Interfacial engineering of semiconductors for highly selective light-driven chemical transformations
Final Report Abstract
Heterogeneous photo(electro)catalysis is a potentially powerful method for driving useful redox chemical transformations using sunlight or low-cost light sources (e.g., LEDs) under mild conditions: at ambient pressure and temperature, and utilizing ubiquitous and sustainable reagents such as water or aerial oxygen. The use of heterogeneous photo(electro)catalysis for synthetic purposes is particularly attractive, as it offers the potential for commercially viable applications on a shorter time scale compared to, for example, light-driven hydrogen production. However, functional photo(electro)catalytic systems for highly selective conversions are still scarce, and the factors governing selectivity in heterogeneous photocatalysis are not well understood, especially when compared to more conventional catalytic processes like thermal catalysis or electrocatalysis. Addressing these challenges, the following key advancements were achieved in this project: i) the hypothesis that interfacial energetics govern the distinct selectivity trends in electrocatalytic versus photoelectrocatalytic conversions was experimentally corroborated for two different photoelectrocatalytic systems; ii) conceptually novel photocatalytic and photoelectrocatalytic systems for selective synthesis of hydrogen peroxide from oxygen were developed; iii) novel photoanodes for selective alcohol oxidation based on ionic carbon nitride were developed, and their unprecedented photoelectrochemical (bias-free photoreforming of alcohols) and photophysical (fast charge extraction and photodoping) properties were identified. The project results establish new examples of photo(electro)catalytic systems for highly selective lightdriven chemical conversions and represent significant advancements in our understanding of fundamental aspects of selectivity in heterogeneous photocatalysis.
Publications
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On the importance of catalysis in photocatalysis: Triggering of photocatalysis at well-defined anatase TiO2 crystals through facet-specific deposition of oxygen reduction cocatalyst. The Journal of Chemical Physics, 152(24).
Adler, Christiane; Mitoraj, Dariusz; Krivtsov, Igor & Beranek, Radim
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A Study in Red: The Overlooked Role of Azo‐Moieties in Polymeric Carbon Nitride Photocatalysts with Strongly Extended Optical Absorption. Chemistry – A European Journal, 27(68), 17188-17202.
Mitoraj, Dariusz; Krivtsov, Igor; Li, Chunyu; Rajagopal, Ashwene; Im, Changbin; Adler, Christiane; Köble, Kerstin; Khainakova, Olena; Hniopek, Julian; Neumann, Christof; Turchanin, Andrey; da Silva, Ivan; Schmitt, Michael; Leiter, Robert; Lehnert, Tibor; Popp, Jürgen; Kaiser, Ute; Jacob, Timo; Streb, Carsten ... & Beranek, Radim
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Facet-dependent activity of tailored anatase TiO2 crystals in photoanodes for photocatalytic fuel cells. Applied Surface Science, 566, 150662.
Mikrut, Paweł; Mitoraj, Dariusz; Beranek, Radim & Macyk, Wojciech
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Photodoping and Fast Charge Extraction in Ionic Carbon Nitride Photoanodes. Advanced Functional Materials, 31(45).
Adler, Christiane; Selim, Shababa; Krivtsov, Igor; Li, Chunyu; Mitoraj, Dariusz; Dietzek, Benjamin; Durrant, James R. & Beranek, Radim
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Sol−Gel Processing of Water‐Soluble Carbon Nitride Enables High‐Performance Photoanodes**. ChemSusChem, 14(10), 2170-2179.
Adler, Christiane; Krivtsov, Igor; Mitoraj, Dariusz; dos Santos‐Gómez, Lucía; García‐Granda, Santiago; Neumann, Christof; Kund, Julian; Kranz, Christine; Mizaikoff, Boris; Turchanin, Andrey & Beranek, Radim
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Benzaldehyde‐Promoted (Auto)Photocatalysis under Visible Light: Pitfalls and Opportunities in Photocatalytic H 2 O 2 Production**. ChemCatChem, 15(3).
Krivtsov, Igor; Vazirani, Ashish; Mitoraj, Dariusz & Beranek, Radim
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Enhancing Photocatalysis: Understanding the Mechanistic Diversity in Photocatalysts Modified with Single‐Atom Catalytic Sites. Advanced Science, 10(35).
Kruczała, Krzysztof; Neubert, Susann; Dhaka, Kapil; Mitoraj, Dariusz; Jánošíková, Petra; Adler, Christiane; Krivtsov, Igor; Patzsch, Julia; Bloh, Jonathan; Biskupek, Johannes; Kaiser, Ute; Hocking, Rosalie K.; Caspary, Toroker Maytal & Beranek, Radim
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Hydrophobized poly(heptazine imide) for highly effective photocatalytic hydrogen peroxide production in a biphasic fatty alcohol–water system. Journal of Materials Chemistry A, 11(5), 2314-2325.
Krivtsov, Igor; Vazirani, Ashish; Mitoraj, Dariusz; Elnagar, Mohamed M.; Neumann, Christof; Turchanin, Andrey; Patiño, Yolanda; Ordóñez, Salvador; Leiter, Robert; Lindén, Mika; Kaiser, Ute & Beranek, Radim
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Polymeric carbon nitride-based photocathodes for visible light-driven selective reduction of oxygen to hydrogen peroxide. Applied Catalysis A: General, 660, 119173.
Braun, Hanna; Mitoraj, Dariusz; Kuncewicz, Joanna; Hellmann, Andreas; Elnagar, Mohamed M.; Bansmann, Joachim; Kranz, Christine; Jacob, Timo; Macyk, Wojciech & Beranek, Radim
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Structure and Optical Properties of Polymeric Carbon Nitrides from Atomistic Simulations. Chemistry of Materials, 35(4), 1547-1559.
Im, Changbin; Kirchhoff, Björn; Krivtsov, Igor; Mitoraj, Dariusz; Beranek, Radim & Jacob, Timo
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Water-soluble ionic carbon nitride as unconventional stabilizer for highly catalytically active ultrafine gold nanoparticles. Nanoscale, 15(47), 19268-19281.
Elnagar, Mohamed M.; Liessem, Johannes; Im, Changbin; Mitoraj, Dariusz; Kibler, Ludwig A.; Neumann, Christof; Turchanin, Andrey; Leiter, Robert; Kaiser, Ute; Jacob, Timo; Krivtsov, Igor & Beranek, Radim
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"Structural Influence on Exciton Formation and the Critical Role of Dark Excitons in Polymeric Carbon Nitrides".
Ch. Im, R. Beranek & T. Jacob
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"Unraveling the Optical Signatures of Polymeric Carbon Nitrides: Insights into Stacking-Induced Excitonic Transitions".
Ch. Im, B. Kirchhoff, D. Mitoraj, I. Krivtsov, A. Farkas, R. Beranek & T. Jacob
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A robust and high performance copper silicide catalyst for electrochemical CO2 reduction. Materials Advances, 5(7), 2917-2925.
Dřínek, Vladislav; Dytrych, Pavel; Fajgar, Radek; Klementová, Mariana; Kupčík, Jaroslav; Kopeček, Jaromír; Svora, Petr; Koštejn, Martin; Jandová, Věra; Soukup, Karel & Beranek, Radim
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High-performance BiVO 4 photoanodes: elucidating the combined effects of Mo-doping and modification with cobalt polyoxometalate. Materials Advances, 5(11), 4932-4944.
Feng, Fan; Mitoraj, Dariusz; Gong, Ruihao; Gao, Dandan; Elnagar, Mohamed M.; Liu, Rongji; Beranek, Radim & Streb, Carsten
