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The design of photocatalytic supramolecular systems composing of semiconductors and molecular metal complexes for CO2 reduction has attracted increasing attention. The supramolecular system combines the structural merits of semiconductors and metal complexes, where the semiconductor harvests light and undertakes the oxidative site, while the metal complex provides activity for CO2 reduction. The intermolecular charge transfer plays crucial role in ensuring photocatalytic performance. Here, we review the progress of photocatalytic supramolecular systems in reduction of CO2 and highlight the interfacial charge transfer pathways, as well as their state‐of‐the‐art characterization methods. The remaining challenges and prospects for further design of supramolecular photocatalysts are also presented. [ABSTRACT FROM AUTHOR]

Crystalline covalent organic frameworks (COFs) are porous polymeric semiconductors with network topologies, which are built from the integration of selected organic blocks with covalent bond linkages. They have shown great promise for artificial photosynthesis, owing to broad light harvesting, high crystallinity, and high carrier mobility. This Minireview introduces state‐of‐the‐art COF photocatalysts based on different linkages and discusses the origin of photocatalytic activities for hydrogen evolution. Three typical COF photocatalysts, with linkages including imine (−C=N−), β‐ketoenamine (O=C−C=C−NH−), and vinylene (−C=C−), are discussed with a particular focus on the advancements in synthetic methodologies and structural design, as well as photoelectronic properties that are relevant to photocatalytic performance. The Minireview is expected to elucidate their structure–property relationships and the way to design photoactive COFs with enhanced performances. [ABSTRACT FROM AUTHOR]

Photocatalytic conversion of CO2 into value‐added chemical fuels is a promising approach to address the depletion of fossil energy and environment‐related concerns. Tailor‐making the electronic properties and band structures of photocatalysts is pivotal to improve their efficiency and selectivity in photocatalytic CO2 reduction. Herein, a covalent triazine‐based framework was developed containing electron‐donor triphenylamine and electron‐acceptor triazine components (DA‐CTF). The engineered π‐conjugated electron donor–acceptor dyads in DA‐CTF not only optimized the optical bandgap but also contributed to visible‐light harvesting and migration of photoexcited charge carriers. The activity of photocatalytic CO2 reduction under visible light was significantly improved compared with that of traditional g‐C3N4 and reported covalent triazine‐based frameworks. This study provides molecular‐level insights into the mechanism of photocatalytic CO2 reduction. [ABSTRACT FROM AUTHOR]

Abstract: MoS2 quantum dots (QDs)‐modified covalent triazine‐based framework (MoS2/CTF) composites are synthesized through an in situ photodeposition method. MoS2 QDs are well distributed and stabilized on the layers of CTFs by coordination of the frameworks to MoS2. The QDs–sheet interactions between MoS2 and CTFs facilitate interfacial charge transfer and separation. As a consequence, the composites exhibit outstanding photocatalytic activity and stability for hydrogen evolution under visible light irradiation (λ≥420 nm), that exceed those over pristine CTFs and MoS2‐modified g‐C3N4 (MoS2/g‐C3N4) composite, making them promising materials for solar energy conversion. [ABSTRACT FROM AUTHOR]

Metal complex-based photocatalysts are promising for CO2 reduction. Their catalytic performances greatly rely on the synergy of ligands and metal ions. Here, we demonstrate an assembly of covalent organic cage (COC) and metal ions for photocatalytic CO2 reduction. The coordinated metal serves as catalytically active site for CO2 reduction, while the cage not only chelates the metal site, but also enhances the local concentration of CO2 around metal site, and decreases the key intermediate reaction energy barrier, thereby promoting the CO2 reduction reaction kinetically and thermodynamically. Accordingly, a Ni metalized COC exhibited outstanding photocatalytic performance in CO2-to-CO conversion under visible light irradiation. This study highlights the feasibility and advantage of organic cages for the construction of photocatalysts for artificial photosynthesis., (© 2024 Wiley‐VCH GmbH.)

The design of photocatalytic supramolecular systems composing of semiconductors and molecular metal complexes for CO 2 reduction has attracted increasing attention. The supramolecular system combines the structural merits of semiconductors and metal complexes, where the semiconductor harvests light and undertakes the oxidative site, while the metal complex provides activity for CO 2 reduction. The intermolecular charge transfer plays crucial role in ensuring photocatalytic performance. Here, we review the progress of photocatalytic supramolecular systems in reduction of CO 2 and highlight the interfacial charge transfer pathways, as well as their state-of-the-art characterization methods. The remaining challenges and prospects for further design of supramolecular photocatalysts are also presented., (© 2024 Wiley-VCH GmbH.)

MoS 2 quantum dots (QDs)-modified covalent triazine-based framework (MoS 2 /CTF) composites are synthesized through an in situ photodeposition method. MoS 2 QDs are well distributed and stabilized on the layers of CTFs by coordination of the frameworks to MoS 2 . The QDs-sheet interactions between MoS 2 and CTFs facilitate interfacial charge transfer and separation. As a consequence, the composites exhibit outstanding photocatalytic activity and stability for hydrogen evolution under visible light irradiation (λ≥420 nm), that exceed those over pristine CTFs and MoS 2 -modified g-C 3 N 4 (MoS 2 /g-C 3 N 4 ) composite, making them promising materials for solar energy conversion., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)