SFB 1633:  Pushing Electrons with Protons – Unifying Multi-Electron Redox Catalysis by Proton-Coupled Electron Transfer

• Subject Area: Chemistry ; Biology ; Materials Science and Engineering ; Physics
• Term: since 2024
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 510228793

The CRC aims at facilitating new strategies for redox catalysis as key enabling methodology of sustainable chemical synthesis and energy conversion based on renewable feedstock (CO2, O2, H2O, N2, biomass). For this purpose, it will focus on the physicochemical phenomenon that controls the redox transformations of these chemically diverse and unreactive substrates, i.e., the thermochemical and kinetic coupling of proton and elec-tron transfer (PCET). The central paradigm of the CRC is that advancing the fundamental understanding of PCET provides unifying strategies across all branches of catalysis (homogeneous, enzymatic, heterogeneous) to obtain new methodologies that mediate energy-efficient redox transformations of chemically inert, regenera-tive feedstock. As grand challenges, the CRC aims at (a) expanding concepts for (photo/electro)catalysis from redox-based to PCET-based strategies, (b) advancing PCET models towards key species relevant to catalysis, (c) connecting PCET models to chemical and electronic structure descriptors of active sites, (d) controlling PCET mechanisms with modular strategies for synthesis, and (e) utilizing quantum effects for selectivity con-trol. The projects will focus on selected PCET-active key species for oxidative and reductive catalysis, i.e., (doped) oxide semiconductors (ZnO), as well as molecular and biological oxo/oxyl, nitrido and hydrido spe-cies. Methodological and conceptual collaborations within and across subdisciplines will be organized in two dimensions: (a) The Project Groups (A: Molecular PCET, B: Biological PCET, C: Interfacial PCET) will close the ‘utilization gap’ between predictive modelling of ground and excited state (multi-)PCET mechanisms and its utilization for PCET-driven (photo/electro)catalytic protocol development. (b) The Working Groups (I: The PCET Site, II: Enabling Catalysis, III: Beyond Catalyst Design) aim at closing the ‘modelling gap’ between disciplines by joint development and transfer of PCET control strategies that are based on nine selected phenomena, which control the interaction of local PECT sites with their tunable environment (proton tunneling, electron/spin dynamics, reorganization energies, hydrogen bonding, electron de-/localization, structural reorganization, pro-ton supply, electric field effects, ionic auxiliaries). The scientific approach of the CRC relies on advanced syn-thetic, spectroscopic, imaging, kinetic, electrochemical, and quantum-chemical methods that cover all neces-sary energy regimes, length scales, and time scales to jointly develop a comprehensive picture for the phe-nomenon PCET and utilize it to control the targeted redox transformations.

• DFG Programme: Collaborative Research Centres

Current projects

• A01 - Dynamics of CT-PhotoPCET with Metal Complexes (Project Heads Heinze, Katja ;  Schwarzer, Dirk ;  Stopkowicz, Stella )
• A02 - Photo-PCET Mediators for Selective Bond Activation and Formation (Project Heads Krewald, Vera ;  Schneider, Sven ;  Streb, Carsten )
• A03 - Controlling the Selectivity of Bioinspired Cu-Mediated O2 Activation for C–H Oxygenation (Project Heads Holthausen, Max C. ;  Meyer, Franc )
• A04 - Controlling the Selectivity of N2 Fixation (Project Heads Holthausen, Max C. ;  Schneider, Sven )
• A05 - PCET Mediators for Selective Electrochemical Bond Activation and Formation (Project Heads Fischer, Malte ;  Siewert, Inke )
• A06 - PCET-controlled Chemoselective Transformations of Renewable Feedstocks (Project Heads Waldvogel, Siegfried R. ;  Zhang, Kai )
• B01 - Multicomponent Local Correlation Methods for PCET (Project Head Mata, Ricardo )
• B02 - Reversible Long-range PCET in Ribonucleotide Reductases (Project Heads Bennati, Marina ;  Tittmann, Kai )
• B03 - Metalloenzymes, Bioinspired Complexes and Hybrids for H2 Activation (Project Heads Glöggler, Stefan ;  Meyer, Franc )
• B04 - Controlling PCET and Radical Transformations in enzyme catalysis (Project Heads Mata, Ricardo ;  Tittmann, Kai )
• B05 - The Effect of Oriented Electric Fields on PCET Reactions (Project Heads Otte, Matthias ;  Siewert, Inke )
• C01 - Electron Dynamics at Hydrated Magnetically Doped ZnO Surfaces (Project Heads Mathias, Stefan ;  Wenderoth, Martin )
• C02 - Site-specific Kinetics and Dynamics of Surface PCET Reactions (Project Heads Schäfer, Tim ;  Wodtke, Alec Michael )
• C03 - Photo-/electrochemical Water Oxidation Using Metal-doped Nanoscale ZnO (Project Heads Streb, Carsten ;  Weitz, R. Thomas )
• C04 - Atomic Scale Mechanisms of the Electrocatalytic Oxygen Evolution Reaction (Project Heads Behler, Jörg ;  Jooss, Christian ;  Techert, Simone )
• C05 - PCET-active Anodes for Electrosynthesis (Project Heads Pezhumkattil Palakkal, Ph.D., Jasnamol ;  Waldvogel, Siegfried R. )
• MGK - Integrated Research Training Group (Project Heads Mata, Ricardo ;  Wenderoth, Martin )
• Z01 - Central Tasks of the Collaborative Research Centre (Project Head Schneider, Sven )
• Ö01 - PCET – OPtimiCED for all (Project Heads Klein, Pascal ;  Waitz, Thomas )

• Applicant Institution: Georg-August-Universität Göttingen
• Participating Institution: Max-Planck-Institut für Multidisziplinäre Naturwissenschaften
• Participating University: Goethe-Universität Frankfurt am Main; Johannes Gutenberg-Universität Mainz; Ruhr-Universität Bochum; Technische Universität Darmstadt; Universität des Saarlandes
• Spokesperson: Professor Dr. Sven Schneider