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。

Preparation of p-CoFe2O4/n-CdS by Hydrothermal Method and Its Photocatalytic Hydrogen Production Activity

A series of p-n coupled p-CoFe₂O₄/n-CdS photocatalysts were prepared by a hydrothermal method. The structure and properties of p-CoFe₂O₄/n-CdS were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), transmission electron microscopy (TEM) and the electrochemical workstation. The photocatalytic activities of p-CoFe₂O₄/nCdS were evaluated by photocatalytic hydrogen production under visible light irradiation. The effects of photocorrosion of CdS in p-CoFe₂O₄/n-CdS were investigated by analyzing the cadmium concentration of the supernatant collected after the photocatalytic reactions. The mechanism of the catalytic activity enhancement, effects of reaction conditions on the photocatalytic hydrogen evolution rate, and cadmium leakage resistance are discussed. The results show that p-CoFe₂O₄/n-CdS exhibits higher photocatalytic activity attributed to stronger light absorption by the two types of narrow band gap semiconductor CoFe₂O₄ and CdS, the formation of a "forest-like" structure of CdS and rapid electron transfer from CoFe₂O₄ to CdS, resulting from band overlap and an inner electric field in p-CoFe₂O₄/n-CdS, to reduce the probability of electron/hole pair recombination. Both the separation efficiency of photo-generated electron-hole pairs and the adsorption performance of photocatalysts had an important influence on the hydrogen production rate. The pH of the CH₃OH aqueous solution influenced the separation efficiency of photogenerated electron-hole pairs and the adsorption properties of the photocatalyst. p-CoFe₂O₄/n-CdS also exhibited resistance against cadmium leakage under light irradiation owing to the presence of methanol in the reaction solution, the band overlap of the semiconductors and the inner electric field in p-CoFe₂O₄/n-CdS. The band overlap and inner electric field had the most influence on the cadmium leakage resistance.