How electron spin coupling affects catalytic oxygen activation
A team at the EPR4Energy joint lab of HZB and MPI CEC has developed a new THz EPR spectroscopy method to study the catalytic activation of molecular oxygen by copper complexes. © T. Lohmiller/HZB
A team at the EPR4Energy joint lab of HZB and MPI CEC has developed a new THz EPR spectroscopy method to study the catalytic activation of molecular oxygen by copper complexes. The method allows insights into previously inaccessible spin-spin interactions and the function of novel catalytic and magnetic materials.
Molecular oxygen (O2) is a preferred oxidant in green chemistry. However, activation of O2 and control of its reactivity requires precise adjustment of the spin states in the reactive intermediates. In nature, this is achieved by metalloenzymes that bind O2 at iron or copper ions, and spin-flip processes are enabled through metal-mediated spin-orbit couplings allowing for mixing of states. In the case of type III dicopper metalloproteins involved in oxygen transport and oxygenation of phenolic substrates, little was known about the pathway leading to a dicopper peroxo key species with a stabilized singlet ground state after triplet oxygen binding.
Through a sophisticated ligand design, the research group led by Prof. Franc Meyer at the University of Göttingen has now succeeded in isolating a series of model complexes that mimic the initial stage of oxygen binding at dicopper sites and exhibit a triplet ground state. Researchers from the EPR4Energy joint lab of HZB and MPI CEC complemented this breakthrough in chemical synthesis with a new approach of THz-EPR spectroscopy. This method, developed in Alexander Schnegg's group at MPI CEC, was applied for the first time to study the function-determining antisymmetric exchange in coupled dicopper(II) complexes.
The new method allowed for detection of the entirety of spin state transitions in the system, which leads to propose antisymmetric exchange as an efficient mixing mechanism for the triplet-to-singlet intersystem crossing in biorelevant peroxodicopper(II) intermediates. Thomas Lohmiller, one of the first authors of the study, explains, "In addition to the knowledge gained about this important system, our method opens up the possibility of studying previously inaccessible spin-spin interactions in a variety of novel catalytic and magnetic materials."
- International consortium to advance decarbonisation of the aviation sectorJOHANNESBURG, SOUTH AFRICA – 24 May 2022: CARE-O-SENE research project will develop advanced catalysts for sustainable aviation fuels
The company Sasol and Helmholtz-Zentrum Berlin (HZB) will lead a consortium to develop and optimise next-generation catalysts that will play a key role in decarbonising the aviation sector through sustainable aviation fuels (SAF).
- Thermal insulation for quantum technologiesNew energy-efficient IT components often only operate stably at extremely low temperatures. Therefore, very good thermal insulation of such elements is crucial, which requires the development of materials with extremely low thermal conductivity. A team at HZB has now used a novel sintering process to produce nanoporous silicon aluminium samples in which pores and nanocrystallites impede the transport of heat and thus drastically reduce thermal conductivity. The researchers have developed a model for predicting the thermal conductivity, which was confirmed using experimental data on the microstructure of the samples and their thermal conductivity. Thus, for the first time, a method is available for the targeted development of complex porous materials with ultra-low thermal conductivity.
- Magnetic nanoparticles in biological vehicles individually characterisedMagnetic nanostructures are promising tools for medical applications. Incorporated into biological structures, they can be steered via external magnetic fields inside the body to release drugs or to destroy cancer cells. However, until now, only average information on the magnetic properties of those nanoparticles could be obtained, thus limiting their successful implementations in therapies. Now a team at HZB conceived and tested a new method to assess the characteristic parameters of every single magnetic nanoparticle.