LAUSR

Conspectus The sustainable synthesis of fuels and chemicals is key to attaining a carbon-neutral economy. This can be achieved by mimicking the light-harvesting and catalytic processes occurring in plants. Solar fuel production is commonly performed via established approaches, including photovoltaic–electrochemical (PV–EC), photoelectrochemical (PEC), and photocatalytic (PC) systems. A recent shift saw these systems evolve into integrated, compact panels, which suit practical applications through their simplicity, scalability, and ease of operation. This advance has resulted in a suite of apparently similar technologies, including the so-called artificial leaves and PC sheets. In this Account, we compare these different thin film technologies based on their micro- and nanostructure (i.e., layered vs particulate), operation principle (products occurring on the same or different sides of the panel), and product/reaction scope (overall water splitting and CO2 reduction, or organics, biomass, and waste conversion). For this purpose, we give an overview of developments established over the past few years in our laboratory. Two light absorbers are generally required to overcome the thermodynamic challenges of coupling water oxidation to proton or CO2 reduction with good efficiency. Hence, tandem artificial leaves combine a lead halide perovskite photocathode with a BiVO4 photoanode to generate syngas (a mixture of H2 and CO), whereas PC sheets involve metal-ion-doped SrTiO3 and BiVO4 particles for selective formate synthesis from CO2 and water. On the other hand, only a single light absorber is needed for coupling H2 evolution to organics oxidation in the thermodynamically less demanding photoreforming process. This can be performed by immobilized carbon nitride (CNx) in the case of PC sheets or by a single perovskite light absorber in the case of PEC reforming leaves. Such systems can be integrated with a range of inorganic, molecular, and biological catalysts, including metal alloys, molecular cobalt complexes, enzymes, and bacteria, with low overpotentials and high catalytic activities toward selective product formation. This wide reaction scope introduces new challenges toward quantifying and comparing the performance of different systems. To this end, we propose new metrics to evaluate the performance of solar fuel panels based on the areal product rates and commercial product value. We further explore the key opportunities and challenges facing the commercialization of thin film technologies for solar fuels research, including performance losses over larger areas and catalyst/device recyclability. Finally, we identify emerging applications beyond fuels, where such light-driven panels can make a difference, including the waste management, chemical synthesis, and pharmaceutical industries. In the long term, these aspects may facilitate a transition toward a light-driven circular economy.