Gas diffusion electrodes (GDEs) are an emerging technology in electrochemical conversion of CO2. Because GDEs are made from black carbon-materials, in such systems light cannot be used to drive reactions like CO2 conversion. Illuminating light-responsive electrodes significantly reduces operating potentials required in electrocatalysis, thus allowing more sustainable energy use. This XS project aims at the development and implementation of novel materials for optically transparent gas-diffusion electrodes, enabling the use of light. In combination with integrated catalysts, novel electrode materials will find application in photo-electrochemical cells for light-driven conversion of gaseous pollutants such as CO2.

The research project HyCARB brings together Dutch clean-tech companies, universities and research institutes to develop the technology base for industrial end users worldwide for carbon-based chemicals production using hydrogen, green electrons and captured carbon dioxide. New scientific approaches will be pursued to achieve breakthroughs for cost- and energy-efficient sustainable production of fuels and chemicals by identifying, developing and testing improved catalysts, key components such as reactors, electrolysers and innovative approaches for electrified heating. Laboratory work using the latest generation analytical equipment will be combined with techno-economic and lifecycle assessments of a range of technologies to help industry decarbonise.

Expensive transition metals are currently the dominant force in the design of new catalysts. This project aims to challenge this principle by focussing on iron, aluminium and zinc based complexes that, when combined with specific redox-active ligands, should be amenable to facilitate radical-type reactions. This concept will be tested in C-H amination reactions that can give access to valuable amine products.

Organometallic catalysis is the cornerstone of sustainable fine-chemical transformations, but we are currently using only a limited part of its full potential. Our understanding of organometallic catalysis is primarily based on studies of closed-shell reactivity, and consequently traditional synthetic catalysis is based on diamagnetic organometallic complexes undergoing a limited number of elementary steps (oxidative-addition, reductive-elimination, insertion/deinsertion, metathesis, and transmetallation). A whole new area of open-shell organometallic catalysis has so far been almost neglected, while offering fascinating possibilities to steer and control radical-type reactions. Radicals are intrinsically reactive, and were long believed to be too reactive to be selective. However, in the coordination sphere of transition metals highly selective radical-type processes are certainly possible. In fact, radical-type reactions are tremendously important in several bio-synthetic pathways mediated by metallo-enzymes. Nature solves its most difficult and most interesting bio-synthetic problems with radical-reactivity. Yet, despite their radical-nature, these reactions proceed with ultrahigh precision and selectivity. Achieving similar selectivities in radical-type transformations employing simpler synthetic systems was long believed to be impossible, which is however an important misconception. This proposal aims at achieving high-precision catalytic radical-type reactions with synthetic organometallic catalysts, making efficient use of a combination of innovative bio-inspired enzyme-like tools. These include redox-(re)activity of ligands, metallo-radical reactivity, cooperative ligand effects and site isolation (molecular caging). These new tools will be employed in selective radical-type ring-closure-, polymerisation-, and hydrocarbon functionalization reactions. An important objective is to achieve these new reactions in an efficient and cost-effective manner. This implies selective catalytic reactions with cheap first-row transition metals. Innovative combinations of electro-synthesis and homogeneous catalysis will be explored to enable selective radical-type transformations with cheaper starting materials. Hence, the newly developed methods in this project will contribute substantially to solving long-standing efficiency and selectivity obstacles in important innovative chemical transformations.

This research proposal aims to make chemical reactions more energy efficient. Small, confined spaces in materials called metal-organic frameworks (MOFs) will be used to convert CO2 and CH4 into basic chemicals using only sunlight. The researcher plans to translate concepts that help to convert molecules in biological systems like in photosynthesis to MOFs. Experimental setups based on spectroscopy will be developed to study photoreactions on nanosecond timescales (for comparison: an eye blink takes about 300 million nanoseconds) to understand the reaction mechanism and to improve the efficiency of the photoreactions.