Hybrid energy generation models based on a variety of alternative energy supply technologies are considered the best way to cope with the depletion of fossil energy resources and to limit global warming. One of the currently missing technologies is the mimic of natural photosynthesis to convert carbon dioxide and water into chemical fuel using sunlight. This idea has been around for decades, but artificial photosynthesis of organic molecules is still far away from providing real-world solutions. The scientific challenge is to perform in an efficient way the multi-electron transfer reactions of water oxidation and carbon dioxide reduction using holes and single electrons generated in an illuminated semiconductor. In this tutorial review the design of photoelectrochemical (PEC) cells that combine solar water oxidation and CO₂ reduction is discussed. In such PEC cells simultaneous transport and efficient use of light, electrons, protons and molecules has to be managed. It is explained how efficiency can be gained by compartmentalisation of the water oxidation and CO₂ reduction processes by proton exchange membranes, and monolithic concepts of artificial leaves and solar membranes are presented. Besides transferring protons from the anode to the cathode compartment the membrane serves as a molecular barrier material to prevent cross-over of oxygen and fuel molecules. Innovative nano-organized multimaterials will be needed to realise practical artificial photosynthesis devices. This review provides an overview of synthesis techniques which could be used to realise monolithic multifunctional membrane-electrode assemblies, such as Layer-by-Layer (LbL) deposition, Atomic Layer Deposition (ALD), and porous silicon (porSi) engineering. Advances in modelling approaches, electrochemical techniques and in situ spectroscopies to characterise overall PEC cell performance are discussed.

The effect of a local proton source on the activity of a bromotricarbonyl Mn redox catalyst for CO₂ reduction has been investigated. The electrochemical behaviour of the novel complex [fac-Mn(dhbpy)(CO)₃Br] (dhbpy = 4-phenyl-6-(1,3-dihydroxybenzen-2-yl) 2,2′-bipyridine), containing two acidic OH groups in the proximity of the metal centre, under a CO₂ atmosphere showed a sustained catalysis in homogeneous solution even in the absence of Brønsted acids.