Hetero-Motif Molecular Junction Photocatalysts: A New Frontier in Artificial Photosynthesis.

ConspectusTo cope with the increasingly global greenhouse effect and energy shortage, it is urgent to develop a feasible means to convert anthropogenic excess carbon dioxide (CO) into energy resources. The photocatalytic CO reduction reaction (CORR) coupled with the water oxidation reaction (WOR), known as artificial photosynthesis, is a green, clean, and promoting strategy to deal with the above issues. Among the reported photocatalytic systems for CO reduction, the main challenge is to achieve WOR simultaneously due to the limited charge separation efficiency and complicated dynamic process. To address the problem, scientists have assembled two nanosemiconductor motifs for CORR and WOR into a heterojunction photocatalyst to realize artificial photosynthesis. However, it is difficult to clearly explore the corresponding catalytic mechanism and establish an accurate structure-activity relationship at the molecular level for their aperiodic distribution and complicated structural information. Standing on the shoulders of the heterojunction photocatalysts, a new-generation material, hetero-motif molecular junction (HMMJ) photocatalysts, has been developed and studied by our laboratory. A hetero-motif molecular junction is a class of crystalline materials with a well-defined and periodic structure, adjustable assembly mode, and semiconductor-like properties, which is composed of two predesigned motifs with oxidation and reduction, respectively, by coordination or covalent bonds. The intrinsic properties make these catalysts susceptible to functional modifications to improve light absorption and electrical conductivity. The small size and short distance of the motifs can greatly promote the efficiency of photogenerated electron-hole separation and migration. Based on these advantages, they can be used as potential excellent photocatalysts for artificial photosynthesis. Notably, the explicit structural information determined by single-crystal or powder X-ray diffraction can provide a visual platform to explore the reaction mechanism. More importantly, the connection number, spatial distance, interaction, and arrangement mode of the structural motifs can be well-designed to explore the detailed structure-activity relationship that can be hardly studied in nanoheterojunction photocatalyst systems. In this regard, HMMJ photocatalysts can be a new frontier in artificial photosynthesis and serve as an important bridge between molecular photocatalysts and solid photocatalysts. Thus, it is very important to summarize the state-of-the-art of the HMMJ photocatalysts used for artificial photosynthesis and to give in-depth insight to promote future development.In this Account, we have summarized the recent advances in artificial photosynthesis using HMMJ photocatalysts, mainly focusing on the results in our lab. We present an overview of current knowledge about developed photocatalytic systems for artificial photosynthesis, introduce the design schemes of the HMMJ photocatalysts and their unique advantages as compared to other photocatalysts, summarize the construction strategies of HMMJ photocatalysts and their application in artificial photosynthesis, and explain why hetero-motif molecular junctions can be promising photocatalysts and show that they provide a powerful platform for studying photocatalysis. The structure-activity relationship and charge separation dynamics are illustrated. Finally, we bring our outlook on present challenges and future development of HMMJ photocatalysts and their potential application prospects on other photocatalytic reaction systems. We believe that this Account will afford important insights for the construction of high-efficiency photocatalysts and guidance for the development of more photocatalytic systems in an atom-economic, environmentally friendly, and sustainable way.