The project Interfacial engineering of semiconductors for highly selective light-driven chemical transformations, led by Prof. Wojciech Macyk, is aimed to study the possibility of selectivity control in photo(electro)catalytic processes through engineering the semiconductor/solvent or semiconductor/gas interfaces.
Photo(electro)catalytic reactions are the solar-driven processes that can be used to produce solar fuels, fine chemicals or to depollute water and air. However, the overall performance of heterogeneous selective photocatalytic systems developed so far is still rather low, and the factors governing the selectivity in heterogeneous photocatalysis are still poorly understood. A good example of a lack of any selectivity of such processes is photocatalytic degradation of pollutants, which encompasses the generation of a strong, non-selective oxidant (hydroxyl radical). Based on our preliminary work on various light-driven selective conversions, the major thrust of this project is to develop novel and more efficient photo(electro)catalytic systems for various highly attractive conversions (i.e., selective oxidations of alcohols and diphenyl sulfides, reduction of oxygen to hydrogen peroxide, reduction of carbon dioxide) and to gain a fundamental mechanistic understanding of the factors governing the kinetics of charge separation, charge recombination and catalytic turnover in direct relation to product selectivity. Specifically, the project aims are:
i) to investigate composites combining materials with optimum surface catalytic properties with well-passivated low-gap semiconductors as light harvesters,
ii) to study the influence of various types of additional metal catalytic sites (single atoms/ions vs. nanoclusters vs. particles),
iii) to develop tandem catalytic configurations of particulate photocatalysts in which the products formed selectively at one component are utilized in-situ by another component for further light-driven selective transformation.
These objectives will be addressed by a combination of synthetic (e.g., atomic layer deposition approach), photoelectrochemical, spectroscopic (e.g., transient absorption/fluorescence spectroscopy, spectroelectrochemistry, intensity-modulated photocurrent/photovoltage spectroscopy) and theoretical studies. The project results are expected to provide unique design rules for the development of highly active and selective photo(electro)catalytic architectures and to advance our understanding of the fundamental advantages and bottlenecks of such systems for selective catalytic transformations.
The project will involve research teams led by Prof. Radim Beránek from Ulm University (project leader), Prof. Timo Jacob (Ulm University), and Prof. Markku Leskelä (University of Helsinki).
Publication
1. Selective and efficient catalytic and photocatalytic oxidation of diphenyl sulphide to sulfoxide and sulfone: the role of hydrogen peroxide and TiO2 polymorph P. Mikrut, A. Święs, M. Kobielusz, L. Chmielarz, W. Macyk
2. Studying the governing factors on the photo(electro)catalytic activity of surface-modified photocatalysts under visible light illumination T. Tabari, P. Łabuz, A. Nowakowska, M. Kobielusz, M. Pacia, W. Macyk
3. Photoelectrochemical Activity of Visible Light-responsive BiVO4@La1-xSrxFeO3-δ (x = 0, 0.2, 0.4) Heterojunction Architectures – Optimizing Activity by Tuning Fe–O Bond in Perovskites T. Tabari, M. Kobielusz, A. Jarosz-Duda, D. Singh, A. Kotarba, A. Błachowski, J. Yu, W. Macyk
4. Optimizing the morphology of titania nanorods for enhanced solar seawater splitting P. Wyżga, T. Tabari, M. Trochowski, W. Macyk
5. Phototransformations of TiO2/Ag2O composite and their influence on photocatalytic water splitting accompanied by methanol photoreforming A. Jakimińska, K. Spilarewicz, W. Macyk
6. New Insights into the Influence of Plasmonic and Non-plasmonic Nanostructures on the Photocatalytic Activity of Titanium Dioxide A. Jakimińska, K. Spilarewicz, W. Macyk
7. How Much is the Plasmonic Effect Worth in Photocatalysis? Mechanisms of Photocatalytic Activity Enhancement in Composites with Metallic Nanostructures A. Jakimińska, W. Macyk
8. Cobalt-/Copper-Containing Perovskites in Oxygen Evolution and Reduction Reactions T. Tabari, M. Kobielusz, D. Singh, J. Yu, W. Macyk
9. Yellow TiO2 from Titanium Peroxo Complexes: Verification of the Visible Light Activity and a Rational Enhancement of Its Photocatalytic Efficiency K. Yaemsunthorn, T. Tatarchuk, N. Danyliuk, A. Shyichuk, W. Macyk
10. Photochemical Transformations of AgCl in the Context of Its Eventual Photocatalytic Applications A. Jakimińska, W. Macyk
11. Selective Photocatalytic Reduction of 3-Nitrophenol to 3-Aminophenol by Anatase and Rutile TiO2 – What Stands Behind the Photoactivity? K. Yaemsunthorn, W. Adamowicz, M. Kobielusz, W. Macyk
12. Polymeric Carbon Nitride-based Photocathodes for Visible Light-driven Selective Reduction of Oxygen to Hydrogen Peroxide H. Braun, D. Mitoraj, J. Kuncewicz, A. Hellmann, M. M. Elnagar, J. Bansmann, C. Kranz, T. Jacob, W. Macyk, R. Beranek
13. Influence of TiO2 Phases and Functional Groups on Photocatalytic Reduction of Nitroaromatics K. Yaemsunthorn, M. Kobielusz, W. Macyk
14. Photocatalytic Transformation of Organics to Valuable Chemicals – Quo Vadis? W. Adamowicz, K. Yaemsunthorn, M. Kobielusz, W. Macyk
15. When the fate of electrons matters — strategies for correct heterojunction classification in photocatalysis K. Spilarewicz, K. Mróz, M. Kobielusz, W. Macyk