Solar-Driven CO2 Reduction Using a Semiconductor/Molecule Hybrid Photosystem: From Photocatalysts to a Monolithic Artificial Leaf

Abstract

The synthesis of organic chemicals from H₂O and CO₂ using solar energy is important for recycling CO₂ through cyclical use of chemical ingredients produced from CO₂ or molecular energy carriers based on CO₂. Similar to photosynthesis in plants, the CO₂ molecules are reduced by electrons and protons, which are extracted from H₂O molecules, to produce O₂. This reaction is uphill; therefore, the solar energy is stored as the chemical bonding energy in the organic molecules. This artificial photosynthetic technology mimicking green vegetation should be implemented as a self-standing system for on-site direct solar energy storage that supports CO₂ recycling in a circular economy. Herein, we explain our interdisciplinary fusion methodology to develop hybrid photocatalysts and photoelectrodes for an artificial photosynthetic system for the CO₂ reduction reaction (CO₂RR) in aqueous solutions. The key factor for the system is the integration of uniquely different functions of molecular transition-metal complexes and solid semiconductors. A metal complex catalyst and a semiconductor appropriate for a CO₂RR and visible-light absorption, respectively, are linked, and they function complementary way to catalyze CO₂RR under visible-light irradiation as a particulate photocatalyst dispersion in solution. It has also been proven that Ru complexes with bipyridine ligands can catalyze a CO₂RR as photocathodes when they are linked with various semiconductor surfaces, such as those of doped tantalum oxides, doped iron oxides, indium phosphides, copper-based sulfides, selenides, silicon, and others. These photocathodes can produce formate and carbon monoxide using electrons and protons extracted from water through potential-matched connections with photoanodes such as TiO₂ or SrTiO₃ for oxygen evolution reactions (OERs). Benefiting from the very low overpotential of an aqueous CO₂RR at metal complexes approaching the theoretical lower limit, the semiconductor/molecule hybrid system demonstrates a single tablet-formed monolithic electrode called "artificial leaf." This single electrode device can generate formate (HCOO^-) from H₂O and CO₂ in a water-filled single-compartment reactor without requiring a separation membrane under unassisted or bias-free conditions, either electrically or chemically. The reaction proceeds with a stoichiometric electron/hole ratio and stores solar energy with a solar-to-chemical energy conversion efficiency of 4.6%, which exceeds that of plants. In this Account, the key results that marked our milestones in technological progress of the semiconductor/molecule hybrid photosystem are concisely explained. These results include design, proof of the principle, and understanding of the phenomena by time-resolved spectroscopies, synchrotron radiation analyses, and DFT calculations. These results enable us to address challenges toward further scientific progress and the social implementation, including the use of earth-abundant elements and the scale-up of the solar-driven CO₂RR system.