TRR 234:  Light-driven Molecular Catalysts in Hierarchically Structured Materials – Synthesis and Mechanistic Studies

• Subject Area: Chemistry ; Materials Science and Engineering ; Thermal Engineering/Process Engineering
• Term: since 2018
• Website: Homepage
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 364549901

The CRC/Transregio CATALIGHT addresses fundamental challenges in materials development for sunlight-driven productive catalysis. Inspired by the design principles of natural photosynthesis, CATALIGHT envisions material innovations which lead up to artificial chloroplasts. To achieve this goal, CATALIGHT uses a molecule-in-matrix approach, where molecular photosensitizers and catalysts are embedded into functional soft matter matrices. This results in ideal model systems to study light-driven reactivity, stability, degradation, and repair. CATALIGHT will develop general synthetic strategies to design and tune molecular photosensitizers and catalysts with a focus on replacing traditional noble-metal-based compounds with non-noble-metal alternatives. Complementary synthetic routes will be established to access functional polymeric matrices for the site-specific anchoring of molecular reactive components. CATALIGHT will harness synergistic reactivity and stability by tuning molecule-matrix interactions as well as hierarchical matrix structuring. Light-driven reductive and oxidative catalyses will be coupled via charge-transport matrices to enable artificial photosynthetic schemes, e.g., for complete splitting of water into H2 and O2. Integration of the most promising systems into flow photoreactors equipped with online analytics will provide unprecedented insights into reactivity for soft matter matrices under light-driven catalytic conditions. In situ/operando experimental methods are combined with theoretical studies to rationalize photochemical reactivity across multiple length- and timescales. CATALIGHT expects that this comprehensive mechanistic approach will lead to in-depth understanding of new – even unexpected – phenomena emerging from molecule-in-matrix assemblies. CATALIGHT will go beyond the state-of-the-art and explore emerging themes in component, materials and reactor design, ranging from active molecular repair to stimuli-responsive reactivity regulation and enhanced catalytic performance using adaptive, dynamic process controls. CATALIGHT will lead to new paradigms, which break down boundaries between the realms of molecule-based reactivity, bottom-up material design and top-down reactor integration. This will result in fundamentally new, knowledge-guided concepts for light-driven productive chemistry in hybrid materials – opening new research opportunities for chemistry, biology, materials science and process engineering.

