular catalyst on Au(111)
Nanoscale, 8, 7958 (2016)
→ DOI: 10.1039/C5NR08953K
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