Heterojunctions combining two photocatalysts of staggered conduction and valence band energy levels can increase the photocatalytic efficiency compared to their individual components. This activity enhancement is due to the minimization of undesirable charge recombination by the occurrence of carrier migration through the heterojunction interface with separated electrons and holes on the reducing and oxidizing junction component, respectively. Metal-organic frameworks (MOFs) are currently among the most researched photocatalysts due to their tunable light absorption, facile charge separation, large surface area and porosity. The present review summarizes the current state-of-the-art in MOF-based heterojunctions, providing critical comments on the construction of these heterostructures. Besides including examples showing the better performance of MOF heterojunctions for three important photocatalytic processes, such as hydrogen evolution reaction, CO2 photoreduction and dye decolorization, the focus of this review is on describing synthetic procedures to form heterojunctions with MOFs and on discussing the experimental techniques that provide evidence for the operation of charge migration between the MOF and the other component. Special attention has been paid to the design of rational MOF heterojunctions with small particle size and controlled morphology for an appropriate interfacial contact. The final section summarizes the achievements of the field and provides our views on future developments.

Metal-organic framework heterojunctions for photocatalysis.

The precise design of the charge carrier relay channel and active sites of semiconductor-based photocatalysts is highly crucial for target selective photoredox synthesis. In this context, we report an atomic-level catalyst design strategy based on depositing Pt single atoms (SAs) onto Cu-doped ultrathin cadmium sulfide nanosheets (CdS/Cu/Pt) to enable an optimized band structure, a directional charge transfer channel, and favorable catalytic sites for efficient and selective dehydrocoupling of amines to imines and hydrogen (H2). The Cu dopant acts as a unique electron bridge to construct a directional Cu–Pt electron transfer channel with the assistance of atomically dispersed Pt sites, thereby promoting charge separation and transfer kinetics. The introduction of Pt SAs not only facilitates the H2 generation by decreasing the overpotential of proton reduction but also improves the selectivity of imines synthesis because the weak adsorption of imines on Pt SAs prevents further hydrogenation of imines to secondary amines. This work is anticipated to inspire a further rational design of semiconductor-based photocatalysts with atomic precision for the coproduction of renewable fuels and value-added fine chemicals. 

Selective Imines Synthesis by Designing an Atomic-Level Cu–Pt Electron Transfer Channel over CdS Nanosheets

With an inexpensive and commercially available WO 

NPh3-Mediated WO3-Photocatalyzed Semiheterogeneous Hydroxylation of Aryl and Alkyl Boronic Acids

A novel stable lead-free copper halide perovskite (ODA)2CuBr4 was prepared by intercalating the long hydrophobic alkyl group octadecyl ammonium (ODA) between the inorganic layers. The as-synthesized (ODA)2CuBr4 shows excellent photocatalytic performance in the visible-light-driven dehydrogenation coupling of quinoxalin-2(1H)-ones with amines at room temperature. In addition, the photocatalyst could be recovered and recycled for up to five consecutive runs without significant losing of its catalytic activity. 

(ODA)2CuBr4: A stable lead-free perovskite as efficient photocatalyst for dehydrogenative coupling of quinoxalin-2(1H)-ones with amines

To overcome the energy and environmental crisis, the development of efficient, sustainable photocatalysts to convert inexhaustible solar energy into chemical energy is of great significance. Due to their unique optoelectronic properties, organic electronic materials have been translated into the photocatalytic field. These emerging photocatalysts are attractive because of their metal-free nature, chemical stability, and structural diversity. However, as many small molecules fail to absorb visible light solely, incorporating them into crosslinked frameworks is found to be an effective strategy to extend the conjugation and enhance visible-light absorption. In addition, the photophysical properties of these heterogeneous materials can be adjusted through structural modification and linkage engineering. Finally, these insoluble photocatalysts exhibit good recyclability and reusability. As a representative illustration, this feature article describes recent examples of the use of two types of organic electronic materials including phenothiazine and truxene in heterogeneous photocatalytic organic transformations. The synthesis and key photophysical properties of both organic electronic material-based photocatalysts are discussed combined with specific synthetic applications. We anticipate this feature article will stimulate the implementation of more diverse organic electronic materials in the field of photocatalysis, which may lead to unprecedented synthetic applications.

Optoelectronic materials as emerging photocatalysts: opportunities in sustainable organic synthesis.

Light absorption by semiconducting materials generates electrons and holes subsequent to charge separation, which is at the core of two different applications: 1) photovoltaics and 2) photocatalysis, intended to generate electric current or to trigger redox events, respectively. Recent developments in photovoltaic applications have been impressive, owing to the introduction of innovative and more efficient materials. This brief review describes recent examples to demonstrate the relative high performance of photovoltaic materials that have been exploited in photocatalytic synthetic applications. These include redox processes (net oxidations and reductions), CC bond formation, and manipulation of cyclic structures. Although several benchmark reactions have been explored routinely, a recent trend highlights the development of ground‐breaking synthetic applications, which demonstrate the importance of converting such highly performing materials from the photovoltaic into the photocatalytic field.

Photovoltaic Materials as Heterogeneous Photocatalysts: A Golden Opportunity for Sustainable Organic Syntheses

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Photovoltaic Materials as Heterogeneous Photocatalysts: A Golden Opportunity for Sustainable Organic Syntheses