Zinc vacancy (VZn) is successfully introduced into 3D hierarchical ZnIn2S4 (3D‐ZIS). The photo‐electrochemical experiments demonstrate that the charge separation and carrier transfer are more efficient in the 3D‐ZIS with rich VZn. Of note, for the first time, it is found that VZn can decrease the carrier transport activation energy (CTAE), from 1.14 eV for Bulk‐ZIS (Bulk ZnIn2S4) to 0.93 eV for 3D‐ZIS, which may provide a feasible platform for further understanding the mechanism of photocatalytic CO2 reduction. In situ Fourier transform infrared (FT‐IR) results reveal that the presence of rich VZn ensures CO2 chemical activation, promoting single‐electron reduction of CO2 to CO2−. In addition, in situ FT‐IR and CO2 temperature programmed desorption results show that VZn can promote the formation of surface hydroxyl. To the best of current knowledge, there are no reports on the photoreduction of CO2 simply by virtue of 3D‐ZIS with VZn and few literature reports on the photocatalytic reduction of CO2 concerned with CTAE. Additionally, this work finds that surface hydroxyl may play a crucial role in the process of CO2 photoreduction. The work may provide some novel ways to ameliorate solar energy conversion performance and a better understanding of photoreaction mechanisms.

Metal halide perovskite quantum dots, with high light-absorption coefficients and tunable electronic properties, have been widely studied as optoelectronic materials, but their applications in photocatalysis are hindered by their insufficient stability because of the oxidation and agglomeration under light, heat, and atmospheric conditions. To address this challenge, herein, we encapsulated CsPbBr 3 nanocrystals into a stable iron-based metal−organic framework (MOF) with mesoporous cages (∼5.5 and 4.2 nm) via a sequential deposition route to obtain a perovskite-MOF composite material, CsPbBr 3 @PCN-333(Fe), in which CsPbBr 3 nanocrystals were stabilized from aggregation or leaching by the confinement effect of MOF cages. The monodispersed CsPbBr 3 nanocrystals (4−5 nm) within the MOF lattice were directly observed by transmission electron microscopy and corresponding mapping analysis and further confirmed by powder X-ray diffraction, infrared spectroscopy, and N 2 adsorption characterizations. Density functional theory calculations further suggested a significant interfacial charge transfer from CsPbBr 3 quantum dots to , which is ideal for photocatalysis. The CsPbBr 3 @PCN-333(Fe) composite exhibited excellent and stable oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic activities in aprotic systems. Furthermore, CsPbBr 3 @PCN-333(Fe) composite worked as the synergistic photocathode in the photoassisted Li−O 2 battery, where CsPbBr 3 and PCN-333(Fe) acted as optical antennas and ORR/OER catalytic sites, respectively. The CsPbBr 3 @PCN-333(Fe) photocathode showed lower overpotential and better cycling stability compared to CsPbBr 3 nanocrystals or , highlighting the synergy between CsPbBr 3 and PCN-333(Fe) in the composite.

This review summarizes the recent progress made in using cobalt-based catalysts for photo/electrocatalytic CO2 reduction.

Intriguing properties and functions are expected to implant into metal–organic layers (MOLs) to achieve tailored pore environments and multiple functionalities owing to the synergies among multiple components. Herein, we demonstrate a facile one‐pot synthetic strategy to incorporate multiple functionalities into stable zirconium MOLs via secondary ligand pillaring. Through the combination of Zr6‐BTB (BTB=benzene‐1,3,5‐tribenzoate) layers and diverse secondary ligands (including ditopic and tetratopic linkers), 31 MOFs with multi‐functionalities were systematically prepared. Notably, a metal–phthalocyanine fragment was successfully incorporated into this Zr‐MOL system, giving rise to an ideal platform for the selective oxidation of anthracene. The organic functionalization of two‐dimensional MOLs can generate tunable porous structures and environments, which may facilitate the excellent catalytic performance of as‐synthesized materials.

Photoreduction of CO2 into value‐added fuels is one of the most promising strategies for tackling the energy crisis and mitigating the “greenhouse effect.” Recently, metal–organic frameworks (MOFs) have been widely investigated in the field of CO2 photoreduction owing to their high CO2 uptake and adjustable functional groups. The fundamental factors and state‐of‐the‐art advancements in MOFs for photocatalytic CO2 reduction are summarized from the critical perspectives of light absorption, carrier dynamics, adsorption/activation, and reaction on the surface of photocatalysts, which are the three main critical aspects for CO2 photoreduction and determine the overall photocatalytic efficiency. In view of the merits of porous materials, recent progress of three other types of porous materials are also briefly summarized, namely zeolite‐based, covalent–organic frameworks based (COFs‐based), and porous semiconductor or organic polymer based photocatalysts. The remarkable performance of these porous materials for solar‐driven CO2 reduction systems is highlighted. Finally, challenges and opportunities of porous materials for photocatalytic CO2 reduction are presented, aiming to provide a new viewpoint for improving the overall photocatalytic CO2 reduction efficiency with porous materials.

Intriguing properties and functions are expected to implant into metal–organic layers (MOLs) to achieve tailored pore environments and multiple functionalities owing to the synergies among multiple components. Herein, we demonstrate a facile one‐pot synthetic strategy to incorporate multiple functionalities into stable zirconium MOLs via secondary ligand pillaring. Through the combination of Zr6‐BTB (BTB=benzene‐1,3,5‐tribenzoate) layers and diverse secondary ligands (including ditopic and tetratopic linkers), 31 MOFs with multi‐functionalities were systematically prepared. Notably, a metal–phthalocyanine fragment was successfully incorporated into this Zr‐MOL system, giving rise to an ideal platform for the selective oxidation of anthracene. The organic functionalization of two‐dimensional MOLs can generate tunable porous structures and environments, which may facilitate the excellent catalytic performance of as‐synthesized materials.

No abstract