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Photocatalytic CO2 reduction is one of the best solutions to solve the global energy crisis and to realize carbon neutralization. The tetradentate phosphine‐bipyridine (bpy)‐phosphine (PNNP)‐type Ir(III) photocatalyst, Mes‐IrPCY2, was reported with a high HCOOH selectivity but the photocatalytic mechanism remains elusive. Herein, we employ electronic structure methods in combination with radiative, nonradiative, and electron transfer rate calculations, to explore the entire photocatalytic cycle to either HCOOH or CO, based on which a new mechanistic scenario is proposed. The catalytic reduction reaction starts from the generation of the precursor metal‐to‐ligand charge transfer (3MLCT) state. Subsequently, the divergence happens from the 3MLCT state, the single electron transfer (SET) and deprotonation process lead to the formation of one‐electron‐reduced species and Ir(I) species, which initiate the reduction reaction to HCOOH and CO, respectively. Interestingly, the efficient occurrence of proton or electron transfer reduces barriers of critical steps. In addition, nonadiabatic transitions play a nonnegligible role in the cycle. We suggest a lower free‐energy barrier in the reaction‐limiting step and the very efficient SET in 3MLCT are cooperatively responsible for a high HCOOH selectivity. The gained mechanistic insights could help chemists to understand, regulate, and design photocatalytic CO2 reduction reaction of similar function‐integrated molecular photocatalyst. [ABSTRACT FROM AUTHOR]

Photocatalytic CO2 reduction is one of the best solutions to solve the global energy crisis and to realize carbon neutralization. The tetradentate phosphine‐bipyridine (bpy)‐phosphine (PNNP)‐type Ir(III) photocatalyst, Mes‐IrPCY2, was reported with a high HCOOH selectivity but the photocatalytic mechanism remains elusive. Herein, we employ electronic structure methods in combination with radiative, nonradiative, and electron transfer rate calculations, to explore the entire photocatalytic cycle to either HCOOH or CO, based on which a new mechanistic scenario is proposed. The catalytic reduction reaction starts from the generation of the precursor metal‐to‐ligand charge transfer (3MLCT) state. Subsequently, the divergence happens from the 3MLCT state, the single electron transfer (SET) and deprotonation process lead to the formation of one‐electron‐reduced species and Ir(I) species, which initiate the reduction reaction to HCOOH and CO, respectively. Interestingly, the efficient occurrence of proton or electron transfer reduces barriers of critical steps. In addition, nonadiabatic transitions play a nonnegligible role in the cycle. We suggest a lower free‐energy barrier in the reaction‐limiting step and the very efficient SET in 3MLCT are cooperatively responsible for a high HCOOH selectivity. The gained mechanistic insights could help chemists to understand, regulate, and design photocatalytic CO2 reduction reaction of similar function‐integrated molecular photocatalyst. [ABSTRACT FROM AUTHOR]

Photosensitization associated with electron/energy transfer represents the central science of natural photosynthesis. Herein, we proposed a protocol to dramatically improve the sensitizing ability of metal–organic frameworks (MOFs) by switching their excited state distribution from 3MLCT (metal‐to‐ligand charge transfer) to 3IL (intraligand). The hierarchical organization of 3IL MOFs and Co/Cu catalysts facilitates electron transfer for efficient photocatalytic H2 evolution with a yield of 26 844.6 μmol g−1 and CO2 photoreduction with a record HCOOH yield of 4807.6 μmol g−1 among all the MOF photocatalysts. Systematic investigations demonstrate that strong visible‐light‐absorption, long‐lived excited state and ingenious multi‐component synergy in the 3IL MOFs can facilitate both interface and intra‐framework electron transfer to boost photocatalysis. This work opens up an avenue to boost solar‐energy conversion by engineering sensitizing centers at a molecular level. [ABSTRACT FROM AUTHOR]

Photosensitization associated with electron/energy transfer represents the central science of natural photosynthesis. Herein, we proposed a protocol to dramatically improve the sensitizing ability of metal–organic frameworks (MOFs) by switching their excited state distribution from 3MLCT (metal‐to‐ligand charge transfer) to 3IL (intraligand). The hierarchical organization of 3IL MOFs and Co/Cu catalysts facilitates electron transfer for efficient photocatalytic H2 evolution with a yield of 26 844.6 μmol g−1 and CO2 photoreduction with a record HCOOH yield of 4807.6 μmol g−1 among all the MOF photocatalysts. Systematic investigations demonstrate that strong visible‐light‐absorption, long‐lived excited state and ingenious multi‐component synergy in the 3IL MOFs can facilitate both interface and intra‐framework electron transfer to boost photocatalysis. This work opens up an avenue to boost solar‐energy conversion by engineering sensitizing centers at a molecular level. [ABSTRACT FROM AUTHOR]

Inspired by nature, improving photosensitization represents a vital direction for the development of artificial photosynthesis. The sensitization ability of photosensitizers (PSs) reflects in their electron-transfer ability, which highly depends on their excited-state lifetime and redox potential. Herein, for the first time, we put forward a facile strategy to improve sensitizing ability via finely tuning the excited state of Ru(II)-PSs (Ru-1 – Ru-4) for efficient CO2 reduction. Remarkably, [Ru(Phen)2(3-pyrenylPhen)]2+ (Ru-3) exhibits the best sensitizing ability among Ru-1 – Ru-4 , over 17 times higher than that of typical Ru(Phen)32+. It can efficiently sensitize a dinuclear cobalt catalyst for CO2-to-CO conversion with a maximum turnover number of 66 480. Systematic investigations demonstrate that its long-lived excited state and suitable redox driving force greatly contributed to this superior sensitizing ability. This work provides a new insight into dramatically boosting photocatalytic CO2 reduction via improving photosensitization. [ABSTRACT FROM AUTHOR]