An overview of heterogeneous photocatalysis for the degradation of organic compounds: A special emphasis on photocorrosion and reusability

Heterogeneous photocatalysis has been extensively investigated for the degradation of organic pollutants from wastewater. The remarkable advantages of the heterogeneous photocatalysis process depend upon its ability to produce reactive oxygen species under visible/UV/solar light irradiation. However, the long-term stability and reuse potential of these catalysts are of great concern these days, yet understudied. This review aims to systematically present a state of the art understanding of such catalysts' reuse potential. Various important surface characteristics of the photocatalysts for improving the photostability and activity of the catalyst are discussed. Besides, the synergistic effect of different surface modified materials, composite materials and their surface characteristics for their enhanced activity are also covered. Finally, a discussion on various regeneration processes used for such catalysts is also presented, identifying some vital research needs in this field.     

水热法制备p-CoFe_2O_4/n-CdS及其光催化制氢性能

水热法制备了系列p-n复合半导体p-CoFe_2O_4/n-CdS。采用X射线衍射(XRD)、冷场发射扫描电子显微镜(SEM)、紫外-可见漫反射光谱(UV-Vis DRS)、透射电镜(TEM)和电化学工作站等对制得的光催化剂进行了结构和性能表征。研究了p-CoFe_2O_4/n-CdS复合光催化剂的可见光催化制氢性能及光腐蚀性能,并对光催化活性的提高、反应条件的影响及光腐蚀行为的抑制机理进行了分析。结果表明:由于CoFe_2O_4和CdS两种窄带隙半导体复合增加了光吸收率;CdS独特的树形结构以及CoFe_2O_4和CdS二者复合所产生的能带交迭和内建电场的三重作用,促进了电子从CoFe_2O_4向CdS的迁移,减少电子-空穴对复合的概率,增强了光催化活性。光生电子-空穴对的分离效率以及光催化剂表面吸附性能都对产氢速率有重要影响。CH_3OH水溶液的pH对光催化剂中光生电子-空穴对的分离效率以及光催化剂表面吸附性能都有影响。牺牲剂CH_3OH的加入以及CoFe_2O_4和CdS二者复合所产生的能带交迭和内建电场的作用都对CdS的光腐蚀起了抑制作用,后者的抑制效果更好。     

Compare the photocatalytic properties of nanocomposites with tandem n (AgBr)-n (Ag2CO3) and p (AgCl)-n (Ag2CO3) heterojunctions

In this work, Ag₂CO₃ nanoparticles (NPs) (as a n-type semiconductor) incorporated in mordenite zeolite (MOR) by a facile precipitation method. Silver halides, AgCl (as a p-type semiconductor) and AgBr (as a n-type semiconductor), with different weight percentage (20%, 40% and 50%) were coupled into Ag₂CO₃-MOR nanocomposite (NC) and producing a series of novel AgCl/Ag₂CO₃ (p-n heterojunction)-MOR and AgBr/Ag₂CO₃ (n-n heterojunction)-MOR NCs. The effects of silver halides on the Ag₂CO₃–MOR catalyst for the photocatalytic degradation of methyl blue (MB) under visible light irradiation have been investigated. The structure, composition and optical properties of NCs were investigated by UV–Visible diffuse reflectance spectroscopy (UV–Vis DRS), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM). The prepared AgX/Ag₂CO₃-MOR NCs with the optimal content of AgX (50 wt%) indicated higher photocatalytic activity than that of the Ag₂CO₃-MOR and Ag₂CO₃. The cycle experiments on the heterojuctions NCs indicated that photocatalytic stability of AgBr/Ag₂CO₃-MOR NC was more than AgCl/Ag₂CO₃-MOR NC in all cycles. On the basis of the experimental results, a possible mechanism for the enhanced photocatalytic activity and photoinduced stability of silver compounds was proposed.     

Recent advances in suppressing the photocorrosion of cuprous oxide for photocatalytic and photoelectrochemical energy conversion

The emergence of cuprous oxide (Cu₂O) as a visible light active semiconductor for photocatalytic and photoelectrochemical applications has elevated significantly over the past decade. With photocorrosion identified as a severe issue for Cu₂O, its photoactivity has been greatly restricted. Given that Cu₂O redox potentials are located in between its band gap, the possible occurrence of self-photoreduction or self-oxidation upon illumination is inevitable. Various efforts have been directed to implement effective strategies in enhancing the photostability of Cu₂O. In particular, most of the studies focused on improving the charge transfer from Cu₂O to reactants or co-catalyst to avoid accumulation of charge within the particles. This review presents recent research progresses for the development of strategies to suppress Cu₂O photocorrosion in regards to its intrinsic properties and charge kinetics. It is shown that effective transport of electrons or holes out of Cu₂O photocatalyst by engineering its crystal structure, tuning its reaction environment or depositing secondary elements could effectively inhibit Cu₂O from experiencing self-photodecomposition. Understanding of the charge dynamics with respect to its photocorrosion is pivotal to optimize the design of Cu₂O photocatalyst for enhanced performance in the future.     

Photostability and visible-light-driven photoactivity enhancement of hierarchical ZnS nanoparticles: The role of embedment of stable defect sites on the catalyst surface with the assistant of ultrasonic waves

Zinc sulfide is a UV-active photocatalyst and it undergoes photocorrosion under light irradiation. In this work, the defect sites on ZnS nanoparticles (NPs) surfaces were induced with the help of powerful ultrasonic waves. The defect sites caused (1) suppression of photocorrosion in a large extent under UV light irradiation and (2) enhancement of visible light photo activity. The photocorrosion inhibition was induced by raising valence band (VB) position through the formation of interstitial zinc and sulfur vacancy states in the ZnS band structure and weakening of oxidative capacity of hole. The enhancement of visible light photocatalytic activity may be related to the generation of more defect energy states in the ZnS band gap. Under visible light irradiation, the electron was excited from the ZnS VB to the interstitial sulfur and zinc vacancy states before injecting into the conduction band of ZnS. Therefore, we modified the band gap of ZnS so that it acts as a visible light active photocatalyst. ZnS NPs were prepared using two different classical and ultrasound methods. The prepared ZnS using ultrasound method, exhibited more outstanding photocatalytic activity for degrading reactive black 5 (RB5) under UV and sunlight irradiation in comparison with the classical method. Details of the degradation mechanism under UV light were investigated. This work provides new insights to understanding the photocorrosion stability and visible light activity of bare ZnS photocatalyst.     

Photodegradation of CuBi2O4 Films Evidenced by Fast Formation of Metallic Bi using Operando Surface-sensitive X-ray Scattering**

CuBi₂O₄ has recently emerged as a promising photocathode for photo-electrochemical (PEC) water splitting. However, its fast degradation under operation currently poses a limit to its application. Here, we report a novel method to study operando the semiconductor-electrolyte interface during PEC operation by surface-sensitive high-energy X-ray scattering. We find that a fast decrease in the generated photocurrents correlates directly with the formation of a metallic Bi phase. We further show that the slower formation of metallic Cu, as well as the dissolution of the electrode in contact with the electrolyte, further affect the CuBi₂O₄ activity and morphology. Our study provides a comprehensive picture of the degradation mechanisms affecting CuBi₂O₄ electrodes under operation and poses the methodological basis to investigate the photocorrosion processes affecting a wide range of PEC materials.