Fiber‑Optic Microfiber:Tracking Activity Enhancement and Suppression of Heterogeneous Photocatalysts

Obtaining detailed insight into the photocatalytic performance of heterogeneous photocatalytic materials,is important for evaluating material properties as well as guiding material design.However,capture of the detailed matter changes on a photocatalyst surface in real time,and in situ during photocatalysis remains challenging.This work reports a promising optical microfiber sensor integrating a photocatalytic reaction monolayer on an optical microfiber surface to monitor reaction kinetics using Cu_(2)O-based heterogeneous photocatalysts,as an example.The evanescent field of microfiber is used to track the photocatalytic process in real time,through the interaction with the catalytic layer,by monitoring the surface refractive index changes caused by adsorption and degradation.Since the catalytic layer is less than 1µm thick,the typical high-power light source can be replaced by low-power light irradiation.This method successfully reveals that relative to the pristine Cu_(2)O microspheres,the photocatalytic activity is enhanced by the incorporation of Ti_(3)C_(2)T_(x) MXene into Cu_(2)O,whereas incorporation of CdS into Cu_(2)O suppresses the activity.Compared with the existing methods used for photocatalysis evalu-ation,this optical microfiber can be directly employed in real matrices to track local photocatalytic performance.It can also provide details about the different adsorption/degradation kinetics of photocatalysts.It is suitable for most photocatalytic processes and is not limited to pollutants with characteristic UV–visible absorption spectra.This study provides important inspiration for the future development of in situ,real-time reaction assessment.

Photocatalytic Degradation of Plastic Waste: Recent Progress and Future Perspectives

Microplastics are persistent anthropogenic pollutants that have become a global concern due to their widespread distribution and unfamiliar threat to the environment and living organisms. Conventional technologies are unable to fully decompose and mineralize plastic waste. Therefore, there is a need to develop an environmentally friendly, innovative and sustainable photocatalytic process that can destroy these wastes with much less energy and chemical consumption. In photocatalysis, various nanomaterials based on wide energy band gap semiconductors such as TiO2 and ZnO are used for the conversion of plastic contaminants into environmentally friendly compounds. In this work, the removal of plastic fragments by photocatalytic reactions using newly developed photocatalytic composites and the mechanism of photocatalytic degradation of microplastics are systematically investigated. In these degradation processes, sunlight or an artificial light source is used to activate the photocatalyst in the presence of oxygen.

Ni-based photocatalytic H_2-production cocatalysts

Photocatalysis is believed to be one of the best methods to realize sustainable H2 production. However, achieving this through heterogeneous photocatalysis still remains a great challenge owing to the absence of active sites, sluggish surface reaction kinetics, insufficient charge separation, and a high thermodynamic barrier. Therefore, cocatalysts are necessary and of great significance in boosting photocatalytic H2 generation. This review will focus on the promising and appealing low-cost Ni-based H2-generation cocatalysts as the alternatives for the high-cost and low-abundance noble metal cocatalysts. Special emphasis has been placed on the design principle, modification strategies for further enhancing the activity and stability of Ni-based cocatalysts, and identification of the exact active sites and surface reaction mechanisms. Particularly, four types of modification strategies based on increased light harvesting, enhanced charge separation, strengthened interface interaction, and improved electrocatalytic activity have been thoroughly discussed and compared in detail. This review may open a new avenue for designing highly active and durable Ni-based cocatalysts for photocatalytic H2 generation.

Robust chromophore-integrated MOFs as highly visible-white-light active and tunable size-selective photocatalysts towards benzothiazoles

Visible-light heterogeneous photocatalyst with high activity and selectivity is crucial for the development of organic transformations, but remains a formidable challenge. Herein, a simple and effective strategy was developed to integrate tetrazine moiety, a visible light active unit, into robust metal-organic frameworks(2D MOF-1(M), M = Co, Mn, Zn, and 3D MOF-2(Co)). MOF-1 series are isomorphous 2D porous frameworks, and MOF-2(Co) displays 3D porous framework. Interestingly, benefiting from the oxidative active species of O_(2)·-, these MOFs all exhibit obviously highly enhanced photocatalytic activities toward the straightforward condensation of o-aminothiophenol and aromatic aldehydes at room temperature in Et OH under visible-white-light irradiation. Notably, compared to 3D MOF, the 2D layered MOF-1(Co) exhibited more excellent catalytic activity with a wide range of substrates possessing preeminent tolerance of steric hindrance. Most impressively, MOF-1(Co) can be recycled at least five times without significant loss of catalytic activity or crystallinity, exhibiting excellent stability and reusability. This study sheds light on the wide-ranging prospects of visible light active 2D MOFs as green photocatalysts for the preparation of fine chemicals.

Metal-organic frameworks as photocatalysts for aerobic oxidation reactions

Metal-organic frameworks(MOFs)are emerging as one of the most intriguing classes of heterogeneous photocatalysts owing to their abundant structures,tunable porosity,and versatile functions.The advantages of bottom-up design and reticular synthesis render MOF materials with desired photocatalytic properties for targeted reactions.In this review,we discussed the design and synthesis of MOF-based photocatalysts as well as strategies for enhancing photocatalytic performance.Recent progress on MOFs as platforms for photocatalytic aerobic oxidation reactions was summarized and categorized according to the types of bond formation.We hope this review will give an in-depth insight into MOF-based photocatalytic systems for not only aerobic oxidation reactions but also other organic transformations.A brief outlook on the challenges and opportunities of MOFs as heterogeneous photocatalysts is provided at the end of the review.

Progress in organic photocatalysts

Organic materials have advantages of diversity,ease of functionality, self-assembly, etc. The varied mechanistic pathways also make it conceivable to design an appropriate photocatalyst for an identical reaction. From this perspective, organic photocatalysts find wide applications in homogeneous, heterogeneous photocatalysis and photoelectrochemical（PEC） solar cells. In this review, the form of the employed organic photocatalysts ranging from molecules, supported molecules, to nanostructures or thinfilm aggregates will be firstly discussed. Rational design strategies relating to each form are also provided, aiming to enhance the photoenergy conversion efficiency. Finally,the ongoing directions for future improvement of organic materials in high-quality optoelectronic devices are also proposed.

Porphyrin covalent organic framework for photocatalytic synthesis of tetrahydroquinolines

A metal-free porphyrin covalent organic framework was employed as the heterogeneous photocatalyst for the synthesis of tetrahydroquinolines under aerobic conditions.With visible light irradiation of a catalytic amount of H_(2)P-Bph-COF at room temperature,various substituted N,N-dimethylanilines and N-aryl maleimides were transformed to tetrahydroquinoline derivatives in moderate to good yields.This was the first example of the synthesis of tetrahydroquinolines via the photocatalytic aerobic annulation reaction employing the metal-free COF as the heterogeneous photocatalyst.