A metal-free organic semiconductor of mesoporous graphitic carbon nitride (C3N4) coupled with a Ru(II) binuclear complex (RuRu') containing photosensitizer and catalytic units selectively reduced CO2 into HCOOH under visible light (λ > 400 nm) in the presence of a suitable electron donor with high durability, even in aqueous solution. Modification of C3N4 with Ag nanoparticles resulted in a RuRu'/Ag/C3N4 photocatalyst that exhibited a very high turnover number (>33000 with respect to the amount of RuRu'), while maintaining high selectivity for HCOOH production (87-99%). This turnover number was 30 times greater than that reported previously using C3N4 modified with a mononuclear Ru(II) complex, and by far the highest among the metal-complex/semiconductor hybrid systems reported to date. The results of photocatalytic reactions, emission decay measurements, and time-resolved infrared spectroscopy indicated that Ag nanoparticles on C3N4 collected electrons having lifetimes of several milliseconds from the conduction band of C3N4, which were transferred to the excited state of RuRu', thereby promoting photocatalytic CO2 reduction driven by two-step photoexcitation of C3N4 and RuRu'. This study also revealed that the RuRu'/Ag/C3N4 hybrid photocatalyst worked efficiently in water containing a proper electron donor, despite the intrinsic hydrophobic nature of C3N4 and low solubility of CO2 in an aqueous environment.

TiO 2 powders have been widely used for photocatalysts, however, why anatase shows higher activity than rutile has been a long standing question. Here, we have elucidated the difference in the behavior of photogenerated electrons and holes by time-resolved visible to mid-IR absorption spectroscopy. In anatase TiO 2 , considerable number of free electrons survives longer than 1 ms, but they are deeply trapped within a few picosecond in the case of rutile TiO 2 . The longer lifetime of free electrons is responsible for the higher activity for reduction processes on anatase TiO 2 . However, deep electron-trapping in rutile TiO 2 elongates lifetime of holes and promotes multi-hole processes such as water oxidation. However, the low reactivity of deeply trapped electrons fails to increase the overall activity. These peculiar behaviors of electrons and holes are induced by defects on the powder particles, and less sensitive to the physical properties such as particle size and specific surface area.

Brookite TiO2 is a promising material for active photocatalysts. However, the principal mechanism that determines the distinctive photocatalytic activity between anatase, rutile, and brookite TiO2 has not yet been fully elucidated. Therefore, in this work, we studied the behavior of photogenerated electrons and holes in these TiO2 powders by using femtosecond to millisecond time-resolved visible to mid-IR absorption spectroscopy. We found that most of the photogenerated electrons in brookite TiO2 are trapped at powder defects within a few ps. This electron trapping decreases the number of surviving free electrons, but it extends the lifetime of holes as well as the trapped electrons because the probability of electrons to encounter holes is decreased by this electron-trapping. As a result, the number of surviving holes increases, which is beneficial for photocatalytic oxidation. In contrast, the reactivity of electrons is decreased to some extent by trapping, but they still remain active for photocatalytic reductions. Electron trapping also takes place on anatase and rutile TiO2 powders, but the trap-depth in anatase is too shallow to extend the lifetime of holes and that of rutile is too deep than the thermal energy (kT) at room temperature for the electron-consuming reactions. As a result of the moderate depth of the electron trap in brookite, both electrons and holes are reactive for photocatalytic reductions and oxidations. These results have clearly demonstrated that the presence of an appropriate depth of the electron trap can effectively contribute to enhance the overall photocatalytic activity.

Localized surface plasmon resonance (LSPR)-induced hot-carrier transfer is a key mechanism for achieving artificial photosynthesis using the whole solar spectrum, even including the infrared (IR) region. In contrast to the explosive development of photocatalysts based on the plasmon-induced hot electron transfer, the hole transfer system is still quite immature regardless of its importance, because the mechanism of plasmon-induced hole transfer has remained unclear. Herein, we elucidate LSPR-induced hot hole transfer in CdS/CuS heterostructured nanocrystals (HNCs) using time-resolved IR (TR-IR) spectroscopy. TR-IR spectroscopy enables the direct observation of carrier in a LSPR-excited CdS/CuS HNC. The spectroscopic results provide insight into the novel hole transfer mechanism, named plasmon-induced transit carrier transfer (PITCT), with high quantum yields (19%) and long-lived charge separations (9.2 μs). As an ultrafast charge recombination is a major drawback of all plasmonic energy conversion systems, we anticipate that PITCT will break the limit of conventional plasmon-induced energy conversion.

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