A Semi-artificial Photoelectrochemical Tandem Leaf with a CO₂ -to-Formate Efficiency Approaching 1 

Semi-artificial photoelectrochemistry can combine state-of-the-art photovoltaic light-absorbers with enzymes evolved for selective fuel-forming reactions such as CO₂ reduction, but the overall performance of such hybrid systems has been limited to date. Here, the electrolyte constituents were first tuned to establish an optimal local environment for a W-formate dehydrogenase to perform electrocatalysis. The CO₂ reductase was then interfaced with a triple cation lead mixed-halide perovskite through a hierarchically structured porous TiO₂ scaffold to produce an integrated photocathode achieving a photocurrent density of -5 mA cm^-2 at 0.4 V vs. the reversible hydrogen electrode during simulated solar light irradiation. Finally, the combination with a water-oxidizing BiVO₄ photoanode produced a bias-free integrated biophotoelectrochemical tandem device (semi-artificial leaf) with a solar CO₂ -to-formate energy conversion efficiency of 0.8 %.