• DFG Programme: CRC/Transregios

Current projects

• A01 - Strategies for Molecular Repair and Self-regulation in Light-driven Catalysis for Hydrogen Evolution (Project Heads Dietzek-Ivansic, Benjamin ;  Rau, Sven )
• A03 - Metal-free Photosensitizers and Their Application as Molecular Chromophore-Catalyst Systems (Project Heads Peneva, Ph.D., Kalina ;  Rau, Sven )
• A04 - Covalently Linked Photosensitizer-Catalyst Dyads for One-step Materials Integration (Project Heads Kupfer, Stephan ;  Rau, Sven ;  Streb, Carsten )
• A05 - Experimental and Theoretical Studies on Molecular Molybdenum Sulfide Hydrogen Evolution Reaction Catalysts (Project Heads Jacob, Timo ;  Streb, Carsten )
• A06 - Organic molecules and materials to promote noble metal-free and coupled light-driven catalysis (Project Head Esser, Birgit )
• A07 - Two-Photon Water Splitting as an Enabling Approach for Coupled Photocatalysis (Project Head Schneidewind, Jacob )
• B02 - Integration of Photoredox-active Complexes in Redox-active Polymers for Light-induced Charging and Discharging by Additional Integrated Molecular Catalysts (Project Heads Rau, Sven ;  Schubert, Ulrich S. )
• B03 - “POMbranes” – Incorporation of Catalytically Active Polyoxometalates into Integral Asymmetric Block Copolymer Membranes (Project Heads Leopold, Kerstin ;  Schacher, Felix H. ;  Streb, Carsten )
• B04 - Bioinspired Photoactive Janus-Membranes for Solar to Fuel Conversion (Project Heads Weil, Tanja ;  Wächtler, Maria )
• B06 - Ionic Carbon Nitride Polymers for Light-Driven Water Splitting and Selective Conversions (Project Heads Beránek, Radim ;  Dietzek-Ivansic, Benjamin ;  Jacob, Timo )
• B07 - Carbon Nanomembranes as a 2D-Platform for the Immobilization, Incorporation and Investigation of Photosensitizers and Catalysts (Project Heads von Delius, Max ;  Turchanin, Andrey )
• B08 - Compartmentalization of Light-induced Reactions in DNA-Liposome Hybrid Structures (Project Heads Pannwitz, Andrea ;  Weil, Tanja )
• B09 - Photocatalytic Molecular Membranes via the Langmuir-Blodgett Technique (Project Heads Presselt, Martin ;  Schubert, Ulrich S. )
• B10 - Modulating the Photocatalytic Properties of Molecularly Functionalized Carbon Nitride Polymers by Nanoconfinement and Pore Structure Engineering (Project Heads Jacob, Timo ;  Oschatz, Ph.D., Martin )
• B11 - Photoactive Nanofibers as Materials for Light-driven Catalysis (Project Heads Anjass, Montaha ;  Dietzek-Ivansic, Benjamin )
• C02 - In Operando Multi-spectroscopic Correlation Analysis of Electronic and Structural Changes During Homogenous and Heterogeneous Catalytic Activity (Project Heads Mizaikoff, Boris ;  Popp, Jürgen ;  Ziegenbalg, Dirk )
• C04 - Characterization of 2D Catalyst-Interfaces – Correlation of Nanoscale Electrochemical and Structural Properties under in situ/operando Conditions (Project Heads Deckert, Volker ;  Kaiser, Ute ;  Kranz, Christine )
• C05 - Multi-scale simulation of light-driven catalytic processes in molecule-in-polymer systems (Project Heads Groß, Axel ;  Gräfe, Stefanie )
• C06 - Control of Photocatalytic Processes within Soft Matter Matrices (Project Head Ziegenbalg, Dirk )
• Z01 - Central Administration (Project Heads Dietzek-Ivansic, Benjamin ;  Rau, Sven )
• Z02 - Core Materials Characterization (Project Heads Kaiser, Ute ;  Schacher, Felix H. ;  Turchanin, Andrey ;  Wächtler, Maria )
• Z03 - Integrated Research Training Group (Project Heads Pannwitz, Andrea ;  Peneva, Ph.D., Kalina ;  Schacher, Felix H. ;  Streb, Carsten ;  Ziegenbalg, Dirk )
• Ö01 - Shedding Light on Chemistry Education: Didactic Reconstruction of current research for formal and non-formal education (Project Head Wilke, Timm )

Completed projects

• A02 - Noble Metal-free Photosensitizer-Catalyst Hybrids for Photocatalytic Hydrogen Generation under Visible Light (Project Heads Bäuerle, Peter ;  Weigand, Wolfgang )
• B01 - Structure-Property Relationships of Functional Copolymers on DNA Nanosheets (Project Heads Schubert, Ulrich S. ;  Weil, Tanja )
• B05 - Self-regulating Photocatalytic Materials Based on pH-responsive Block Copolymers (Project Heads Khokhlov, Alexei R. ;  Schacher, Felix H. )
• C01 - Spatially and Temporally Resolved Spectroelectrochemistry (Project Heads Deckert, Volker ;  Dietzek-Ivansic, Benjamin )

• Applicant Institution: Friedrich-Schiller-Universität Jena
• Co-Applicant Institution: Universität Ulm
• Participating University: Johannes Gutenberg-Universität Mainz; Universität Wien
• Participating Institution: Leibniz-Institut für Photonische Technologien e.V. (IPHT); Max-Planck-Institut für Polymerforschung
• Spokespersons: Professor Dr. Benjamin Dietzek-Ivansic, since 7/2022; Professor Dr. Sven Rau, until 6/2022