Control of the overpotential of a [FeFe] hydrogenase mimic by a synthetic second coordination sphere

Hydrogen as a renewable fuel is viable when produced sustainably via proton reduction catalysis (PRC). Many homogeneous electrocatalysts perform PRC with high rates, but they all require a large overpotential to drive the reaction. Natural hydrogenase enzymes achieve reversible PRC with potentials close to the thermodynamic equilibrium through confinement of the active site in a well-defined protein pocket. Inspired by nature, we report a strategy that relies on the selective encapsulation of a synthetic hydrogenase mimic in a novel supramolecular cage. Catalyst confinement decreases the PRC overpotential by 150 mV, and is proposed to originate from the cationic cage stabilizing anionic reaction intermediates within the catalytic cycle

Burnout in university students: the mediating role of sense of coherence on the relationship between daily hassles and burnout

International audienc