Li Zhijun, Luan Yunbo, Qu Yang, Jing Liqiang
Key Laboratory of Functional Inorganic Material Chemistry (Heilongjiang University), Ministry of Education, School of Chemistry and Materials Science, International Joint Research Center for Catalytic Technology , Harbin 150080, People's Republic of China.
ACS Appl Mater Interfaces. 2015 Oct 21;7(41):22727-40. doi: 10.1021/acsami.5b04267. Epub 2015 Oct 8.
Efficient photocatalysis for degrading environmental organic pollutants on semiconductors requires photogenerated charge carrier separation to drive the photochemical processes. To ensure charge separation, it is indispensable to make charges captured effectively. Generally, the step for capturing the photogenerated electrons by the surface adsorbed O2 is relatively slow as compared to that for capturing holes by the surface adsorbed hydroxyl groups so that it is taken as the rate-determining step. However, it is frequently neglected. Thus, it is greatly desired to develop feasible strategies to promote the adsorption of O2 for efficient photocatalysts. In this paper, we have mainly discussed surface modification with inorganic acids, such as H3PO4, HF, and H3BO3, to enhance photogenerated charge carrier separation based on oxygen adsorption promotion for photocatalytic degradation of environmental pollutants. Among these acids, the function and mechanism of H3PO4 are highlighted because of its good performance and universality. Several important photocatalyst systems, mainly including TiO2, α-Fe2O3, and g-C3N4, along with the nanostructured carbons as electron acceptors in nanocomposites, are addressed to improve the ability to adsorb O2. A key consideration in this review is the development of a strategy for the promotion of adsorbed O2 for efficient photocatalysts, along with the process mechanisms by revealing the relationships among the adsorbed O2, photogenerated charge carrier separation, and photocatalytic performance. Interestingly, it is suggested that the enrichment in surface acidity be favorable for promotion of O2 adsorption, leading to the improved charge carrier separation and then to the enhanced photoactivities of various semiconductor photocatalysts. Moreover, several outlooks are put forward.
半导体上用于降解环境有机污染物的高效光催化需要光生电荷载流子分离来驱动光化学过程。为确保电荷分离,有效捕获电荷是必不可少的。一般来说,与表面吸附的羟基捕获空穴的步骤相比,表面吸附的O₂捕获光生电子的步骤相对较慢,因此被视为速率决定步骤。然而,这一点经常被忽视。因此,迫切需要开发可行的策略来促进O₂的吸附,以获得高效的光催化剂。在本文中,我们主要讨论了用无机酸(如H₃PO₄、HF和H₃BO₃)进行表面改性,以基于促进O₂吸附来增强光生电荷载流子分离,从而实现环境污染物的光催化降解。在这些酸中,H₃PO₄因其良好的性能和通用性而被重点突出其功能和作用机制。文中讨论了几种重要的光催化剂体系,主要包括TiO₂、α-Fe₂O₃和g-C₃N₄,以及纳米复合材料中作为电子受体的纳米结构碳,以提高吸附O₂的能力。本综述的一个关键考虑因素是开发一种促进高效光催化剂吸附O₂的策略,以及通过揭示吸附的O₂、光生电荷载流子分离和光催化性能之间的关系来阐明过程机制。有趣的是,研究表明表面酸度的富集有利于促进O₂吸附,从而改善电荷载流子分离,进而提高各种半导体光催化剂的光活性。此外,还提出了一些展望。