Metal–Organic Framework‐Based Photocatalysis for Solar Fuel Production

Abstract

Metal–organic frameworks (MOFs) represent a novel class of crystalline inorganic–organic hybrid materials with tunable semiconducting behavior. MOFs have potential for application in photocatalysis to produce sustainable solar fuels, owing to their unique structural advantages (such as clarity and modifiability) that can facilitate a deeper understanding of the structure–activity relationship in photocatalysis. This review takes the photocatalytic active sites as a particular perspective, summarizing the progress of MOF‐based photocatalysis for solar fuel production; mainly including three categories of solar‐chemical conversions, photocatalytic water splitting to hydrogen fuel, photocatalytic carbon dioxide reduction to hydrocarbon fuels, and photocatalytic nitrogen fixation to high‐energy fuel carriers such as ammonia. This review focuses on the types of active sites in MOF‐based photocatalysts and discusses their enhanced activity based on the well‐defined structure of MOFs, offering deep insights into MOF‐based photocatalysis.

Exfoliation of a Two-Dimensional Metal–Organic Framework for Enhanced Photocatalytic CO2 Reduction

“…Metal–organic frameworks (MOFs) offer an ideal platform for this purpose. MOFs are porous crystalline materials built through coordination bonds between metal or metal clusters and organic linkers. − Compared to other solid-state materials, MOFs have unique advantages with regard to the capability of precise structure control and prediction, giving MOF materials great potential in various applications such as gas storage, , separation, − sensing, − catalysis, − and so on. In particular, these features endow MOFs with the unique opportunity to integrate light-harvesting and catalytic components in a single solid in an orderly manner. − This approach has been validated in several reports of MOF-based integrated photocatalysts for CO 2 reduction. − However, exciton and mass transfer through the framework remains a challenge for MOF photocatalysis despite the porous catalyst structure.…”

Donor–Acceptor Mixed-Naphthalene Diimide-Porphyrin MOF for Boosting Photocatalytic Oxidative Coupling of Amines

“…As a category of newly emerged crystalline porous materials, metal–organic frameworks (MOFs) have been proposed as potential photocatalysts for selective oxidation reactions because of their unique excitation and charge transition mechanisms. − Recently, some MOFs have been reported for the photocatalytic aerobic oxidative coupling of amines, − but the reaction kinetics caused by the low efficiency of the photogenerated charge separation still needs to be greatly improved to meet the potential practical application requirements. There are many reported strategies in optimizing the photocatalytic activities of MOFs, in which the electron/energy transfer representing the central science of natural photosynthesis is widely introduced. − Assembling electron donor and acceptor chromophores in a single MOF can realize the photoinduced electron transfer (PET). − However, due to the construction of MOFs, in which donor and acceptor chromophores with similar geometry and connectivity both as ligands, is a great challenge, most of the current reported MOFs with the PET process are organized via using either the donor or the acceptor as the guest molecule, − which damages the porosities of MOFs and severely limits their applications in photocatalysis.…”

Methylthio-functionalized UiO-66 to promote the electron–hole separation of ZnIn2S4for boosting hydrogen evolution under visible light illumination

“…With the increasing consumption of fossil fuels, there is already a shortage of fossil energy. 1,2 The survival of human beings is inseparable from energy, which stimulates an urgent need to find a new energy source with abundant reserves that does not depend on fossil fuels. 3 Hydrogen has attracted much attention as a renewable and clean energy source.…”